Libro Spot Test

Qualitative Analysis by
SPOT T E S T S
Qualitative Analysis by
SPOT TESTS
Inorganic and Organic Applications
by FRITZ FEIGL, Eng., Dr. Sc.

Laboratorio da Produ?ao Mineral, Minist^rio da Agricultura,
Rio de Janeiro, Brazil
Member of the Brazilian Acadejny of Sciences
Formerly Professor of AnalyticalTind' Inorganic Chemistry
at the Uniwersity of Vienna
.6
Third, completely revised, English edition

translated by
R A L P H E. O E S P E R , P h . D .
Professor of Chemistry, UciTersity of Cindnaati
1947
ELSEVIER PUBLISHING COMPANY, Inc.

NEW YORK AMSTERDAM
X. r V .Hition 1937 (translation by J . W. Matthews
SocondEng .shed on 19 ^ ^^^^^^^.^^ by R. B . Oesper
''"^' o?tl s ' H^' translation by J. W. Matthews)
Copyright, 1946, by
Elsevier Publishing Company, Inc.
N e w Y o r k , N . Y.
53 Ht
DEDICATED in grautude to the
Chemistry Department of the
United College of St. Salvator
and St. Leonard in the University
of St. Andrews, Scotland.
PREFACE
The second English edition of the author's Qualitative Analysis by
Spot Tests appeared in 1939'. '* The text had been translated from the
third German edition. Several reprintings of this translation were issued
because the author, for various reasons, simply was not in a position to
comply with the publisher's request to prepare a revised edition. In
the meantime, the available material was increasing at a tremendous
rate. Only within the past year has it become possible to assemble and
arrange the contents of these recent publications with the view of incor-
porating this later information into this book.
The present edition includes the newer spot reactions, together
with details of the pertinent procedure and applications. Furthermore,
the previous text has been subjected to a thorough critical examination.
So many additions and improvements resulted that this edition can truly
be described as thoroughly revised. The author has tried to assemble
and present the entire literature on spot test analysis in such form that
the reader will be able to secure here a rapid survey of the available spot
tests and their application. Tested directions for carrying out the tests
are, of course, an integral part of the. text.
Since the present volume was designed to offer a complete picture
of all the phases of spot test analysis, it was thought advisable to include
a section on technique and apparatus. Permission was therefore obtained
from the Academic Press, Inc., New York, to include the chapter: "Work-
ing Methods and Special Aids" from the author's recent (1943) Labora-
tory Manual of Spot Tests. Consequently, in contrast to the previous
editions, this issue also presents a detailed account of all the manipulations
involved in satisfactory spot test analysis. Other new features are a
chapter on the detection of free elements and a bibliography on the appli-
cation of spot reactions for special scientific and technical purposes. Al-
though a previous chapter is devoted to an extensive treatment of the
practical use of spot tests, this bibliography contains about 140 additional
entries (with title, author, and place of publication) which seemed to
demand inclusion in any comprehensive text. This considerable number
is excellent testimony to the growing recognition and ever-widening useful-
ness of spot test analysis. Consequently, and despite certain abridgments
and a more economical format, the text has increased in size, but the
growth is amply justified by the necessity of including all the material
on the subject.
The previous practice of dividing the material into comprehensive
chapters has been retained. Likewise, no change has been made in the
general method of describing the spot reactions that have been found
useful in inorganic and organic qualitative analyeis. In each case, as
viii PBEPACE
before, the chemistry is outlined, the procedure is given, and the strength
and preparation of the requisite reagents aijd the use of the eqmpment
are discussed in adequate detail. All tests that have been used success-
fully for a good many years are described in particularly.full detail. Last,
but not least, the citations to the original literature are provided. For
the benefit, especially, of English-reading chemists the references to obscure
or inaccessible papers are given, when possible, to Chemical Abstracts
rather than to Chemisches Zentralblatt, as in the previous editions. Certain
spot reactions, which have not yet come into general use and accordingly
must still stand the test of time, are briefly described. The reference
to the original literature, which is especially important in such instances,
is, of course, given. Numerous observations and improvements that
are the fruit of years of experience and that have not been published else-,
where are included here. Altogether, the present text contains about
350 detailed and about 115 orienting sets of directions concerning the
detection or identification of about 150 elements, compounds, and typical
radicals or groups. In addition, about 175 suggestions and procedures
are given for, solving special problems that may confront the analyst.
Typical instances are the detection of accompanying materials, tests of
purity, studies of minerals, etc. The foregoing figures do not include the
entries in the bibliography that makes up Chapter VIII.
Every effort has been made to include or take account of all the
published material on spot test analysis. If, inadvertently, items have
been omitted, the fault perhaps may be laid to the disturbed world con-
ditions that prevailed during the prepara,tion of the manuscript. The
author will be grateful to his fellow chemists for any cooperation in the
way of suggestions, communications, and inquiries that will make it easier
to keep the book up to date, as it is planned; to issue new editions when they
are warranted. ^ - .^
The necessary studies involved in issuing a new edition of this text
could not possibly have been brought to a satisfactory conclusion in a
comparatively short time unless the author liad been given a favorable
atmosphere in which to carry out both his literary and experimental labors.
Special thanks are therefore due to the Brazilian government,' in particular
the Ministry of Agriculture, for establishing a separate research laboratory
and staflSng it with competent assistants. These facilities made it possible
to carry out numerous new studies on spot test analysis, and to accumulate
a rich fund of experiences on the practical applications of this special
type of analysis. Dr. Mario da Silva Pinto, "dii-ector of the Laboratorio
da Producao Mineral, has supported all our work in most generous fashion.
My special assistant, H. A. Suter, has earned my heartfelt gratitude by
his willing and helpful active collaboration.
PREFACE ix
Dr. Janet W. Matthews ^ of London translated the two previous

English editions. The writer wishes to express again his appreciation
of her cooperation, and now particularly for her gracious consent to forego
her role as translator of this new edition. The physical difficulties of
communication between Brazil and England and the desire to print the
text in the United States made a change of translators unavoidable. A
large part of the Matthews rendition is carried into the present text.
Dr. Ralph E. Oesper of the University of Cincinnati consented to
substitute for Dr. Matthews. He and the writer have similarly collaborated
on many previous occasions. The writer owes him thanks for his usual
excellent translation. However, his efforts have gone far beyond mere
translating. He has been actuated by a deep interest in the project, and
has brought to his task the spirit of a true co-worker, thoroughly in sym-
pathy with the objectives of the writer.
In April, 1939, the writer closed the preface to the second edition
with the paragraph:
"Owing to the annexation of Austria by the German Reich I, as well as many
other scientists, lost my position as a Professor at the Vienna University. At this
time the University of St. Andrews in Scotland offered me an opportunity to continue
my researches in the Chemical Department of that University and was ready to give
all necessary help. Though I did not make any use of that generous offer, it has helped
me to maintain my faith in the community of science, in a time of deepest depression.
"I therefore dedicate this book to my honoured colleagues of the Chemical
Department of the University of St. Andrews, Scotland, as a sign of my sincerest
gratitude for their comradeship and liberal attitude."
This dedication is here renewed, as a token of lasting gratitude and
a very slight repayment of the debt which the writer, along with many
of his expatriated fellow scientists, owes to his colleagues in many countries
to whom we have been and have steadfastly remained the nonforgotten
Allies.
Rio de Janeiro FRITZ FEIGL
July, 1945
Translator's Note
The translation of the earlier editions was entrusted to Dr. Janet Matthews;
much of this rendition of Dr. Feigl's text survives here. The present translator
has kept in constant touch with the author, and this close collaboration is re-
flected in many of the altered passages and enlarged sections. The considerable
lapse of years between the present and the last English editions is due entirely
to difficulties arising from the war.
CONTENTS
PAGE
PREFACE vii
General Remarks on the Development, Present State, and Methods of Spot Test
Analysis 1
I. WORKING METHODS AND SPECIAL AIDS IN SPOT TEST ANALY-
SIS 8
1. Preparation and Storing of Solutions 9
2. Grinding and Mixing Solids 12
3. Taking and Application of Drops 14
4. Spot Reactions on Filter and Reagent Papers 17
5. Spot Reactions in Porcelain and Glass Vessels 23
6. EvaporationDryingIgnitionFusion 26
7. Action aiid Liberation of Gases (Vapors) 29
8. Heating of Solutions 32
9. Separation of Solid and Liquid Phases 34
10. Other Special Aids 39
II. TESTS FOR METALS 41
Cations and Anions of Metallic Acids 41
A. Hydrogen Sulfide Group . 42
(a) Basic Sulfide Group^, 42
Silver .- 42
Mercury 48
Lead 55
Bismuth 59
^ Copper 63
Cadmium 74
(b) Acid Sulfide Group 79
Arsenic 79
Antimony 83
Tin 86
Germanium 89
Molybdenum 92
Tungsten 94
Vanadium 97
Gold 100
Platinum Metals 101
Platinum HH
Palladium 104
Osmium and Ruthenium... . .^...._ ^. , 107
B. Ammonium Sulfide Group 1 (W
Cobalt : 109
Nickel 114
Thallium 119
Iron 122
Chromium 128
Manganese 132
Zinc -. 137
xi
Xii CONTENTS
PAGE
Aluminum , 142
Beryllium , i 147
Titanium , 150
Zirconium 153
Uranium 157
Cerium , 160
Indium and Gallium 162
C. Ammonium Carbonate Group 165
Barium 165
Strontium 169
Calcium 169
D. Alkali Metals, Ammonia, and Derivatives of Ammonia 171
Magnesium 171
Sodium 176
Potassium 177
Lithium / 180
Cesium / 182
Ammonia (Ammonium Salts).., 182
Hydrazine 186
Hydroxylamine <' 186
III. TESTS FOR ACID RADICALS 191
Anions 191
Hydrochloric Acid 191
Hydrobromic Acid 194
Hydriodic Acid 197
Hydrofluoric Acid 202
Hydrocyanic Acid 208
Mercuric Cyanide * 210
Thiocyanic Acid I 212
Hydrazoic Acid 1 215
Ferrocyanic Acid (Hydroferrocyanic Acid) 215
Ferricyanic Acid (Hydroferricyanic Acid) 218
Chloric Acid 221
Bromic Acid , .^^. 222
Iodic Acid .,^-. 223
Periodic Acid -.-........ 224
Hydrogen Sulfide 226
Sulfurous Acid : 231
Sulfuric Acid 236
Thiosulfuric Acid '. ( 240
Persulfuric Acid ' , 242
Nitric Acid 243
Nitrous Acid ^ 248
Phosphoric Acid /. 250
Silicic Acid /. 252
Carbonic Acid ."....-..'.... 254
Boric Acid. 256
Permanganic Acid 261
Chromic Acid 282
CONTENTS XIU
PAGE
Selenious Acid 263
Telluric (Tellurous) Acid 266
Hydrogen Peroxide 268
IV. T E S T S F.OR F R E E E L E M E N T S 272
A. Free Metals and Alloys , , 272
Mercury (Mercury Vapor) 274
. B . Free Non-metals 276
Free Halogens 276
Free Sulfur..'?. 277
Free Selenium.. i ,. 279
Free Carbon 281
V. T H E SYSTEMATIC ANALYSIS OF M I X T U R E S BY SPOT REAC-
TIONS 282
Gutzeit's Analytical Scheme 283
Analysis Scheme According to Heller and Krumholz 287
Analysis Scheme According to Krumholz 289
Spot Analysis of Alloys According to Heller 291
Application of Spot Tests in Preliminary Examination 294
Scheme of Analysis for Anions in a Mixture 298
Identification Tests for Substances Insoluble or Sparingly Soluble in
Acids"Insoluble Residue'- . 300
VI. T H E USE OF SPOT REACTIONS IN QUALITATIVE ORGANIC
ANALYSIS 309
A . Detection of Elements in Organic Compounds 310
Halogens 311
Sulfur 313
Nitrogen 315
Phosphorus 317
Arsenic 318
Oxygen 319,
B. Detection of Characteristic Groups in Organic Compounds 320
Nitroso Compounds (NO-Group) 321
N i t r e Compounds (NO2 -Group) 322
Alcohols 321
Phenols 329
Enols -..332
Carbonyl Compounds ( ^ C O - G r o u p ) 333
o-Dioxo and Oxomethylene Compounds (COCO and
- C H 2 CO Groups) 334
Aldehydes (CHO-Group) : 339
a, (J-Unsaturated and Aromatic Aldehydes ( ^ C = C C H O - G r o u p ) . 349
Methyl Ketones (CHsCO-Group) , 349
Oximes and Hydroxamic Acids ( ^ C = = N O H Group) . , 352
Thioketones and Mercaptans ( ^ C = S and ^ C S H Groups) 353
Carboxylic Acids and Their Derivatives 355
1,2-Dicarboxylic Acids /CCOOH GroupX 360

I
\CCOOH )
XIV CONTENTS
PAGE
Sulfonic Acids (SO3H Group) , 363
Amines ?..., {j. 368
Primary Aliphatic Amines 373
Secondary Aliphatic Amines , 374
Aromatic Amines , 375
Acid Amides and Acid Nitriles 375
Pyrrole Derivatives 378
a-Amino Acids (CH(NHj)COOH Group) 384
Hydrazines .' 385
Reactive CHj and NH2 Groups 389
Tertiary Ring Bases 392
C. Identification of Specific Organic Compounds 393
Formaldehyde 396
Chloroform 395
Methyl Alcohol 396
Formic Acid < 397
Acetic Acid ,. . 397
Glycolic Acid 399
Lactic Acid 400
Glyceric Acid '... 401
Pyruvic Acid 402
Oxalic Acid 402
Malic Acid 405
Tartaric Acid . 405
Citric Acid ,407
Glycerol 408
Carbohydrates ' 409
Tyrosine 411
Protein ' 412
Pyridine 414
p-Phenylenediamine 415
Phosgene 416
Carbon Disulfide 417
Ascorbic Acid (Vitamin C) 419
Test for Enzymes "... ^, 421
VII. APPLICATION OF SPOT REACTIONS IN TESTS OF PURITY,
EXAMINATION OF TECHNICAL MATERIALS, AND STUDIES
OF MINERALS _ 425
Silver in Alloys and Silver Plating .,.,.,.. 425
Copper in Alloys , 426
Copper in Pharmaceutical Products or Foodstuffs 427
Copper in Water 427
Lead in Tin Platings and Enamels 427
Lead in-Alloys and Crude Metals 428
Lead in Ores, Minerals, and Pigments 429
Lead in Water, Alkali Salts, and Sulfuric Actd. , 430
Lead in Bismuth Compounds 432
Tin in Minerals, Metallic Objects, etc 432
"CONTENTS XV
PAGE
Molybdenum in Tungsten Ores and Technical Materials 433
Differentiation between Palladium and Platinum Foil 434
Nickel Plating and Nickel Alloys 434
Nickel in Cobalt Salts 434
Zinc in Plated Metals 437
Iron in Fluorides 437
Iron in Mercury Salts 438
Iron in Alumina and Pyrolusite 438
Chromiiim in Rocks and Steel 438
Uranium in Minerals -. 439
Titanium in Minerals 440
Magnesium in Silicate Rocks .' 440
Potassium in Silicate Rocks 441
Alkali Metals in Silicates 441
Differentiation between Magnesite and Dolomite or Braunerite 442
Lime in Magnesite 444
Differentiation between Calcite and Aragonite 444
Identification of Calcium Sulfate (Gypsum and Anhydrite) 445
Differentiation between Gypsum and Anhydrite 447
Orienting Tests of Glass 448
Free Metals in Oxides, Printing on Paper, etc 449
Procedure for Testing Woods Impregnated with Solutions of S a l t s . . . . 450
Testing Leather to Find Method Used in Tanning (Mineral-Tanned
Leather) 451
Chemical Identification and Determination of Age of Ink Writing 452
Fixed Alkalis and Ammonia in Alkali Cyanides 455
Alkali Earths and Alkali in Paper and Coal Ash 455
Ammonium Salts in Chemicals 456
Imprint and Developing Procedure foi* Chemical Identification of
Heterogeneities in Manufactured Metals, Minerals, etc 457
Electtographic Methods 461
Fluorine in Rocks and in Mineral Waters 463
Sulfide Sulfur in Rocks 464
Selenium in Minerals, in Sulfur, and Tellurium 465
Sulfates in Hydrofluoric Acid or Fluorides 465
Sulfate in Inorganic Fine Chemicals 466
Bichromate in the Presence of Alkali Monochromates 467
Alkali Monochromate in the Presence of Alkali Bichromate 467
Carbonate in Alkali Cyanides, Sulfites, and Sulfides 468
Silica in Caustic Alkalis and Alkaline Solutions. Testing the Vulnera-
bility of Glass and other Siliceous Products to Attack by Alkalis 469
Silicic Acid in Minerals 470
Boron in Rocks and Enainel 471
Phosphates in Minerals and Rocks 471
Free Acids and Basic Compounds in Solutions of Aluminum Salts and
of Free Acids in Solutions of Copper and Cobalt Salts , 472
Hydrogen Sulfide in Water 473
Hydrogen-Ion Concentration of Aqueous Solutions 474
Orienting Reactions for Judging Samples of Water 476
Xvi CONTENTS
I
PAGE
Hardness of Water; Differentiation of Distilledand Tap Water 478
Inorganic and Organic (Basic) Materials that React with Mineral Acids. 479
Sulfur in Carbon Disulfide, Ether, other Organic Solvents, and Motor
Fuels 480
Sulfide Sulfur in Animal Charcoal and in Dyes 481
Free Sulfur in Solid Inorganic and Organic Products 482
Distinction between Acid and Basic Dyes 483
Carbon Disulfide in Benzene and Carbon Tetrachloride 483
Lead Tetraethyl (-phenyl) in Motor Fuels. ...- ,. 484
Differentiation^^f Animal and Vegetable Fibers ' 484
Test for Esters in Mixtures of Hydrocarbons 485
Oxalic Acid in Leather 485
Tests for Added Materials and Undesirable Admixtures in Organic
Substances 486
Application of Spot Tests in the Examination of Powder and Explosives 488
VIII. BIBLIOGRAPHY ON THE APPLICATION OF SPOT REACTIONS
FOR SPECIAL SCIENTIFIC OR TECHNICAL PURPOSES 489
A. Journals 489
B. Books : 494
IX. TABULAR SUMMARY of the Limits of Identification Attained by the
Spot Tests ~ 496
A. Inorganic Analysis. Cations 496
B. Inorganic Analysis. Anions 502
C. Inorganic Analysis. Free Elements 605
D. Organic Analysis. Certain Elements 606
E Organic Analysis. Characteristic Groups 606
F. Organic Analysis'. Compounds 608
AUTHOR INDEX 511
SUBJECT INDEX 519
General Remarks or^ the Development, Present State,
and Methods pf Spot Test Analysis
Analytical chemists have long used single chemical tests carried
out in drops of solutions on filter paper or on impermeable surfaces. A
familiar example is the use of indicator papers to detect rapidly an excess
of hydrogen or hydroxyl ions in a single drop of solution. Likewise, the
end point of certain reactions used in titrimetric analysis, or the completion
of electrolytic depositions, can be established by removing a drop of the
test solution and bringing it into contact with a suitable reagent on filter
paper, on a watch glass, or on a porcelain plate.
I t has not been definitely established who made the first use of spot reactions
for analytical purposes. Probably the earliest published instance was given by H
Schiff.1 He used paper impregnated with silver carbonate to reveal uric acid in urine.
A drop of the specimen produced a brown fleck of free silver. This appears to be the
first-precise description of a spot test, because the great sensitivity of this reaction
was determined by testing a series of dilute solutions of pure uric acid. The funda-
mental work for that division of spot test analysis in which filter paper functions as
the reaction medium is a study by C. F. Sch6nbein. He showed that when aqueous
solutions rise in filter paper the water precedes the dissolved material and that the
relative height of ascent of solutes can differ enough so that the cosolutes can be de-
tected in separate zones. These observations gave the impetus for the classic works
(1861-1907) of Fr. Goppelsroeder that were compiled in his Kapillaranalyse published
at Dresden in 1910. He made a very extensive study of the capillary rise of solutions
and the capillary spreading of drops of solutions in paper and the analytical use of
these effects, particularly in the examination of organic compounds and dyes.
Efforts to detect, if not all, at least a large number of cations and

anions by sensitive reactions in the form of spot tests or drop tests were a
later development. These are characterized particularly by the fact
that no recourse is made to optical aids and the drops used are considerably
larger than those employed in classical qualitative microanalysis. All
such chemical tests for individual materials and the constituents of a
mixture are included in the name "spot test analysis."
The writer, together with numerous collaborators and students,
has been systematically working in' the field of spot test analysis since
1918. The prime goals have been the employment of these procedures
on a microfchemical scale and the simplifications of the analytical methods.
It became'evident that these studies could not be limited to a consideration
of the special manipulations involved and the judicious extension of the
technique of spot analysis. Above all, researches on the sensitivity and
specificity of the reactions had to be made. Furthermore, comprehensive
H. Schiff, Ann., 109, 67 (1859).
' C. F. SchSnbein, Ann., 114, 275 (1881).
1
2 GENERAL REMARKS ON SPOT TESTS
1
experimental investigations were necessary to discover possible new sen-

sitive and conclusive tests that could be conducted as spot reactions.
Only through an extensive use of all the varieties of reactions involving
coordination compounds, and of the reactions of inorganic materials
with organic reagents and vice versa, of catalyzed and induced reactions,
offluorescencephenomena, of flotation and extraction processes, combined
with due consideration and utilization of the capillary and adsorption
processes accompanying reactions on filter paper, did spot analysis even-
tually develop into a recognized branch of analytical chemistry, especially
of microanalysis. Research in this field and application of this method-
ology no longer need any special defense.
Among the possibilities of utilizing spot procedures, special significance is at-
tached to the employment of organic reagents. Without them, spot analysis in its
present form would not be possible. Consequently, it should be emphasized that the
use of organic reagents in inorganic macro- and microanalysis is indissolubly linked
with the pioneer work of M. Ilinskiand G.v. Knorre (a-nitroso-/5-naphthol, 1885), P.
Cazeneuve (diphenylcarbazide, f900), L. Tschugaefif (dimethylglyoxime, 1906), F.
RaschigandG.DenigSs(benzidine, 1903,19J3),andO.Baudisch(cupferron, 1909). The
analytical activity of organic reagents almost always is closely connected with the
chemistry of complex compounds originated by A. Werner. If the analytical signifi-
cance of purely inorganic complex compounds is also taken into account, many divisions
of spot analysis can justifiably be termed "applied complex chemistry."
Because of the variety of chemical and physical effects that are called
on in spot analysis to attain the desired analytical goals, sensitivity and
certainty, spot analysis is more closely identified than is classical macro-
analysis with many fields of chemistry. The theoretical bases of spot
analysis, therefore, are entitled to a special discussion. This will be found
in considerable detail in one of the writer's previous books.'
The publication of the findings of tte first systematic studies on
spot analysis and reaction specificity were fortunately followed by valuable
contributions from numerous investigators, who promoted the development
and extension of this field. Anger, Atack, Clarke, Dubsk;^, Eegriwe,
Fischer, Frehden, Hahn, Glazunow, Gutzeit, Kolthoff, Komarowsky,
Kul'berg, Krumholz, Poluektoff, Szebelfedy, Wenger, Yagoda, Yoe,
some of them students of the writer, and above all, Tananaeif, are among
those who by their important original studies and pioneer investigations
of new fields of application have contributed decisively to the chemistry
of specific and special reactions and to the propagation of spot test analysis.
The first objective of systematic spat test anal/sis was merely the
solution of problems presented by qualitative inorganic analysis. So
much proved material is now available along these lines (see Chapters
F. Feigl, Specific and Special Reaction*, with Particular Reference to Spot Test
Analysis. Translated by R, E. Oesper, Elsevjer, New York, 1940.
GENERAL BEMARKS ON SPOT TESTS 3
II to V) that the description and recommendation of many spot reactions

are now included even in elementary texts and laboratory manuals of
qualitative inorganic analysis, as well as in special technical books.
The use of spot reactions in laboratory practices in institutions of higher learn-
ing datgs from 1929 when they appeared in the official syllabus of the Institute of
Analytical Chemistry at the Technical High School in Delft (Professor C. J. van
Nieuwenburg). The writer had practical experience with student courses in the labo-
ratories of the University and the Volkshochschule in Vienna from 1921 to 1938. His
pedagogical findings were utilized in his Laboratory Manual of Spot Tests.*
Since 1943, the author, his collaborators, and students have found that spot
reactions succeed so well for the detection of elements and characteristic
groups in so many organic compounds that qualitative organic analysis
has grown to be a special division of general spot test analysis (see Chapter
VI).
Sensitive and characteristic spot reactions for inorganic and organic
compounds (or atoms, or groups of atoms in them) often make it possible
to detect with certainty individual materials and constituents of mix-
tures in an astonishingly simple manner. Such spot reactions, if specific,
that isîf they show characteristic effects with only one material, or
"under restricted reaction conditions, can be carried out directly with small
amounts of the sample. Selective reagents, that isthose that apply
to a limited number of materiaLs or reaction conditions, often necessitate
a preliminary separation into groups. Group separations and other
separations preceding the actual spot test almost always can be accompHshed
on a semimicro- or microscale (see Chapter II). This varied applicabiUty
of spot reactions has made spot analysis a special technique of systematic
semimicro- and microanalysis. If the reaction conditions of a spot test
are known, it is frequently possible to transform the procedure to the
macroscale, which sometimes may be desirable. Furthermore, it is often
advantageous, in the course of a macroanalysis, to make certain tests
of identity by means of spot reactions. If tests of different sensitivities
are used, significant information can often be deduced as to the quantity
of material present from the positive or negative response to the various
tests. The foregoing do not exhaust the uses of spot reactions. A very
important and constantly growing application is the use of spot reactions
for the' solution of special problems in applied analytical chemistry. Among
these are the studies of minerals and rocks, the examination of technical
materials, the tests of the purity of drugs and foods and the like, the
detection of certain compounds in biological materials, and the securing
of evidence in forensic investigations. All these special fields present
* F. Feigl, Laboratory Manual of Spot Tests. Translated by R. E. Oesper,
Academic Press, New York, 1943.
4 GENERAL REMARKS ON SPOT TESTS
instances in. which spot reactions are not only asi good as macromethods,
but in some cases the problems can be brought i to a successful solution
more quickly and more conclusively than, when the earlier and more faT
miliar procedures are used. See Chapters VI and VII.
This book presents all the divisions of practical applied spot test
analysis. All the important publications in this field have been consulted.
The material has been divided into suitable chapters to facilitate the "
comprehension of the quite varied topics which necessarily are included.
The description of the individual tests give detailed procedures,
the preparation of the required reagents, and a discussion of the chemistry
involved. The sensitivity attainable is given for each test. In accord
with the writer's suggestion,' which has now been generally adopted,
the sensitivity of a test is characterized by the figures for its U'mit of iden-
tification and its concentration limit. The former is the absolute quantity
of the material that can still be just detected under the test conditions.
It is expressed in 7 (1 7 = 1 microgram). Consequently, the limit of
identification is a measure of the quantity sensitivity of a test. ^ Its correlate
is the concentration sensitivity, thaj; is, the degree of dilution at which
a test will still just respond under the test conditions; this is the concen-
tration limit. It should be emphasized that the identification limit and
limiting concentration should not be regarded as characteristic data of
a chemical reaction, but only as characteristic and reproducible figures
pertaining to the particular conditions and procedure of an analytical
test reaction. In spot test analysis, the aun always is to attain the total
maximima sensitivity by an intelligent use of chemical and physical effects.
In other words, to reach the lowest possible value of the identification
limit and the highest possible value of the colicentration limit. The
tabular summary in Chapter IX gives the attainable identification limits
of a large number of spot reactions. It reveals that values greater than
2 y per 0.d5 ml. drops (concentration limit, l:25i0Q0) are infrequent.
In most cases, this value lies below 0.2 7 (concentration Imiit-, 1:250,000).
Often, far lower identification limits and correspondingly high concen-
tration limits are reached. A comparison of the identification limits
and concentration limits attainable by spot reactions with the corresponding
figures for tests by the classical methods of microanalysis (particularly
precipitations of crystals) shows that the former are superior to practically
all the precipitations with respect to concentration sensitivity (concen-
tration limit). As to quantity sensitivity (identification limit), spot
reactions are sometimes as good as precipitations, sometimes better,
seldom inferior. Consequently, if the objective of qualitative micro-
analysis is not the use of a particular technique but the detection of absolute
' F. Feigl, Mikrochemie, 1, 4 (1923).

GENERAI/ REMABKS ON SPOT TESTS 5
and relatively (with respect to dilution) small quantities of material, spot

jeactions indubitably, in the great majority of cases, should be regarded
as microchemical tests.
Sometimes spot reactions are called semimicro reactions, and spot test analysis
is' referred to as semimicroanalysis. Siich terms, in light of the statements that
have just been made, are false and lead to error by such generalization, since logi-
cally a spot reaction which is more sensitive than a microchemical precipitation can
never be "semimicrochemical." It is only permissible and correct to distinguish
between semimicro- and microanalytical tests in order to draw the limits between
these two classes and to contrast these two with macrochemical tests. Semimicro-
abalytical tests refer to quantities (identification limits) of 10 to 200 y; microanalyti-
cal tests involve identification limits below 10 -y.' Spot test analysis, regarded as
"microanalysis without a microscope" because of the identification limits of its tests,
can accomplish the solution of the problems of semimicro as well as of microanalysis.
The detection of individual metal salts in solution can almost always

be carried out by spot reactions of different intensity. The same holds
in the qualitative organic analysis for elements, many characteristic groups,
and frequently for organic compounds as such. The data on identification
limits and concentration limits given for the various tests refer to pure
salt solutions unless otherwise stated. These values, together with the
statements concerning any unpairment by accompanying materials, give
an indication of the analytical effectiveness of the particular test. The
efficacy determines whether spot reactions can be used for semimicro- or
microanalytical purposes. The use of spot reactions is also advisable
for economic reasons, even though there is enough sample to make the
test without difficulty in a test tube or by the usual procedures of macro-
analysis. On the other hand, the use of spot reactions is often imperative
because only slight quantities of solutions or solids are available, or if
there are special reasons for employing not more than a part of the spec-
imen, or if the information must be obtained without visibly damaging
the test material. In most cases, 0.6 ml., or a few milligrams of the sub-
. stance will suffice for the definite identification of metals, characteristic
groups, or compounds, even though the spot tests are repeated several
times. Much smaller quantities are adequate for particularly sensitive
tests. The selection of the test to be used will differ from case to case,
depending on circumstances.
Spot test analysis in its present form is characterized particularly
by the fact that it reveab extremely small quantities by means of a very
simple technique, with simple apparatus, and with the greatest possible
economy of material, time, and space. There is no doubjt that the most
favorable identification limits and concentration limits of many of the
spot tests described in this book could be improved even more by suitable
6 GENERAL REMARKS ON SpOT TESTS
measures. For instance, almost all reactions caln be carried out with
drops smaller than 0.05 ml. Observation of spot jreactions under magni-
fication (reading glass or microscope) often Jâkes possible the recognition
of much smaller quantities of reaction products than are detected in the
usual spot reaction procedures. Considerable enhancement of sensitivity
is obtained if difficultly soluble reagents are incorporated in filter paper."
A drop of a test solution placed on such reagent papers reacts immediately
and, since capillary migration is excluded, the resulting flecks are smaller,
and consequently their colors are more ir^tense. If snialler drops are
employed, impregnated silk threads can sometimes be used in place of
paper, or minute volumes of the test solution are allowed to rise in a porous
thread, which is then pressed against suitable reagent papers.' Frequently,
spot reactions can be carried out on media other than paper, silk.threads,
or porcelain. Thus, magnesia rods or grooves are sometimes suitable.
Drops of neutral or alkaline test solutions can be evaporated on these and
the spot reaction made with the evaporation residue. Sintered glass is
suitable in some cases. Gefatin gels containing the reagent can also
be used. Characteristic colored flecksôr crystals imbedded in the gelatin
are produced.^ An advantage of this procedure, which has thus far not
been applied very widely, though doubtless it is capable of considerable
development, is that the completed tests f;an be dried and made into
permanent preparations by familiar methods.'
The choice of the particular procedures for spot reactions will not
be difficult for the experienced chemist for whom the directions given in
this book will suffice. Likewise, he is competent to select the test most
suited for his purpose. In any case, spot te^t analysis, as the suggestions
given here should show, ought to provide a wide opportunity for improvmg
the technique employed for special purposes. Likewise, the discovery
of new identifying reactions for inorganic i^nd organic compounds, and
their adaptation as spot tests, will doubtless provide many improvements
and amplifications and lead to an extension of the field of application of
spot test analysis.
An extension of our present knowledge concerning the influence of
B. L. Clarke and H. W. Hermance, Ind. Entj^ Chem., Anal. Ed., 9, 292 (1937).
' E. M. Przibram, Chem. Zentr., 1939,1, 475.
J. Winokelmann, Mikrochemie, 10, 437 (193i). IJ 127 (1932)- 14, 171 (1934)-
16,203(1936).
In this connection, the somewhat remarkaljie phenomenon should be noted,
that, when chemical reactions are carried out on cellophane, or transparent paper
impregnated with the reagent or the solution of the metal salt,, the product of the
reaction frequently remains in the paper in the co\ioidaMorm. For instance, when
metallic sulfide or nickel dimethylglyoxime are fornigd, the paper is stained brown-
black or red, although no solid particles are visible vith the naked eye. Unpublished
work, G. Hirsch, Dissertation, Vienna, 1927.
GENERAL REMARKS ON SPOT TESTS 7
accompanying materials on the certainty and sensitivity of spot tests

would be of great significance in the application and further development
of spot tfest analysis. The tremendous possibilities of varjang the kinds
and quantities of accompanying materials presents an extensive field in
which empirical trials can furnish valuable statistical material which,
later, may perhaps result in the recognition of certain new regularities
in the effects of foreign materials on reactions.""
In conclusion, it may be pointed out that spot reactions that give
colored reaction products make it possible not only to detect materials,
but also to estimate the quantities present. The color intensity of the
spot test given by the test solution is compared with that obtained with
drops of standard solutions containing known quantities of the material.
This procedure has been suitably named "spot colorimetry" by N. A.
Tananaeff. If colorless or only shghtly colored insoluble reaction products
are involved, the turbidities can be compared, if the spot tests are made
on black porcelain plates This procedure can logically be called "spot
nephelometry." H. Yagoda" introduced the use of confined spot test
papers. This was a considerable improvement and refinement of spot
colorimetry. The use of known, and the discovery of new and more
sensitive, color and precipitation reactions that can be applied as spot
reactions will doubtless lead to the development of a new branch of quanti-
tative microanalysis. Such quantitative spot methods admittedly will
not give values as accurate as those obtained by the classic methods of
microanalysis, but they have the advantage of simpUcity and speed.
Ponsequently, they will often be adequate for preliminary examination
of materials and will serve for control purposes. A discussion of spot
colorimetric determinations is given in the writer's Laboratory Manual
of Spot Tests.*
Valuable studies along this line have been made by L. Smith and P. West,
Proc. Iowa Acad. Sci., 46,189 (1939); /red. Eng. Chem., Anal. Ed., 13, 271 (1941).
" H. Yagoda, Ind. Eng. Chem., Anal. Ed., 9, 79 (1937).
I. WORKING METHODS AND SPECIAL AIDS
IN SPOT TEST ANALYSIS
1
The tenn "spot reaction" is a generic name applied to microchemical
and semimicrochemical tests for inorganic and organic compounds or for
characteristic atoms and groups of atoms contained in them. All of
these tests are accomplished by sensitive and characteristic chemical
changes which can be carried out directly or indirectly. In these tests
an important part is played by manipulation with drops (micro- or macro-
drops) with no auxiliary optical magnification. Accordingly, spot reactions
can be made:
1. By bringing together one drop each of the test solution and rea-
gent on porous or nonporous supports (paper, glass, or porce-
lain).
2. By placing a drop of the test solution on a medium impregnated
with appropriate reagents (filter paper, asbestos, gelatin).
3. By placing a drop of reagent solution on a small quantity of the
solid specimen (fragments or pulverized; evaporation or ignition
residues).
4. By subjecting a drop of reagent or a strip of reagent paper to the
action of the gases liberated from a drop of the test solution or
from a minute quantity of the solid specimen. ,
6. In an extended sense, spot reactions may also include tests accom-
plished by adding a drop of reagent solution to a larger volume
(0.5 to 2 ml.) of test solution and then extracting the reaction
products with organic solvents.
The choice of the foregoing procedures; will be determined by the
nature of the sample, the reagents required, and the desire to attain the
highest possible certainty and sensitivity of the test.
The actual "spotting" is the most essential manipulation in spot.test
analysis but it is not always the only operation involved. "Frequently,
preliminary measures are necessary to produce appropriate reaction condi-
tions. Such preliminary operations may be either physical or chemical:
drying, evaporation, ignition, solution, oxidation, reduction, adjustment to
definite pH values, etc. Occasionally in organic analyses, it is necessary
to carry out separations, disintegration processes, etc., with the material
in question. Sometimes even syntheses on a small scale are required as a
preliminary step. Special apparatus'is required in such preparative
operations. Special expedients must sometimes be employed to make
the reaction products as visible as possible (ex-traction, treatment with
acids or bases). Accordingly, the technique of spot test analysis neces-
sarily employs many of the familiar operations of macroanalysis but, of
8
PREPARATION AND STORING OP SOLUTIONS 9
course, always on an appropriately diminished scale, and, so far as is feasible,

without significant losses. Spot analysis, however, utilizes certain oper-
ations peculiar to itself and that cannot be applied at all in macroanalysis.
These include the widest use of capillary surface actions on paper and
other substrates and the direct use of solid reagents.
* The equipment and manipulations required in spot test analysis
are all simple; the technique can be learned without difficulty. The
essential requirements for a successful application of spot tests include
(/) a knowledge of the chemical basis of all details of the tests so that
every step of the procedures can be understood and executed intelfigently;
(f) strict observance of trustworthy experimental conditions; (S) scrupu-
lous cleanliness of the laboratory and all equipment; (4) the use of the
purest reagents.
Whenever possible, tests should be carried out several times. In
student exercises, where solutions of known content can'be used, parallel
tests should be made at various decreasing concentrations of the material
being detected. The reaction picture is thus fixed in the learner's memory
and, furthermore, he learns to appraise and compare the effectiveness of
tests. .
1. Preparation and Storing of Solutions
The preparation and storing of the solutions required for spot reactions
vary with their particular purpose, their stability, and the frequency with
which the solutions are to be used. Some solutions can be kept in readi-
ness at all times, others must be prepared freshly when the occasion de-
mands. Solutions of the test material, comparison solutions^ and reagents
which change on standing are examples of the latter class.
Stock solutions include the same auxiliary reagents that are employed in
macroanalysis: acids, bases, neutral salts; also, stable (water, alcohol, or
acetone) solutions of the actual spot reagents;and,finally,organic solvents,
^t is very convenient to keep on hand water solutions of metal salts (nitrates
or sulfates) and alkali salts of the various acids, containing 0.1 mg. per ml.
of metal or acid radical. These are used to prepare test solutions of the
pure salt, or solutions of known dilution, for comparison when analyzing
unknoAvn materials. The determination of the sensitivity of certain pro-
cedures, the comparison of the sensitivities of various reactions, and also
spot colorimetry require these standard solutions. Stock solutions should,
therefore, be accurately prepared from the purest chemicals. For this
purpose, the calculated quantities of salts of analytical grade can be weighed
out directly, and the solutions made up to the proper volume in caUbrated
flasks. For solutions made from hygroscopic or efflorescent compounds,
the approximate quantity is weighed out, the solution made up to a known
10 I. WORKING METHODS IN SPOT TEST ANALYSIS
volume and the actual concentration then determined gravimetrically or

titrimetrically. Neutral solutions of salts should be iprepared, if possible.
If acid must be added to prevent hydrolysis, as Uttle as possible should be
used, and the content of free acid noted on the label. Standard solutions
of organic materials, in inorganic solvents if necessary, can also be prepared
for use in spot testing organic samples.
Considerable quantities of all stable solutions, such as auxiliary rea-
gents, spot reagents, standard solutions, should always be on hand. Since
the actual spot reactions, as a rule, require only drops of the reagent, it is
well to keep a small supply of all the necessary solutions on the work table
in 50 ml. pipet or dropping bottles (Figs. 1 and 2). Storage bottles (2 1.
îj-^4mra^
5 mm/!
-43 mm./-
Fig. 1. Dropping bottle (i actual size) Fig; 2. Pipet bottle (i actual size)
for auxiliary reagents, 500 ml. for spot reagents, 1 1. cahbrated flasks for
the standard solutions) should be kept in a separate part of the laboratory.
The small bottles can be filled from these ^vith the aid of short-stem funnels.
All bottles, as well as all glassware used in spot test analysis, should be
made of the best resistant glass. Before being filled, the bottles must be
cleaned thoroughly and steamed but. Alkaline solutions that may attack
glass are best stored in bottles whose interior is coated with paraffin to
about three-fourths of their height. Pure melted paraffin is poured into
the bottle, which is then steadily swirled while it is being lowered up to
its neck in boiling water. The coated bottle is allowed to cool in the air.
All dropping (or pipet) bottles should be labeled plainly as to the
nature and concentration of their contents. It is convenient to keep the
PKEPARATION AND STORING OF SOLUTIONS 11
auxiliary reagents, solvents, and spot reagents in racks or blocks on the

work table; the auxiliary reagents are grouped according to acids, bases,
and neutral salts, and the actual spot reagents arranged alphabetically.
Solutions should be taken from the small bottles only by means of
their pipet or through the channel in the neck and stopper, never by pouring.
Since the drops delivered by the pipets or dropping bottles are often too
large, it is well to transfer several drops from these bottles to a "solution
dish" (Fig. 3) and then take the reagent from this by means of a glass rod,
pipet, or the like. The solution dishes are glass beakers with 1 mm.
walls and a capacity of 1 to 2 ml. A considerable stock of these should
alwi^ys be on hand.
As soon as solution dishes have been used, they should be put into
basins filled with water. The basins should have handles, and separate
basihs should be provided for acid, basic, and neutral solutions. Td clean
the dishes, the water is poured off, and the basins containing the dishes
are placed under the tap for a while. The dishes are finally rinsed several
times with distilled water. The dishes can be cleaned quickly in this way;
they are then placed on a double
layer of filter paper and allowed to
5 ml.
drain ,nd dry in the air.
If a solution cannot be used 4
at its original strength, but must 3
be- diluted, this can be done, de- 2 1 ml.
pending on the desired accuracy,' 1

either in a graduated cylinder (5 to
25 ml.) or with the aid of a stand- Fig. 3. Solution dishes (actual size)
ardized pipet and volumetric flask.
When an approximate dilution will suffice, or if several water solutions
of salts are to be mixed to carry out exploratory trials, one drop of
the solution to be diluted, or of the salt solution to be mixed, can be
placed in the depression of a spot plate. The necessary nmnber of drops
of water or of the other aqueous solutions are added and the solutions then
made uniform by blowing into them through a dry pipet, or by stirring
with a fine glass rod. The drops for the spot reactions and Uke purposes
can then be withdrawn directly. This is a rapid procedure and suffices
for many purposes.
Solutions of solid samples that are to be subjected to spot reactions can
be prepared in microcrucibles or test tubes. The smallest feasible volume
of the suitable solvent (chosen or found by trial) should be used. The
circumstances prevailing in each case will detennine whether such solutions
can be tested without further manipulation or whether the imdissolved
portions of the sample or the excess solvent must be removed before pro-
12 I. WORKING METHODS I N SPOT TEST ANALYSIS
ceeding. This point requires special consideration. As a rule, it is unwise

to test solutions that are too strongly .acid or too alkaline. Consequently,
and especially when dealing with acid solutions, it is often necessary to
remove the excess acid.
Test solutions which are not t o be used immediately should never -be
allowed to stand uncovered on the working table. This is particularly
important when small quantities are involved. The crucible can either
be covered with a small watch glass or placed in a small desiccator, whose
lower compartment contains a dish filled with water. Undesirable evapo-
ration can thus be avoided. On the other hand, if cautious evaporation
at ordinary temperatures is desired the crucible is allowed to stand over-
night in a desiccator charged with solid calcium chloride or concentrated
sulfuric acid, ora.small vacuum desiccator may be used (see also page 26).
"2. Grinding and Mixing "Solids P
Solid specimens must often be subjected to definite chemical changes
or special treatment in the course of analytical examination. These proc-
esses include solution in water, acids, or alkalis; fusion with disintegrating
agents (sodium carbonate, peroxide, pyrosulfate); volatilization of certain
components (fuming with hydrofluoric acid, sulfuric acid, etc.); extraction
with organic solvents. The maximum reactive surface of the solid should
be provided in such cases so that rapid and complete reactions may occur.
This requirement is .met in the case of slightly soluble compounds only
when they are freshly precipitated and gently dried if need be. Ignited
materials, especially natural or technical products, as a rule, must be
pulverized beforehand, since a direct testing on compact surfaces for
purposes of identification is only feasible in exceptional cases.
Samples are best pulverized in agate xaortars. A set of these with dif-
ferent capacities (0.5 to 6 ml.) should be provided. Mortars and pestles
of good porcelain or glass are less resistant Taut are good "enough for many
pinposes. Very hard specimens should be "broken up in a steel diamond
mortar before being pulverized in agate. Figure 4 shows a micromortar of
correct dimensions.
Mere grinding of hard materials in mortars usually produces a mixture

of aggregates of different sizes which must be homogenized before further
treatment. This is accomplished by bolting the powder through a tightly
stretched fine silk cloth. When the bolting cloth is tapped, the finest
particles of the powder fall through the meshegâfid the coarser fragments
remain behind. The latter are reground and the sifting and grinding
continued until the total sample has passed through the cloth. Only when
a perfectly homogeneous material is being examined may the coarser
GRINDING AND MIXING SOLIDS 13
residue be rejected and the first portion that has passed through the sieve
be taken for the chemical examination.
The arrangement shown in Figure 5 is suitable for bolting small
samples. It consists of an open glass tube with a flared rim. The tube is
easily obtained by cuf,ting off the bottom of a wide hard glass test tube. A
circle of very fine silk is stretched over the end and fastened with a string.
The powdered sample is placed in the center of the cloth, and the open end
of the tube is pressed against a square of white or black glazed paper. The
cloth is then tapped at the side of the powder with a glass rod. After the
Fig. 4. Microiaortar Fig. 5. Microsieve

(actual size) (actual size)
Fig. 6. Microspatula (nickel) (actual size)

fine powder has passed through the silk, the paper is folded into a V and
the powder brushed into a crucible or other reaction vessel.
Pulverized samples are mixed with powdered reagents only if the mate-
rials are well dried. The mixing can be done in crucibles, oh watch glasses,
and frequently on squares of glazed paper. Dry powders, that are not
hygroscopic, can be weighed satisfactorily on tared sheets of glazed paper
and can be brushed off the paper quantitatively. Microspatulas, platinum
wires, or thin glass rods are suitable for mixing powders; wooden splints
(toothpicks) often can be employed for this purpose. Paper and tooth-
picks offer the advantage that they can be thrown away after they have
been used once. Small horn spoons are used for transferring powders;
nickel microspatulas (Fig. 6) are employed for very small quantities. Dis-
secting needles, a good magnifying glass, forceps, streak plates of unglazed
porcelain (for testing the hardness and streak, lof a powder), and small
weighing bottles for storing specimens, are among the other aids required
for handling and working with solid samples.
3. Taking and Application of Drops
Taking drops from a test solution or reagent can be done in vari-

ous ways depending on the particular conditions surrounding the experi-
ment. The simplest method is to plunge a glass rod into the solution and
then let a drop fall off. The size of the drop depends on the thickness of
the rod (these are usually 20 cm. long). A glass rod 3 mm. thick delivers
drops whose volume is about 0.05 ml., while smaller drops are delivered
by rods approximately 1 mm. thick. The use of glass rods is, however,
permissible only for orientation trials, because it is impossible to regulate
the size of the drops. If the rod is not wetted sufficiently, there is danger
that the drops flow off too slowly, and the operator is tempted to
touch the filter paper or other substrate with the rod. This results in the
liquid being sucked off the rod with resultant loss of control of the size
of the drops. If a precipitate is being formed, parts of it may stick to
the rod, and in some cases this impairs the typical reaction picture.
An exact controlled delivery of drops can be secured by using pipets.
Simple glass pipets about 20 cm. long can be made easily by drawing out
tubes of resistant glass (4 mm. inside diameter). The width of the capillary
constriction determines whether macrodrops (0.05 ml.) or microdrops
(up to 0.001 ml.) are delivered by the pipets. Pipets with longer (up to
5 cm.) drawn-out capillary ends (inside diameter 1 to 0.5 mm.) are suitable
for smaller volumes of liquid and the delivery of smaller drops. The
transfer of smaller volumes of liquid from microcrucibles, centrifuge tubes,
and so forth can be done with the dropper pipets shown in Figure 7.
When drops are delivered from pipets, care must always be taken
that their outer surfaces are dry so that excess liquid is not carried along.
This can be avoided by wiping the filled pipet with soft filter paper, which
is then discarded.
If liquids are drawn into a pipet by mouth, the pipet should be held
so that the index finger is free and is kept so that it can easily be placed
over the end of the pipet. The thimib presses the tube of the pipet agamst
the three other fingers. The capillary end of the pipet is placed in the
liquid, the operator inhales slowly taking .care that no air bubbles get
into the capillary. The pipet is then closed quickly with the index finger.
The finger must not be clamped down tightly but should exert only a
slight pressure. The dropwise delivery of solutions from the pipet is
TAKING AND APPLICATION OF DROPB 15
accomplished by a very slight, partial raising of the finger. A little prac-

tice will give the correct and confident feeling for delivering single drops.
A pipet must never be discharged or closed with wet fingers because of
the danger of slippage with consequent loss of control of the delivery of
drops. The taking and delivery of liquids and drops by means of a dropping
pipet provided with a rubber cap must also be practiced to secure com-
plete mastery in the handling of drops.
When drops of liquid are placed on paper or spot plates by means of
pipets, the latter should be held at a very obtuse angle to the horizontal
surface. The capillary point should not be more,
than 1 cm. above the place where the drop is to
be delivered. If drops of the test solution and the
reagent are to be brought onto filter paper one after
the-other, care must be taken that the second drop
falls as nearly as possible in the center of the first
drop. However, sometimes there are particular
reasons, such as to secure better visibility of the
reaction, for spotting from the side.
It is often an advantage when carrying out spot
reactions on reagent paper not to drop the test solu-
tion onto the paper, but to flow it on from a capillary
pipet by lightly pressing the tip onto the paper.
The solution then spreads concentrically from the
point of contact; dissolved materials or reaction
products are thus retained in the immediate vicinity
of this point.'
Drops of a reagent may be taken directly from
the pipet or dropping bottles in which they are
stored, but it is always preferable to transfer a,small
volume of the reagent to a solution dish (see page 11)
and then to take the desired quantity from this by
Fig. 7. Dropper pipet
(i actual size) means of a pipet. This procedure offers the advan-
tage that any necessary dilution of the reagent can be
made in the dish.
An adequate number of glass rods and pipets, in sufficient variety of
sizes, should always be kept in readiness. It is best to store pipets with
the constricted ends down. Porcelain beakers about 10 cm. high, contain-
ing a layer of cotton to prevent chipping of the glass, are excellent holders
for pipets and glass rods. They and their contents can be protected
against dust by keeping them under cellophane shields.
Pipets should never be laid on the work table lest they become dirty,
or their contents trickle out. If the same pipet is used several times for
'Compare F. L. Hahn, Mikrochemie, 10, 39 (1931).
parallel tests, it is best to lay it on a holder (Pig. 8), easily made from glass '
rod. As soon as pipets and glass rods have been used, they should be
plunged into beakers filled with water. This prevents interchanges. It
alsc facilitates cleaning, because solutions easily evaporate on the glass,
particularly in the capillaries, and may leave salt crusts.
Very small and uniform drops are obtained by means of platinum wire
loops. The size of the loop can be varied, and the corresponding volume of
liquid delivered can be determined fairly accurately by weighing the drops.
The loops, of different sizes, are made by bending; platinum wire of proper
thickness and soldering the junction. A handle is provided by inserting
the wire in the usual manner into a length of softened glass rod or tubing.
These wires are kept in Pyrex test tubes provided with corks or rubber
Fig. 8. Support for pipets, rods, etc. <i actual size)
stoppers; the labels should show the size of the drop delivered. Smooth
new platimim wire allows liquids to drip oif too readily^ and hence it is nec-
essary to roughen the wire by dipping it into platinic chloride solution and
then heating it to redness. This treatment should be repeated sevei-al
times.
A storage bottle for water and solutions, which do not deteriorate on
standing, and permitting easy delivery of drops, is shown in figure. 9. It
consists of a Pyrex flask into which a tube with a capillary end has been
fused. The constricted neck,, which is provided with a hole to admit air,
is closed with a small rubber bulb.
A simple and practical apparatus for delivering drops of water is
shown in Figure 10. It has a capacity of al)u| 30 ml. It is filled through
the funnel-shaped arm, while suction is being simultaneously applied
through the side arm by means of a water pump.
REACTIONS ON FILTER AND REAGENT PAPERS 17
Eigure 11 shows a small apparatus for delivering uniform drops of

mercury; it consists of a storage vessel and is closed by a glass cock whose
plug has a depression in place of the usual bore. The size of the drop is
determined by the size of the depression and, consequently, different sized
drops can be delivered by varying the depression. One advantage of this
"mercury dropper," which can also be used to deliver drops of other Hquids,
is the tight closing of the storage vessel and the unvarying size of the drops
discharged. The vessel is filled by taking out the cock and inserting a
short-stem funnel in the delivery tube. ^
Fig. 9, Fig. 10 Fig. 11

Fig. 9. Storage bottle for solutions, which permits controlled delivery of drops
{{ actual size)
Fig. lOÔevice for delivering drops of water (capacity: 30 ml.)
Fig. 11. Apparatus for delivering uniform drops of mercury (f actual size)
- Burets can also be used to deliver drops. In qualitative spot test

analysis and in spotcolorimetry^ it is well to use microburets with a capacity
of 0.5 to 1 ml. when sensitivity determinations are being made. Micro-
burets are indispensable in spot colorimetry.
4. Spot Reactions on Filter and Reagent Papers
Spot reactions are performed either by bringing together a drop of the
test solution and of the reagent on filter paper, or by placing one drop of
the test solution on filter paper impregnated with an' appropriate reagent.
Not all papers are suitable for these operations and the quality of the paper
' Compare F. Feigl, Laboratory Manual of Spot Tests. Academic Press, New
York, 1943, Chapter 9, "Spot Colorimetry."
must therefore be considered in every case. The purity of the paper is an

important factor, but the abnost complete absence 6f mineral constituents,
which may be considered primarily as contaminants, is frequently less
significant than the correct structure of the paper] that is, its thickness,
texture, permeability, and shape of the fibers, which determine the absorb-
ability.
The most frequent contaminant is ferric iron. This is detected easily
by placing a drop of acidified, saturated solution of potassium thiocyanate
on the paper; on drying, a red spot or ring of iron thiocyanate will be seen.
Practically all varieties of paper contain minute quantities of silica; also
traces of barium, calcium, magnesium, and, occasionally, phosphate.
Alkali metals, particularly potassium, are found only in qualitative papers.
They are absent in good quantitative papers which have been washed with
acids and water.'
Practically all filter papers contain small quantities of sterch. I t
should also be noted that the cellulose of filter paper is by no means an inert
material. It can be oxidized and can, therefore, act as a reducing agent.
The relatively small moisture content of properly stored filter paper does
not interfere with spot reactions, but it must be remembered that strong
caustic alkalis and concentrated acids rapidly swell the fibers or make
them brittle. Consequently, filter paper, as a rule, is suitable only for
working with solutions that are not extremely acid or basic. The purity,
and resistance toward chemicals, of most of the good papers on the market
are adequate for the majority of spot reactions. This is not true, however,
with respect to the requirement of suitable imbibition.*
It is particularly important that the paperisoak up liquids rapidly, but
on the other hand, the drop placed on the paper^ the so-called "spot" or
"fleck," should not spread too much. The typical reaction picture of a
spot test on filter paper always appears within the bounds, of the spot, and
consequently too much spreading interferes with the detection-of small
quantities of colored reaction products. Very thin filter paper; on which
capillary spreading results in spots that are too large, is therefore inherently
unsuited for spot reactions.
' The mineral constituents of filter paper come froin the inorganic 'materials
contained in the cellulose fibers and from the salts in the well water used in the manu-
facture of the paper. The ash content of the better grades x>{ qualitative paper, that
have not been washed with acids, average 10 V per sq. cm. "Ash-free" papers, which
have been extracted with hydrochloric and hydrofluoric .acids and tlên washed with
distilled water, have an ash content of 0.8 y per sq. cm. About half of this is silica.
* The differences in imbibition shown by various kindg*of filter paper are a result
of the nature of the raw materials (linen and cotton fibers), the method of beating,
and the drying of the finished moist paper. The shorter the fibers and the lower the
drying temperatures, the softer and more absorbent the paper.
REACnONB ON FILTER AND REAGENT PAPERS 19
The capillarity of the paper" is responsible for the fact that the sensi-
tivity of spot reactions is often greatly dependent on the type of paper
employed. Consequently, it is important to use types or varieties of paper
that are pre-eminently suited to the purpose, when minute quantities of
material are being sought (especially in the vicinity of the identification
limit), and when utilizing capillary separations in paper. Many spot reac-
tions have been worked out with the aid of the following Schleicher and
Schull papers. -Whatman papers give approximately the same results.
The following papers may be regarded as equivalent:
Schleiohw
and BohOU Whatnuu
No. 601 "Spot Paper" No. 120 Drop reaction paper, double
thicknesa
508 3MM First quality
589 42 or 542
Filter papers intended for spot reactions should be stored in vessels

with tight lids, in boxes, or in petri dishes. The type of paper should be
stated on the label of the container. The paper should be cut into strips (2
X 2 or 2 X 6 cm.); these make for economy and convenience. Beginners
are urged to carry out spot reactions with dilute solutions under constant
conditions on various types of filter paper to acquire a background of
experiences.
Filter paper should not be held in the hand, nor laid on the table or on
a paper, when drops are placed on it from pipets and so forth. Losses due
to run-off and imbibition by the support should be avoided. The proper
method is to lay the strip across an open porcelain crucible and, to place the
drops in the middle of the horizontal paper. An unhindered capillary
spreading follows and circular spots result. A number of comparison spots
can be produced if a longer strip and a larger crucible are used.
Spots are dried by aliowing the strips to remain on the crucible, or the
entire set-up is placed in a drying oven or subjected to a current of warm
air (see page 32). So far as possible, manipulations with filter papers
should be accomplished without contact with the fingers. If it is necessary
to dry the strip in a current of warm air, or to plunge it into an acid bath, or
to subject it to the action of a gas, one comer of the strip should be held with
a pair of forceps. Obviously, care must be taken not to bring the forceps
into contact with the moist spot, nor with acids, etc.
Spot reactions on paper do not always involve the union of a drop of
the test solution and one of the reagent. Sometimes filter paper is im-
' Compare F. Feigl, op. cit.. Chapter 3, "Surface and Capillary Effects in Spot
Reactions."
pregnated with the proper reagent and the dry reagfent paper is spotted with
a drop of the test solution. This procedure, which assumes, of course, the
availability of stable reagents, has the advantage that there is no mutual
dilution of the reagent and test solution. A betterilocaHzation and visibil-
ity of the reaction products at the place where the spot has formed is
achieved, as compared with the result of bringing two drops together.
A still better effect is obtained by impregnating filter paper with reagents
that are so slightly soluble in water that no bleeding occurs when a drop
of the test solution strikes the paper. Organic reagents that are only
slightly soluble in water, but that dissolve readily in alcohol or other
organic solvents, have this advantageous characteristic. Slightly soluble
compounds, that can be precipitated on paper and in its capillaries by
certain chemical reactions, can also be used in this way.
Spotting on reagent paper impregnated with an insoluble compound
involves a reaction of dissolved materials with an insoluble reagent. This
procedure cannot be used in macroanalysis because compact materials, in
general, react too slowly. If, however, these same solids are finely divided
by precipitation in the capillaries of paper and thus endowed with an exten-
sive reactive surface they will undergo chemical changes almost as rapidly
as soluble reagents.' The localization of characteristic reaction products,
with consequent better visibility and increase in the sensitivity of the
test, is not the sole advantage of using reagent papers impregnated with
insoluble compounds. In many cases, a highly desirable homogenizing and
stabilization can be accomplished by impregnating filter paper with in-
soluble compounds which then behave like soluble materials. For instance,
it is not possible to prepare a good stable alkali sulfide paper; it oxidizes to
sulfate too rapidly and the highly soluble alkali sulfide is washed away when
the paper is spotted with an aqueous solution. On the other hand, it is
easy to impregnate filter papers with slightly soluble sulfides (ZnS, CdS,
SbaSs, etc.). Such papers are stable; each has its maximum sulfide ion
concentration (controlled by its solubility product) and hence precipitates
only those metallic sulfides whose solubility products are sufficiently low.
Antimony sulfide paper precipitates only silver, copper, or mercury in the
presence of lead, cadmium, tin, iron, nickel, cobalt, and zinc. Another
striking example is the detection of iron by spotting on paper impregnated
with the difficultly soluble white zinc ferrocyanide. In this form the test
is far more sensitive than when it is made by uniting drops of a ferric solu-
tion and an alkali ferrocyanide, or by spotting on potassium ferrocyanide
paper. The latter also is less stable than zinc ferrocyanide paper. Conse-
quently, if possible, it is always better to impregnaiejilter paper with "insol-
uble" reagents than with soluble ones.
Compare F. Feigl, op. cit., Chapter 3, "Surface and Capillary Effects in Spot
Reactions." ''
REACTIONS ON FILTER AND REAGENT PAPERS 21
It is easy to impregnate filter paper with reagents that are soluble in

water or in organic solvents. The proper solutions are prepared in beakers
or dishes and the strips of filter paper are bathed in them. Care must be
taken that the strips do not cling to the sides of the container, that they do
not touch each other or stick together, because this may prevent a uniform
impregnation. The immersion should last for 20 to 30 minutes, the solu-
tion should be stirred quite frequently, or the vessel swirled, to produce
uniformity. The strips are taken from the bath, allowed to drain, pinned
to a cord (stretched horizontally) and allowed to dry in the air.
Instead of soaking the strips in the solution, reagents can be sprayed
onto filter paper. The atomizing tip shown in Figure 12 is excellent for this
purpose. The impregnating solution is placed in a wide test tube which is
then closed with the atomizing head. The
paper is held horizontally and the spray ex-
pelled by blowing into the apparatus. The
paper is sprayed first on one side and then
on the other.
Filter paper is impregnated by soaking it
in the appropriate solutions or by spraying
when it is desired to prepare a stock of reagent
papers. The following procedure' is recom-
mended for single experiments or when, for
speciahreasons, the spot produced by a drop
of a solution must be dried before adding a
drop of the other reactant. V-shaped strips of
filter paper are spotted on each side, taking care
t h a t the spots stay in the center of the strips
as nearly as possible. The strips then remain
Fig. 12. Atomizer head
for spraying reagents so stiff that they can be stood on the table and
(i actual size). allowed to dry. The impregnated strips are
cut at the crease before they are used.
Homogeneous impregnation can only be accomplished through grad-
ual uniform drying on all sides. If paper is soaked with a salt solution and
then dried by exposing it to a stream of heated air from the drying appar-
atus, the rapid evaporation and the subsequent capillary diffusion always
leads to an accumulation on the side of the paper turned toward the blast.
This effect can be detected immediately in the case of colored reagents, be-
cause the color is far less intense on the side of the paper turned away from
the blast. The localization of a reagent on one side of the paper is an
advantage, particularly for water-soluble reagents, because it is desirable to
have the largest possible quantity of reagent available at the place where
' F . L. H a h n , Mikrochemie, 11, 34 (1931).
the spot is made, so that there will be a rapid and complete reaction with the
materials in the test drop.
If strips of filter paper are dried in a blast?: of hot air, they should
either be held on both ends with forceps, or laid on a ribbed porcelain plate
at such distance from the hot air apparatus that the current of warm air
presses the paper against the porcelain plate. The completion of the drying
is determined easily because the moist paper, which adhered to the. plate,
rises and flutters in the current of air.
There are no general procedures for impregnating filter paper with
compounds produced by precipitation on and in the paper. As a rule, the
strips are soaked with the solution of one of the reactants, dried, and then
immersed in the solution of the appropriate precipitant. The excess rea-
gents are then removed by washing, and the paper dried. If this method is
used the order in which the solutions are applied, as well as their concentra-
tions, makes a difference. The best conditions must always be determined
by trial. It is a general rule that filter paper should be plunged quickly
and uniformly into the particular reagent solution to avoid the production
of zones (layers) of different concentrations. When highly impregnated
reagent papers are being prepared, the'precipitation of a difficultly soluble
reaction product must never be accomplished by a single treatment with
concentrated solutions. The moistening and precipitation must be carried
out separately with dilute solutions, and the reagent paper should be dried
between the successive individual precipitations. If this procedure is
not followed, a film rather than a homogeneous impregnation will result,
and the reagent will fall of! the paper, after it is either washed or dried.
The excess liquid is removed after each phase of the impregnation by
passing the paper through a small wringer with the pressure between the
rolls kept constant. To insure complete uniformity, the paper must
be fed into the wringer at a uniform rate. The paper is best washed by
spreading it on an inclined glass or porcelain plate. J'he stream of dis-
tilled water used for washing is distributed by means of a glass tube pro-
vided with a number of openings. In case the product precipitated in the
paper is not particularly insoluble, it is best to wash slightly with water and
then with dilute alcohol. Overheating must be avoided when drying
the paper; as a rule 60 to 80 C. suffices. Sometimes it is preferable
to use a reagent if possible in the gaseous form (hydrogen sulfide for pre-
cipitating sulfides or ammonia for precipitating oxides) rather than in
solution; there is then no danger of washing away the precipitate. For
the same reason it is often advantageous first to form an adherent compound
which cannot be washed off the paper and then-xarry but the reaction
producing the desired reagent. For instance, a good lead sulfide paper is
produced^not by soaking the paper in a lead salt solution followed by
treatment with hydrogen sulfide water or gaa^but rather by forming
BBACrnONS IN POKCBLAIN AND QhASS VESSELS 23
zinc sulfide on the paper and converting this into lead sulfide by bathing
in a solution of a lead salt.
I t must be remembered that iew reagent papere are as stable as the
familiar indicator papers, which owe their permanence to an irreversible
adsorption of dyes on the paper. In general, the impregnation with amor-
phous compounds is more permanent than with crystalline materials. The
latter recrystallize, their surfaces are diminished, they become detached
from the capillaries of the paper and the original homogeneity and high
reaction rate are lost. The decreased activity of old reagent papers is due
therefore, in general, not to chemical but to physical (surface) changes.
These occur to quite different degrees with different compounds. In most
cases, careful storage in closed containers and protection from light will
insure adequate stability for several weeks.
5. Spot Reactions in Porcelain and Glass Vessels

In the performance of spot reactions, and particularly in the course of
preliminary operations, it is often necessary to use glass, porcelain, or metal
apparatus. These are required to
carry out, on a small scale, certain
operations, such as treatment with
concentrated acids, caustic alkalis,
ignitions, fusions, etc.
The use of nonporous materials
is especially imperative when one (or
. , , ^ .,, , more) of the reactants is so stronglv
Fig. 13. Spot plate with depressions ,. , ^ j "
of different capacities (i actual size) alkalme or acid that a rapid swelling
or weakening of the fibers of filter
paper is likely. In such cases, it is convenient to use spot plates "(FJg- 13).
These may be either white or black and made of glazed porcelain or
resistant glass. They have 6 to 12 similar depressions, each with a
capacity of 0.1 to 1 ml. An adequate supply of spot plates with dif-
ferent sized depressions should be kept on hand. The white porcelain
background makes it possible to detect very small differences in color
intensity or slight changes in color. This is particularly true if parallel
blank tests with drops of water are made in adjacent depressions. Com-
parison tests with drops of solutions of known content can also be car-
ried out in adjoining depressions. Black spot plates are an advantage if
light colored (or colorless) precipitates or turbidities are formed. Glass
spot plates are excellent.* They can be placed over glossy paper of various
colors; thus the observation of minute quantities of precipitate or soluble
colored reaction products is often made easier.
Compare H. Schafer, Mikrochim. Acta, 1, 144 (1937).
24 I . WORKING METHODS I N SPOT T E S T ANALYSIS
The drops of test solution and reagent brought together on a spot

plate must always be well mixed. This is done witli a glass stirrer (Fig. 14)
or, still better, by blowing onto the solution through a fine pipet. During
the blowing, the end of the pipet is held about 0.5 cm. away from the
surface of the liquid and moved over it.
Even a slight coating of grease in the depression of the spot plate will
prevent drops from coalescing. In delicate tests with microdrops it is
therefore imperative to clean the depressions by wiping them with cotton
moistened with a mixture of alcohol and ether.
Precipitates that are formed by the addition of
reagents dissolved in alcohol or ether will creep up
the walls of the depression as the organic solvent
evaporates. The same is true for the. dissolved
reagent and, in case it is colored, blank tests are
necessary without exception.
Porcelain is attacked on long contact with alka-
0.3 cm 10 cm. line solutions and the smooth surface becomes rough.
bore-
Careless cleansing may also damage the porcelain.
These evils may be avoided if it is made a matter of
routine not to allow the spot plates to stand after use
nor to permit solutions to dry up in the depressions.
The plates should be placed, as soon as possible, in
glass dishes filled with rinse water. This prevents
troublesome adherence of precipitates and incrusta-
4 cm. tions and, as a rule, the plates can be cleaned com-
pletely by merely swabbing them with a cloth. In
case the porcelain still retains the precipitate, a suit-
able acidic or basic solvent is used. This should
Fig. 14. Stirrer 'glass)
(i actual size) be as dilute as possible. Spot plates should not be
cleaned with the ordinary chromic acid solution; it
attacks them badly after some time.
Some spot reactions can be carried out on paper just as well as on spot
plates and with equal sensitivity. Often, however, a typical reaction prod-
uct can be detected more easily, and in smaller amounts, on one, rather than
the other of these backgrounds. Spot tests on paper are more sensitive
and consequently are preferable when adsorption or other capillary action
of the paper, that lead to an accumulation and localization of colored reac-
tion products, are involved. On the other hand^ weakly colored com-
pounds, particularly yellow ones, or slight color differences produced by
colored reagents, generally can be distinguished more readily on spot plates.
The beginner is urged to try tests on a spot plate even though the directions
recommend the use of paper, and vice versa. ^ He will thus obtain his own
R E A C T I O N S I N P O R C E L A I N A N D GLASS VESSELS 25
opinion of the characteristic reaction picture and the range of application

of the two most iiiiportant methods of conducting spot reaction.
If a comparison with blank tests is not necessary, spot reactions can be
made on small watch glasses, in microcrucibles (Fig. 15), in the bowl of a
small porcelain spoon, or on a grooved
pipcc! of magnesia. Crucible covers or
watch glasses made of quartz or quartz
glass are sometimes suitable. A drop
of solution can be easily evaporated or
even ignited on them as a preliminary
to the actual spot reaction.
Microcrucibles are excellent if
solids must be brought into solution by Fig. 15. Microcrucibles (actual size)
digestion with acids or alkalis prepara-
tory to the spot reaction, or when a small volume of liquid is to be concen-
trated or evaporated. The test tubes sho-wn in Figure 10 serve the same
purpose." By properly inclining them it is possible to dissolve small quanti-
ties of alloys and similar materials, make the evaporation, taJke up the
"
r^ Ji
]J u
Fig. 16 Fig. 17
LJ Fig. 18
Fig. 16. Special test tube for solution of sampleand delivery of drops of the resulting
solution (actual size)
Fig. 17. Micro test tubes (actual size)
Fig. 18. Emich centrifuge tube (J actual size)
residue in water, and deliver drops of the resultant solution thrpugh the
side arm onto filter paper or a spot plate.
Spot reactions that produce tiny lirecipitates or faint turbidities, or
those requiring subsequent extraction With organic solvents to concentrate
"Described by F. I'avelka, Mikrochemie, 4, 200 (1926).
26 I. WORKING MSTHODS IN SPOT TEST ANALYSIS
the reaction product are conveniently carried out in micro test tubes,
either open or provided with glass stoppers (Fig. 17). Solutions can be
heated or boiled in these without serious loss due|to evaporation or spatter-
ing. Such micro test tubes should be made of resistant glass, kept in suit-
able racks, and cleaned with fine brushes. Turbidities or colors can easily
be seen in these test tubes when viewed against a white or black back-
ground. Rectangles (6 X 12 cm.) of black or white glazed paper or luster-
less cloth pasted on thick cardboard are excellent for this purpose. Dull
aluminum foil sometimes can be used to advantage.
If small quantities of precipitates are to be made visible, it is well to
make the spot reaction in the glass tubes'" shown in Figure 18, and to
centrifuge after allowing the reaction mixture to stand for a while. The
precipitate collects in the capillary end of the tube, and can be detected with
a magnifying glass if viewed against a suitable background.
Fine platinum wires are used to stir solutions in crucibles, micro test
tubes, or centrifuge tubes. The glass stirrers, whose proper dimensions are
shown in Figure 14, are excellent.
The methods recommended for cleianing spot plates should also be
used for crucibles, micro test tubes, aiid the like. They should be put into
water immediately after use. Care must be taken that all glass apparatus
is thoroughly dry and free from dust and grease.
6. EvaporationDryingIgnitionFusion
Concentration of solutions, that is, diminution in volume by removal
of most of the water, evaporation of solutions to dryness, or removal of
volatile acids by warming, are carried out chiefly in porcelain or platinum
microcrucibles. The apparatus shown in Figure 19 is very convenient for
all these operations. It consists of an aluminum block provided with
wells for a thermometer (T) and for two or three microcrucibles. A small
glass bell with a stop cock is fitted tightly to the block. With this appara-
tus it is also possible to remove water and volatile compounds under reduced
pressure and at temperatures below the normal boiling points. If the bell
is placed on a well-fitting ground glass plate, the assembly can be used as a
microdesiccator."
Small volumes of liquid can be concentrated,or taken to dryness in
centrifuge tubes at water bath temperature by blowing in dry filtered air.
This is sent through a glass capillary and impinges on the surface of the

"Compare F. Emich, Microchemical Lahoratory Manual. Translated by F.
Schneider, Wiley, New York, 1932, p. 12. f
" An electrically heated-aluminum block for holding and heating microoruciblee
nd test tubes within a constant temperature range wsis described by F. Pavelka, ,
Mikrochemie, 28, 247 (1937).
BVAPORA.TION^DBTINOIGNITIONFUSION 27
liquid to be evaporated. Details of the apparatus for this operation are

shown in Figure 20.
I 'Rubbar stoppef
X=l^Clamp
(; i^^Purified cotton
' '^ wool
Fig. 10. Aliuuinum block for concentrs- Fig. 20. Set-up for concentrating a BOIU-
ting solutions, etc. (i actual sise) tion in a centrifuge tube (i actual size)
Wire triangle
Microbeaker
or crucible
Nickel crucible
Fig. 21. Air bsth constructed from nickel crucible (} actual size)
If water bath temperatures are not sufficient to remove volatile com-

pounds, air or sand baths can be employed to furnish the higher temperature
required. A simple air bath is shown in Figure 21. It consists of.a nickel
crucible with a copper wire triangle suspended in it through lateral slits.
The triangle supports a microcrucible or microbeaker. The nickel crucible
28 I, WORKING METHODS IN SPOT TEST ANALYSIS
can be heated directly by a burner or placed on a hot plate. The tempera-

ture can be determined by suspending a thermometer in the crucible. If
filled with fine sand, the crucible can be used as a sand bath. In this case
the vessel containing the liquid to be evaporated is placed on or in the sand.
The apparatus should be set up in a hood if clouds of acid vapors or am-
monium salts are expected. An alternative arrangement is to place a glass
funnel (see Fig. 22) over the crucible and draw the fumes away with a good
filter pump. The heating bath can then be set up on the lahoiatoey bench.
ing fumes away (i actual size)
7-8 cm.
Fig. 2.3. Grooved magnesia for ignitions (actual size)
A silica watch glass can be used when evaporating small volumes of

liquid and igniting the dry residue. This has the advantage, that the
evaporation or ignition residue can be inspected directly, particularly when
the watch glass is held against black glazed paper.
Products can be ignited or ashed in porcelain or platinum crucibles, on
silica watch glasses, or on a piece of grooved magnesia (Fig. ^3). The direct
flame of a microburner is used. Ashing and ignition are advantageously
carried put in electrically heated furnaces provided with temperature indi-
cators. The action of the gases from the burner and losses through spatter-
ing and decrepitation are thus avoided.
ACTION AND LIBERATION OP GASES 29
The examiixation of silicates and other materials, that are not soluble in
acids, often necessitates fusion with a disintegrating flux. Oxidizing fusions
are sometimes required. Small quantities of the sample can be mixed with
sodium-potassium carbonate, sodium bisulfate, or alkali peroxide and then
heated in the loop of a platinum wire. A small platinum spoon, capacity
about 0.5 to 1 ml., that has its handle fused into a glass tube (see Fig. 24), is
highly recommended for these fusions. SiUcates can also be decomposed
in a platinum spoon by fuming with hydrofluoric and sulfuric acids; volatile
silicon tetrafluoride is formed. The residue can be readily examined or
subjected to further treatment. A magnesia groove or rod sometimes
suffices for the decomposition of ^certain samples.
<
Fig. 24. Platinum spoon with handle fused into a glass tube (actual size)
7. Action and Liberation of Gases (Vapors)
Two kinds of manipulations with gases or vapors are usra in spot test
analysis. Gases (vapors) are employed as auxiliary reagents for precipita-
tion, alkalization, or oxidation of solutions. On
the other hand, the liberation of small quantities
of gases (vapors) as characteristic products which
can be identified by subsequent reactions is the
basis of certain tests. The apparatus required for
handling gases (vapors) is determined by the
purpose at hand.
Spot reactions on paper involving the action
of gases or vapors (HS, NHs, halogens, steam) can
be conducted by leading the gas directly from
the generator, or by placing a strip of filter paper
over the neck of an open flask filled with hydrogen
sulfide water, ammonium hydroxide, etc. The
steamer (Fig. 25) can be used is a gas generator,
if the flask is filled with hydrogen sulfide water, Pig. 25. Apparatus for
bromine water, or ammonia water, warmed, and treating paper with
the material to be gassed placed on the side g/ases or vapors (actual
size)
arm.
The separation of certain groups of metals by treating the acid or am-
moniacal solution with gaseous hydrogen sulfide is a common step in chemi-
cal analyses. In spot test analysis, this precipitation can be accomplished
by saturating a small volume of the solution with hydrogen sulfide in a
microcentrifuge tube. Thp hydrogen sulfide is admitted through a fine
capillary to prevent loss by spattering. The delivery tube is made by draw-
ing out 6 mm. glass tubing to form a capillary of 1 to 2 mm. bore and 10 to
20 cm. long. A plug of bleached cotton wool is inserlJed in the wide part of
the tubing; then the capillary end is heated in a microbumer and drawn
down to a finer tube of 0.3 to 0.5 mm. bore and about 10 cm. long. Figure
26 shows the complete arrangement. The fine capillary delivers a stream
of tiny bubbles; consequently, the solution does not spatter from the
microcentrifuge tube. The gas must be started through the tube before
plunging the end of the capillary into the solution. Otherwise, the solution
will rise in the capillary and, when the hydrogen sul-
fide is admitted, a precipitate will form in the
capillary and clop it. The end of the sulfide pre-
cipitation can be easily detected by an increase in.
-Rubber stopper' the size of the rising bubbles. At room temperature,-
this point is usually reached in about 3 minutes.
X3
^ Clamp An adequate supply of various types of special
apparatus of small capacity must be kept on hand.
- Purified cotton
wool These are required for the hberation of volatile com-
pounds after decomposing small quantities of solid
materials or solutions with acids or alkalis. An
apparatus" designed for the detection of carbonate,
sulfide, etc., is shown in Figure 27. It consists of a
micro test tube of about 1 ml. capacity and can be
closed with a small ground glass stopper fused to a
glass knob. The gas is evolved in the tube, aided if
necessary by gentle wanning, and is absorbed by the
reagent. Since the apparatus is closed, no gas es-
v
Fig. 26. Set-up for pre-
capes, and if enough time is allowed it is absorbed
quantitatively. A drop of water may replace the
reagent on the knob. In this case the^gas is dissolved,
cipitating sulfides by and the drop then may be washed onto a spot plate
leading in hydrogen or into a microcrucible and treated there with the
sulfide (i actual size) reagent. The apparatus shown in Figure 28 is some-
times preferable, particularly when minute quantities of gas are involved.
The tube is closed ,by a rubber stopper and the glass tube, blown into
a small bulb at the lower end, may be raised or lowered at will. A change
of color, or the reaction products, may be made more distinct by filling
the bulb with powdered gypsum or magnesia." In some cases, such as
the test for ammonia, it may be desirable to suspend a small'strip of reagent
paper from a glass hook fused to the stopper (Fig. 29). The apparatus
shown in Figure 30 is used when a particular gas is to be identified in the
" F. Feigl and P. Kmmholz, Mikrochtmie {Pregl FeaUchrift), 1M9, p. 83.
" According to a suggestion by H. Kappelmacher.
ACTION AND UBEBATION OF GASES 31
Fig. 27 Fig. 28 Fig. 29

Fig. 27. Apparatus for detecting COi,. H^, el. (actual siie)
Fig. 28. Modifications of apparatus shown in Figure 27, especially suitable for detection'' ^
of minute quantities of gas (actual size) /
Fig. 29. Apparatus for detection of gases, with provisioti for suspending it reagent
paper (actual size) / .
/=Q\
Fig. 30
0
Fig. 32
Fig. 30. Apparatus for detecting a gas in the presence of indifferent gases (actual size)
Fig. 31. Apparatus for detecting a gas that forms a colored product with the reagent
solution (actual size)
Fig. 32. Apparatus for detecting a gas whose release requires high temperatures
(actual size)
presence of other gases. In this arrangement the stopper of the micro test
tube is a small glass funnel, and the impregnated jSlter paper is laid across
it to absorb the gas. The impregnated filter paper permits the passage of
the indifferent gases and retains only the gas to be detected. The latter
forms a nonvolatile compound which can be identified by a subsequent
spot test. Another useful apparatus (Fig. 31) consists of a micro test tube
containing a loosely fitting glass tube narrowed at both ends. The lower
end isfilledto a height of about 1 mm. with an appropriate reagent solution.
If the gas evolved forms a colored product with the reagent, it can be
seen easily in the capillary.
A simple hard glass tube, supported in a circular hole in an asbestos
plate (Fig. 32), can be used if high temperature or ignition is required to free
Fig. 33. Apparatus for distilling small voliunes of a liquid (actual size)
the gas. The open end of the tube is covered with a small piece of reagent
paper kept in place by a glass cap.
Microdistillation is sometimes required; the chromyl chloride test for
choride is an example. Very small quantities of material can be distilled
in the apparatus shown in Figure 33. A microcrucible or microcentrifuge
tube can be used as the receiver.
8. Heating of Solutions
There are various ways of heating solutions to hasten chemical re-
actions in spo test analysis.
Filter paper, on which drops of liquid have been placed, can be warmed
by holding it over an electric hot plate or over an asbestos plate heated by
a burner. A blast of hot air is still better. More or less^ evaporation can
be expected because of the great surface exposed J)y the liquid when taken
up in the capillaries of the paper. When thespots are subjected to a cur-
rent of warm air, it must be remembered that the material will be localized
on that side of the paper nearest the heat.
HEATING OP SOLUTIONS 33
Sometimes it is advantageous to heat spots on paper with avoidance of

evaporation. This can be done by means of steam. A suitable apparatus
is shown in Figure 25. Its operation is self-evident. The filter paper is laid
on the side arm support, kept in place with the concave side of a small
watch glass, and exposed to the action of the issuing steam.
Steam jacket
for nnicrobeaker-
Fig. 34. Support for holding beakers, etc., on a water bath (i actual size)
If small volumes of liquid are toê heated with as little rapid evapor-
ation as possible, or if a material is to be dissolved by warming with acids,
alkalis, etc., small vessels of glass, porcelain, or platinum are necessary.
Microcrucibles are placed on a water bath or on an asbestos plate heated by
a microbumer. The liquid in the crucible is stirred with a microstirrer to
avoid spattering and super heating.
A support designed to hold microcruci-
bles, microbeakers, or microcentrifuge tubes on
the water bath is shown in Figure 34. It con-
sists of a hard glass tube constricted at the bot-
tomand held in a metal ring. About 3 cm.
from the bottom of the tube is a glass support pjg 35 ^j^^ gu^^g f^^ folding
for the crucible, etc., whicli can thus be test tubes, etc. (i actual size)
warmed by the current of steam.
The simple arrangement shown in Figure 35 is excellent for heating
liquids in micro test tubes. It is made by twisting together two thin alum-
inum wires. The flared ends of the test tubes are easily held in place in
these slings. If the wire stand, together with the test tubes, is suspended
over a beaker filled with water it is easy to heat them and to carry out
duplicate or parallel tests.
Whenever possible, it is best not to boil liquids; instead, solutions
should be heated at water bath temperatures, in order to avoid losses by
spattering.
34 I. WOBKING METHODS IN SPOT TEST ANALYSIS
9. Separation of Solid and Liquid Phases

The detection of certain elements and groups df atoms can often be ac-
complished directly in the presence of other materials by calling on every
possible means to increase the sensitivity and positiveness of chemical tests.
The usual operations of separating by precipitation and filtration, which
are essential in the solution of analogous problems in the classical methods
of qualitative inorganic and organic analysis, sometimes cannot be used.
In many cases, however, the surest procedure is still to make a division into
the familiar main groups of the systematic scheme of analysis and to follow
this partial separation by spot reactions to identify the individual members
of the groups. This is particularly advisable in the analyses of imknown
inorganic mixtures, and in the investigation of natural or artificial products.
Likewise, when the analyst is asked to determine the presence or absence
of a given material in a specimen, it is occasionally best, after the sample
has been dissolved, to .make a preliminary precipitation. The identity
tests can then be carried out by means of characteristic spot reactions on
the precipitate or filtrate. Furthermore, since the isolation and rendering
visible of minute quantities of precipitated materials is often of great
moment in spot reactions, it follows, from all the foregoing, that the separa-
tion of solid and Uquid phases is a very important operation in spot test
analysis, where it often has to be accomplished on a microscale.
When spot reactions are made on paper, either by bringing together
two drops or by spotting a reagent paper with a drop of the test solution,
any insoluble compoimds formed are precipitated directly in the paper, and
the unchanged constituents of the solutions undergo capillary diffusion.
The latter will then be present throughout the whole spotted area, par-
ticularly in the circular zone surrounding the precipitate. Precipitation
and filtration are thus accomplished in the surface of the paper. Additional
spot tests can be made then on the spotted area, either on the product that
has precipitated there, or on the circular zone surrounding the precipitate.
Spot reactions on paper not only accomplish a direct precipitation and
filtration but also make it possible to purify precipitates by washing. This
can be done by placing drops of water, or of a suitable wash liquid, on the
center of the spotf the concentric ring around the precipitate is thus ex-
tended by capillary diffusion. If the filtrate is of no importance for
additional tests, it is better to bathe the spotted paper in an appropriate
wash liquid, which can be renewed if necessary. When it is desired to wash
a precipitate by repeated treatment with drops of water, edch drop should
be completely absorbed before the next drop is-added.
It is generally better to dry the spots before washing them. This
fixes the precipitate more firmly in the capillaries of the paper, and there is
lees likelihood of its being washed away. Spots are dried best aud most
SEPARATION OF SOLID AND LIQUID PHASES 35
quickly by a blast of warm air. This localizes the material that has re-
mained in solution and undergone capillary diffusion; the accumulation will
be greatest on the side of the paper toward the blast. This is an advantage
if further tests by later spot-reactions we to be made on the filtrate that has
been separated by capillary action.
The testing for dissolved materials that have diffused out of a patch of
precipitate should be made by spotting laterally. It is best to place a drop
of the appropriate reagent on the dry paper beyond the primary spot. The
reagent will spread uniformly from the point of application, and character-
istic reaction pictures will be produced at the junction of the two spots. If
colored reagents are used in this manner, even slight changes in color are
quite apparent.
Solids, or components of mixtures, can often be tested directly to deter-
mine their solubility in dilute acids, alkalis and the like, by spot reactions
on paper. A small quantity of the pulverized sample is heaped on a strip
of filter paper and spotted with 1 or 2 drops of the solvent. The action is
hastened by wanning in a current of heated air. Complete solution is
obviously established if the sample disappears. Partial solution can be
detected by applying suitable reagents near the site of the original reaction.
Direct spotting of solids on paper is not limited to the determiaation of
solubility, but can be used also if soluble colored reaction products are
formed by the action of reagents and then diffused away through the capil-
laries of the paper. Frequently, characteristic spot reactions can be made
directly on white paper through this type of filtration.
The precipitation and filtration following spot reactions on paper may
not be applied to all cases, because strongly acid or alkaline solutions cannot
be used, nor is it feasible to subject reaction mixtures to prolonged and
intensive heating. Neither-is it possible, as a rule, to detect and isolate
small quantities of colorless reaction products on paper. Consequently,
other means must be employed to separate solid and liquid phases. The
choice of the method is determined by the particular needs of the moment.
If considerable quantities of liquid are involved, and if the solid or pre-
cipitate is of no further interest, a portion of the liquid can be withdrawn
by a pipet for examination. The fine constricted end of the pipet is
closed with a wad of cotton drawn out to a point. If the suspension is
sucked into the pipet, the liquid that arrives in the tube will be free of
precipitate. The pipet will deliver a perfectly clear liquid if the tip is
carefully washed after removing the cotton.
A useful filter pipet" is shown in Figure 36. It is constructed of glass
tubing (6 mm. diame'ter). A rubber bulb is attached to the short arm A;
arm B is ground flat; arm C is drawn out to afinecapillary. A short piece
" E. R. Caley, Ini. Enj. Chem., Anal. Ed., 2, ft (1930).
of rubber tubing D is fitted over the top of B. i A disk of filter paper of

the same diameter as the outside diameter of the tube is cut from a sheet
of filter paper by a sharp cork borer or hand punch, and is placed on the
flat ground surface of B. Tiibe F is placed on the paper, which is held
in position by sliding the rubber tubing over it just far enough to hold it
when F is removed. The filter pipet can be used either by placing a drop
of the solution on the filter disk or by immersing B into the crucible, test
tube, or other container holding the liquid to be filtered. The bulb is
squeezed between the thumb and middle finger and the dropper point is
closed with the index finger; the solution is thus allowed to pass through
the paper when the bulb is released. The pipet is inverted over the spot
plate, etc., in an inclined position with the bulb uppermost when it is de-
sired to discharge drops of the filtered liquid. The hquid in the tip is
Fig. 36. Filtering pipet (actual size)
forced onto the spot plate, etc., by manipulating the bulb. The precipitate
on the pa-per can be removed for any further treatment by simply sliding
the rubber tubing D over the arm B.
Another method of filtration employs an Emich filter stick, fitted into
a heavy-wall suction tube by means of a rubber stopper. The suction tube
contains a micro test tube to receive the filtrate (Fig. 37). The filter stick
contains a small asbestos pad.
Often filtration is not the best method of separating solid and liquid
phases. Sedimentation of insoluble materials by centrifuging is sometimes
preferable. In addition to greater speed, this procedure has the following
advantages: no retention of the mother liquor by the filtering medium;the
precipitate, freed from most of its moisture, is compressed into a small
volume; the structure of the solid phase (crystalline .or amorphous) has no
effect on the sharp separation of the phases. The receptacles for centri-
fuging (centrifuge tubes) can be so chosen for size that the isolation of
8EPABATI0N OF SOLID .AND LIQUID PHASES 37
minute quantities of precipitate or of small volumes of filtrate can be

effectively accomplished.
A microcentrifuge tube is shown in Figure 38, together with a glass
support. This arrangement is useful for heating or evaporating on the
water bath. A variety of centrifuge tubes with capacities of from 0.5 to
3 ml. should be available.
Centrifuge tubes are conveniently supported on a rack consisting of a
wooden block provided with 6 to 12 holes, evenly spaced and | of an inch
in diameter, inch deep. Microcentrifuges are now on the market. Those
that are driven electrically (1500 to 3000 r.p.m.) are preferable to hand
Fig. 37. Set-up for microfiltration, using Fig. 38. Microcentrifuge tube and sup-
filter stick and suction (actual size) port (I actual size)
operated centrifuges. The centrifuge should be provided with a metal

shield and cover to protect the operator. Dangerous vibration of the
instrument is avoided by always loading the carrier equally. This is done
by counter balancing the tube containing the sample by an opposing tube
containing an equal weight of water or an approximately equal volume of
the liquid being centrifuged. The cover of the centrifuge must not be
lifted until the rotor has come to rest.
Precipitations are usually made in conical microcentrifuge tubes.
The precipitate collects at the bottom of the tube when the suspension is
centrifuged. A dropper pipet can be used to remove the supernatant
liquid from centrifuge tubes of about 2 ml. capacity. The liquid cannot be
. poured off because a large proportion will always remain in the tube. A
I. WORKING METHODS IN SPOT TEST ANALYSIS
dropper pipet suitable for this operation can be Laade easily from glasa
tubing; the dimensions are given in Figure 7. A transfer capillary pipet
is convenient for removing the mother liquid or cehtrifugate, particularly
from smaller tubes (0.5 to 2 ml. capacity). The pipet is made of glass tub-
ing (internal diameter about 2 mm.) which can be drawn from wider tubing.
The length is 20 to 25 cm. One end is drawn to a tip with a fine opening
by heating in a microflame. The correct method of transferring the liquid
to the capillary pipet is-made evident by Figure 39. The centrifuge tube is
held in the left hand, and the pipet slowly pushed toward the precipitate
Fig. 39. Removing supernatant liquid from a centrifuge tube by suction

a actual size)
so that the point of the capillary always remains just below the surface of
the liquid. This is continued until almost the entire solution is in the
pipet and the tip is about 1 mm. above
the precipitate. The liquid is drained from
the pipet into a clean, dry centrifuge tube.
Precipitates are washed by adding the
wash solution directly to the precipitate in
the centrifuge tube and stirring thoroughly
either with a platinum wire or by means of
a stirrer (Fig. 14). This is readily constructed
from a glass rod. The suspension is then
centrifuged and the clarified liquid removed
with the aid of a pipet as just described.
This operation may have to be repeated two
or three times to insure complete washing.
Centrifuge tubes are cleaned with a
Fig. 40. Device for withdrawing feather or a small test tube brush. They
liquid from a centrifuge tube
by suction (i actual size) arefilledthen with distilled water and emptied
by suction using the device shown in Fig. 40.
After the suction has been started and the liquid drawn out, the tube is
filled several times with distilled water without removing the suction device
between emptyings. Dropper pipets are cleaned by repeated fillings with
water; the bulb and tube arefinallyseparated and both rinsed with distilled
water from a wash bottle. Transfer capillary pipets are cleaned by blowing
a stream of water from a wash bottle through,them.
Small quantities of a precipitate can be collected by centrifuging in a
microcentrifuge tube, and thus made more visible and accessible to further
treatment. This method of separating solid and liquid phases can there-
fore be substituted for filtration in many instîces. K the problem ia merely
OTHER SPECIAL AIDS 39
the detection of the fomuition of minimal quantities of precipitate, that can

produce not more than a slight opalescence if the precipitate i^ colorless, it
is frequently necessary to centrifuge for considerable periods to accomplish
the separation of the colloidally dispersed solid phase. In such instances,
a separation can often be accomplished quickly by shaking the suspension
with an organic liquid that is not^miscible with water. The surface tension
is altered and the fine particles of the soUd aggregate and collect as a thin
film in the water-oiâiiic interface. This method is recommended par-
ticularly when it is necessary to detect the formation of a precipitate in
a considerable volimae of solution after a reagent has been added, or in a
reagent solution following the addition of one drop of a test solution. The
a|;gregation and localization by extraction or shaking out succeeds best
in neutral and acid solutions. This treatment with an organic solvent is
conveniently done in macro or micro test tubes provided with glass stoppers.
10. Other Special Aids

The actual detection reactions used'in spot tests are carried out as a
rule with drops of solutions. If tê specimen is solid, the solvent should be
chosen judiciously and the slightest possible excess used. This holds par-
ticularly for solvents which function by chemical 'action. Sometimes
metals, alloys, and ores may be put into solution without resorting to a
chemical solvent. An anodic solution is used instead and the anodically
dissolved metal is allowed to react directly on a suitable reagent paper.
This is known as the electrographic method. The principle of this proce-
dure is that the test substance is used as anode with aluminum foil as
cathode; filter paper moistened with the reagent is i)laced between these
poles. The reagent paper is not in direct contact with the aluminum foil
but is placed on a second filter paper moistened with potassium chloride
or sulfate. The electrolyte facihtates the passage of the current. When
the circuit is closed, the metal dissolves at the anode, and the solution reacts
directly with the reagent in the paper, where it forms a typical colored
stain. A simple apparatus for such electrographic tests is illustrated in
Figure 45.
Alloys or minerals showing no appreciable resistance to the passage of
the current may be tested with the same apparatus for anodically deposited
metals. Sections of metallic specimens may be tested for the location of
constituents without damaging the sample, since the electrical method
has the advantage that no acid reagents are required in the anodic solution
. of metals.
In addition to the mechanical aids already described for spot reactions,
several other special devices and appliances for the preliminary operations
should be available in the laboratoiy devoted to spot analysis. The most
important of these are:
Microcentrifuge: For collecting precipitates in microcentrifuge tubes

and capillaries.
Distillation ajrparatus: The ordinary macrodistiUation apparatus is
usually suitable when testing residues in organic solutions. Microdis-
tillation apparatus should be used for working up small volumes of liquids.
Extraction apparatus: A inicroextraction apparatus should be pro-
dded, in addition to the usual Soxhlet apparatus, for the extraction of
solid materials with organic solvents.
Sublimation apparatus: A microsublimation apparatus and tem-
perature indicator is suitable for testing the purity of organic preparations.
Melting point apparatus: For testing the purity (melting point) of
organic preparations.
Hot air apparatus: For drying impregnated filter paper and for heating
flecks on one side of the paper.
Electric rnuffle [ignition) furnacewitli\
temperature regulator: I For drying and ignition of
Electric hot plates: (precipitates and specimens. -
Portable drying oven: , ]
Analytical quartz lamp: For detecting fluorescent reaction products;
observation of photochemical reactions; comparison of samples.
Microscope: For identification of crystalline precipitates.
Magnifying glasses: For closer examination of spot tests on paper.
MicTobalance: For weighing quantities less than 1 mg.
Rough balance: For approximate weighing of preparation, etc.,
before using the analytical macrobalance.
Small vmnger with rubber rolls: For squeezing soaked filter paper when
preparing reagent papers.
pH meter.
Portable electrolysis apparatus: For electrolytic deposition of metals.
Colorimeter: For colorimetric determination of dissolved colored
materials.
Stop watch.
Microbumer.
Microburets.
Alcohol lamp.
Equipment for working and blowing glass.
Heatable spot piate."
Automatic pipet rinser.^' ^
Apparatus for rapid drying.^'' ^
Laboratory apparatus for redistillation ofwater.^^
" E. FrSnkel, Mikrochemie, 13, 179 (1932).
" A. P. Harrison, Chemist-Analyst, 32, 93 (1913).
" M. Burger, Chemist-Analyst, 32, 92 (1943^.
" F . Rappaport, Mikrochemie, 16, 302 (1934).
II. TESTS FOR METALS
Cations and Anions of Metallic Acids
4
In spot analysis, as in qualitative macro- and semimicroanalysis, the

metals are almost always detected by characteristic reactions of their
hydrated ions. Consequently, it is assumed that solutions of the material
being investigated are available, or that they can be prepared. Since spot
tests uniformly employ more sensitive and more certain reactions, it is often
possible to carry out decisive tests with as little as one drop of the dilute
test solution, even though considerable quantities of other materials are
present. This permits the microchemical accomplishment of many so-
called "ultimate" afialyses, which demand only a decision as to the presence
or absence of one particular substance. The detection of the constituents
of a mixture of common metals can be successfully achieved, without a
preliminary separation, by an intelligent application of specific and selec-
tive spot reactions. In many cases, however, it is often better to make
a preliminary separation into definite groups and then to examine each
group. Such group separations can be carried out on a semimicro- or mi-
crochemical scale. I t is then possible to identify the individual members
of the groups by spot reactions (see Chapter V).
The sample should always be subjected to preliminary tests before
beginning any systematic investigation. These will give information about
the presence or absence of certain materials, and thus make possible a
considerable simplification of the systematic analysis. Spot reactions can
also be used for these preliminary tests; which will then require only small
amounts of the sample (see Chapter V).
In choosing spot reactions, it must be remembered that tests of
different sensitivities are available for most metals. Therefore, suitable
microchemical, semimicr'ochemical, or macrochemical tests can be selected,
depending on the problem at hand.
If the operator has had no previous experience with a particular spot test,
it is essential that he try out the reaction with pure solutions containing
a series of concentrations of the material to be detected. The knowledge
of the pertinent reaction picture is of great value in assessing the cer-
tainty of a test and in estimating the quantity of material present. I t is
necessary to adhere strictly to the conditions prescribed in the procedure,
to use reagents of proper concentration, to add them in correct order, etc.
In the following discussion, the metals to be tested for are arranged
in groups. These are distinguished by the fact that the metals in any
particular group are precipitated by a special group reagent. The data
relative to the sensitivity of the various tests are valid, unless otherwise
41
42 U. T3BSTS FOB METALS
stated, for pure salt solutions tested under 'the conditions given in each
case. I
A. HYDROGEN SULFIDE GROUP
(a) Basic Sulfide Group
SILVER
1. Test with manganese nitrate' and alkali. On mixing manganese and
silver salt solutions with alkalis, a black precipitate* is formed of manganese
dionde and metaUic silver:
Mn++ + 2 Ag+ + 4 0 H - = MnO, + 2Ag + 2 H , 0
The reaction takes place in very low silver ion concentration, so that
even silver in silver chloride solution can be detected by the dark colored
reaction product. The latter is probably not a mixture of silver and
manganese dioxide, but rather an adsorption complex. This is evidenced
by the fact that its color is much more intense than that of a mere mixture
of these materials (see page 160). "
Mercurous salts should not be present, as they also give a dark
coloration with alkalis, due to finely divided elementary mercury. Salts
of noble metals, stannous salts, and mercuric salts give the same reaction
with alkali and manganese salts; therefore, when these are present, the silver
should be isolated beforehand as silver chloride. This is also advisable in
the presence of such metals as give colored hydroxides, which would reduce
the sensitivity of the test.
^ProcedureÂ drop of hydrochloric acid is placed on the filter paper
followed by a drop of the test solution in the middle of the moist fleck,
and then a further drop of hydrochloric acid. On the addition of a drop
of manganese nitrate and a drop of alkali the fleck is blackened.
Limit of Identification: 2 7 silver ^ ~ - ~. _
Concentration Limit: 1:25,000
Reagents: / ) 0.1 JV manganese (II) nitrate solution
2) 0.1 JV" sodium hydroxide
The sensitivity of the test may be increased as follows: One drop
of hydrochloric acid is placed on a filter paper, and then a capillary contain-
ing about 0.025-0.03 ml. of the test solution is placed on the moist fleck
so that only a portion of its contents escape on to the paper. A second
drop of hydrochloric acid is placed on the paper, and the capillary touched
on to it again. This alternate addition of_the test solution and hydro-
' N. A. Tananaeff aad I. Tananaeff, Z. anorg. aUgem. Chem., 170, 120 (1928).
Compare also Z. anal. Chem., 106^ 167 (1936).
' Compare also D. Balarew, Z. anal. Chem., 60, 392 (1921).
8ILVSB 43
chloric acid is repeated 3 to 5 times. Finally the manganese nitrate and

alkali are added. In this way 0.3 7 of silver can be detected in a drop of
0.025 ml. volume.
2. Test with p-dimethylaminobeiuylidene rhodanine.' Rhodanine -(I)
and similar compounds with an intact NH group form insoluble silver salts
in acid solution, in which the silver atom replaces the hydrogen of the
cyclic NH (imine) group.* The silver salt of p-dimethylaminobenzylidene
rhodanine ( I I ) :
HN CO HN CO
SC CH, SC C=CH< >N(CH,),
(I) ' (11)

is red violet and is formed from slightly acidified silver salt solutions on
adding a solution of the reagent in acetone. This specific action of the
p-dimethylaminobenzylidene rhodanine occurs" only in add solution. In
alkaline solution, owing to a tautomeric change of the radical component,
HN CO - NCOH N CO
I 1 "to I I or il I
SC CH, SC CH. HSC CH,
\ s / Xs/ Xs/
it forms OH or SH groups in such quantity that a precipitation reaction

with almost all heavy nietals is possible; in part, this leads to a decomposi-
tion of the rhodanine molecule with formation of a sulfide.
In acid solution the p-dimethylaminobenzylidene rhodanine also
reacts with mercury, gold, platinum, and palladium, as well as with cuprous
salts. The latter, as usual, exhibit here an ability to form insoluble com-
pounds similar to the corresponding silver salts. However, under suitable
conditions that are easily secured (see pages 44, 45), the detection of sil-
ver can be made decisively, even in the presence of mercury, gold, plati-
num, and palladium salts.
IfProcedureFilter paper (Whatman 120, double thickness) is
impregnated with a saturated solution of the reagent in acetone, and when
dry, a drop of the slightly acid test solution is added. According to the
silver content, a red-violet precipitate or stain is formed on the paper. A
positive reaction is easily distinguished against the yellow-brown color
' F. Feigl, Z. anal. Chem., 74, 380 (1928).
* F. Feigl, Specific and Special Reactions. Translated by R. E. Oesper, Inter-
science, New York, 1940, p. 110.
44 II. TESTS FOB METALS
I
of the reagent, even with minute amounts of silver, if the unused reagent is
removed by bathing the reagent paper in acetone.
Limit of Identification: 0.02 y silver (in 0.2 N HNO3)
Concentration Liimit: 1:2,5(X),000
Reageni: Saturated solution of p-dimethylaminobenzylidene rhoda-
nine* in acetone.
The silver test may also be carried out in a micro test tube; the unused
reagent should be extracted with ether. As little as 0.2 y Ag (violet flecks
of the silver compound) may then be seen under the yellow ethereal layer.
Test in the presence of mercury. In the presence of mercury salts, which
also give colored precipitates with p-dimethylaminobenzylidene rhodanine,
silver can be detected as follows:
IfProcedure(a) A drop of the test solution is mixed on the spot
plate with a drop of a 5% potassium cyanide solution, whereby the soluble
compounds KAg(CN)2 and Hg(CN)2 are formed. If a drop of the reagent
solution is added and a drop of 2 N nitric acid, the colored silver p-dimethyl-
aminobenzylidene rhodanine is formed, whereas the undissociated mercuric
cyanide does not react with the reagent.
(b) A drop of the test solution is precipitated with the reagent, either
on the spot plate or on filter paper, and then a few drops of dilute hydro-
chloric acid or ammonium chloride are added. The organic mercury
compound is dissolved to form sparingly dissociated mercuric chloride,
while the silver precipitate remains, as the silver rhodanine is less soluble
than silver chloride. Method (6) is recommended when copper as well
as mercury salts are present, since the cuprous cyanide is sufficiently
dissociated when potassium cyanide is used to react with the reagent, giving
a red insoluble cuprous salt, which resembles the silver compound.
In order to detect silver in a mixture of leadj mercurous, and silver
chlorides^ as produced in the systematic group analysis^ the mixture is
treated with a 5% solution of potassium cyanide, whereby both Hg(CN)3
and metallic mercury are formed as well as KAg(CN)2. The mixture is
filtered and the clear filtrate is treated on the spot plate with a drop of the
acetone solution of the reagent and 2 drops of 2 A^ nitric acid.
In the presence of silver, a red coloration is formed, which should
be compared with a blank, if small amounts of silver are suspected.
, . . , . , , , . - ^. ., fin the presence of 1000 times
Lamit of Identijication: O.od 7 silver I., . , T>U/~.I A
' . ; : . . , , . __' < the amount of PbCU and
Concentration Dimtt: 1:80,000 m PI '
Detection of silver in silver plating and in alloys, see page 425.
' For preparations of this reagent see R. Andreasch and A. Zipser, Monalsh.,
26, 1203 (1905).
K. Heller and P. Krumholz, Mikrochefnie, 7, 214 (192i().
SILVER 45
Detection in the presence of gold, platinum, and palladium.^ Gold, plati-

num, and palladium salts also give colored precipitates in acid solution with
p-dimethylaminobenzylidene rhodanine. Nevertheless, silver (in the
absence of copper salts) can also be detected in the presence of these metals
when the reaction takes place in solutions containing cyanide ions. A
solution of KAg(CN)2, after acidifying with dilute nitric acid, reacts with
the reagent; under the same conditions gold, platinum, and palladium salts
do not react.
Procedure A "drop of the test solution, as slightly acid as possible,
is stirred on a spot plate with a drop of potassium cyanide solution. A
drop of the reagent solution is added, and dilute nitric acid is stirred in
until the mi.xture is acid. A pink coloration shows the presence of silver.
Limit of Identification:- 1 7 silver fin the presence of 4000 times
lAmit of Concentration: 1:50,000 1 the amount of gold
Limit of Identification: 2.5 7 silver fin the presence of 300 times the
Limit of Concentration: 1:20,000 (amount of palladium
Reagents: 1) 10% potassium cyanide solution
2) 0.03%'solution of p-dimethylaminobenzylidene rhoda-
nine in alcohol
3) Nitric acid (1:4)
3. Test by deposition.^ It is well known that after exposure to light, a
picture is formed on a photographic plate (or film) on treatment with a
developer. This is always a reducing substance which reacts with the_
silver |?romide, that has been subjected to the influence of light (latent
image), to give precipitation of silver. A physical developer,^ which con-
tains some silver salt as well as the reducing substance, may also be used.
Such physical developers can precipitate'" appreciable amounts of silver
itself on traces of silver bromide, which have been exposed to light. In
this way, physical development can be used as a spot test for silver.
ProcedureA small circle of about 15 mm. diameter is drawn on a
piece of filter paper (S & S 589) to designate the spot. A drop of the very
dilute test solution is put in this circle. After the drop has soaked in, the
paper is placed in a dish of potassium bromide for about half a minute.
The bromide solution is then poured off and replaced by distilled water.
The dish is kept in motion and the wash water changed every half minute
' F. Feigl, P. Krumholz, and E. Rajmann, Mikrochemie, 9, 295 (1931).
A. J. Velculescu, Z. anal. Chem., 90, 111 (1932).
' E. V, Angerer, Wissenschaftliche Pholographie. Akadem. Verlagsgesellschaft,
Leipzig, 1931, p. 19.
'" The theory of this is discussed by W. Ostwald, Outlines of General Chemistry.
Translated by W. W. Taylor, Macmillan, New York, 1912, p. 530. See also F.
Ephraim, Inorganic Chemistry. Translated by P, Thorne and A, Ward, 3rd ed.,
Nordeman, New York, 1939, p. 252.
(6 to 8 times in all) to remove all traces of soluble materials from the dish
and paper. It is not necessary to expose the paper expressly, because the
silver bromide retained in thefibersof the paper is attacked by the physical
developer, even though the halide has not been light-struck. After the
last wash water is poured away, the developer is poured into the dish. la
a few minutes, or as long as half an hour, according to the silver content of
the drop of test solution, a grey fleck of metallic silver, which turns blacker
in time, develops within the circle. The developer, which is clear and
colorless at first, becomes violet in time with the separation of colloidal
silver, and is finally quite cloudy. Usually, the action of developer is
complete before it becomes cloudy. However, in very great dilutions it
may happen that the developer becomes cloudy before the fleck is distinct
enough. In this case the paper is removed, thoroughly washed, and placed
in fresh developer. The greatest cleanliness is essential for the success of
this test.
If the filter paper is dirty, or contains foreign bodies, black flecks
may appear in the developer, due to the formation of silver on these im-
purities. However, as these do liot have the outline of a drop, and appear
elsewhere than in the circle, they do not interfere with the correct inter-
pretation of the test.
It is important that all the potassiimi bromide be washed out of the
paper before development. Otherwise, any KBr that remains will'combine
with silver from the developer, and the resulting silver bromide, in its turn,
will cause the deposition of silver. Consequently, the entire surface of the
paper will be blackened.
Limit of IderUificalion: 0.006 y silver
Limit of CoTuxntration: 1:10,000,000
Reagents: I) 0.02 N potassiunf bromide solution
2) Preparation of developer: 500 ml. water, 10 g. metd
(monom'ethyl-p-amidophenol),'50 g. citric acid; imme-
diately before use 2 ml. of a 0.1 M silver nitrate solution
are poured into 50 ml. of the metol solution."
Silver sulfide" can also be used as a-reduction nucleus, provided other
metals precipitable by hydrogen sulfide and nitric acid are absent.
fProcedureOne drop of the test soliition is placed'on filter paper
and exposed to a hydrogen sulfide atmosphere for about 30 seconds. The
spot is thoroughly washed and then developed.
" The developer prepared as described will only keep for a limited time,
owing to the formation of traces of nuclei of 8ilYer.-"^he stability of the solution can
be appreciably increased by the addition of 1 part per 1000 of gum arable. (Personal
communication from Dr. G. Schwarz, Antwerp.)
" A. Velculescu, C?iem. Abstracts, 34, 2278 (1940).
SILVER =1 47
Limit of Identification: 0.(H)5 y silver

Concentration Limit: 1:10,000,000
Reagents: The stoCk solution contains 2 g. pyrogallol and 2 g. citric
acid in 500 ml. water. Sixty ml. are treated with 2 ml.
0.1 A'' silver nitrate shortly before using.
4. Test by catalytic redaction of Mii(III) and Ce(IV) salts.'' The^ brawn
solutions of Mn(III) and Mn(IV) salts are stable in 2.5 N hydrochloric
acid solutions at room temperature, and liberate little or no chlorine. Qn
the addition of silver nitrate these brown solutions rapidly decolorize, with
evolution of chlorine." The silver chloride, in solution in the hydrochloric
acid, acts as a catalyst in the reaction between the higher manganese oxides
and hydrochloric acid. Ceric salts in hydrochloric acid solutions behave
similarly; when alone, their yellow color fades very slowjly with develop-
ment of chlorine, but on the addition of silver nitrate the reaction is instan-
taneous. The fact that the silver chloride has a catalytic effect only in the
presence of chloride ions is due to an activation of hydrochloric acid by silver
chloride. Probably the complex compound HAgCl, which may be formed
in these conditions, takes part in the reaction. This catalyzed liberation
of chlorine is effected by such small amounts of silver that the reaction
may be used as a test for silver. It is carried out most conveniently as a
spot test.
^[ProcedureIn two adjoining depressions of a spot plate are placed
3 drops 6f the reagent solution [Mn{III) or Ce(IV) solution, and 2 drops
of dilute hydrochloric acid]. In one depression is placed a drop of the
test solution and in the other a drop of water. The reagent is decolorized
more or less quickly according to the amount of silver present.
Limit of Identificaiion: OA y BilveT / . , , , ,
Concentration Umit: 1:120,000 1 ""'8 ^^^^^^ ^*
Limit of Identification: 0.05 y silver / . _, _^,. ,
Concentration Umit: 1:1,000,000 \ "'"''^^ ^^^^^ '^^^
Reagents: Mn(III) solution. 0.6 g. MnSOi is dissolved in 60 ml.
water and 20 ml. cone. HCl. Ten ml. of a 0.1 N KMnOi
solution are added, and the mixture well shaken. From
tliis solution 15 ml. are diluted with 50 ml. HCl (1:2).
Cerium (IV) solution. 0.25 g. cerium ammonium nitrate
is mixed with 10 ml. dilute nitric acid and the solution
diluted to 100 ml. with water.
This catalytic test for silver can also be used to detect silver in the
presence of thallium in the mixture of precipitates formed by HCl in the
" . Feigl and E. Frankel, Ber., 65,544 (1932).
'< R. Lang, Z. anorg. allgem. Chem., IBS, 201 (1926); Ber., M, 1389 (1927). -
48 H- TESTS FOR METALS
I
course of the systematic qualitative analysis. The precipitates of the
chlorides of Ag, Hg, and Tl are washed with hot (water, and a small portion
heated in a microcrucible to weak glowing, to remove the Hg2Cl2 and TlCl.
The residue in the crucible is treated, after cooling, with 1 to 2 drops of the
Mn(in) or the Ce(IV) solution.^^
Quantities of silver that are not too small can be detected in the HCI
precipitate of the systematic scheme of analysis. The precipitate is stirred
with ammonia water and 20% KOH solution, and then formalin is added.
Free silver is precipitated .i'
5. Other tests for silver. 1. On treating an acetic acid solution of a silver
salt with K2Cr04 , the silver may be recognized by the red Ag2Cr04 formed
(Zd". Limit: 2 7 Ag). It is advisable to use the filtrate after precipitation
with (NH4)2COs.
2. By the reduction of ammoniacal silver solutions with SnCIi, 1 7
Ag can be detected.i'
5. With a solution of dithizone in CCU," a violet precipitate, insoluble
in e c u , is formed from neutral solutions of silver salts {Id". Limit: 0.05 7
Ag), As dithizone reacts with other metals, special precautions must be
taken when any of these are present.
4. A black stain is formed on treating silver salts with SnClj and
chromotropic acid.'* With chromotropic acid alone, silver salts give a
white precipitate, that rapidly turns brown." (/d". Limit: 0.1 mg. Ag);
free acids and Ag salts interfere with this reaction.
6. Acid solutions of silver salts, spotted on a paste of CuCNS, form a
smoke brown color.*"
MERCURY"
1. Test with diphenylcarbazone.^' Mercury salts, in acid solution, give
violet to blue insoluble inner complex salts (IH)"' with diphenylcarbo-
hydrazide (I) and its oxidation product diphenylcarbazone (II).
H H
NNCH. N==NC,H* N=NC.H,
0=C^ 0=0^ 0=</ ^Hg/2
NNCeH, NNC,H, NNC.H,
H H H H H
(I) (II) (III)
" A. V. Atta, J. Chem. Education, 16,164 (1939).
>' N. A. TananaefF, Z. anorg. allgem. Chem., 140, 320'(1924).
" H . Fischer, Z.onêw. Chem., 42, 1025 (i929); Mikrochemie, 8. 319 (1930),
" G. Gutzeit, Helv. Chim. Acta, 12, 837 11929).
" E. A. Kocsis and G. Gelei, Z. anorg. allgem. Chem., 232, 202 (1937).
V. I. Occleshaw, / . Chem. Soc, 140,1438 (1937).
" See page 210 concerning the detection of rdereuric cyanide.
" P. Caeneuve, Compt. rend., 181,546 (1900); F. Feigl and F. Neuber, Z. anal.
Chem., 62, 370 (1923).
F. Feigl and F. Lederer, Monaf*h.. 46. 63,115 (1S24).
MEHCtTHY 49
The sensitivity of the mercury test with diphenylcarbazone depends

on the acidity of the test solution, and decreases with increasing acid con-
tent. In neutral or very weakly acid solutions, however, other hsavy
metals (such as Cu, Fe, Co, and other salts) also give colored compounds
with diphenylcarbazone.^* In 0.2 N nitric acid solution, the diphenyl-
carbazone reaction is specific for mercury, in the absence of chromates
and molybdates (which give colored compounds under the same conditions,
see page 128). The interference of chromates is prevented by reducing
them with sulfurous acid or hydrogen peroxide to nonreacting chromium
(III) salts. Molybdates may be treated with oxalic acid, as the complex
molybdenum-oxaUc acid does not react with diphenylcarbazone.
The presence of chlorides affects the test, owing to the fojrmation of
slightly dissociated mercuric chloride; for the same reason the diphenyl-
carbazone test is less sensitive for a solution of mercuric chloride.
^[ProcedureÂ drop of the test solution is placed on a filter paper
impregnated with a freshly prepared alcoholic solution of diphenylcarba-
zone. According to the concentration of mercury, a violet or blue fleck
appears.
Hydrolyzable acid
Limit of Identification: 0.1 y mercury
Hg(N0j)2 solution
0.1 iV nitric acid
0.2 y mercury
Hg(N08)i solution
0.2 A'' nitric acid
1.0 Y mercury Hg(NOj)j solution
Concentration Liimit: 1:500,000
1:250,000
1: 50,000
Reagent: 1% alcoholic solution of diphenylcarbazone.*'
2. Test with dithizone.*' Diphenylthiocarbazone (dithizone)
H
K^:
NNHCHi
=NC,Hi
reacts with salts of many of the heavy metals (also with the free metals,
sulfides and carbonates) to give colored compounds, which are usually
soluble in carbon tetrachloride. When water solutions of mercury salts
are shaken with the green solution of dithizone in carbon tetrachloride, the
e c u layer turns orange.
R. Alexejeff, Chem. Abstracts, 32, 451 (1938), states that many interfering
metal ions are masked by adding alkali pyrophosphate to the solution at pH 7 tc 7.2.
" F o r preparation, see K. H. Slotta and K. R. Jacoby, Z. anal. Chem., T7,
346 (1929).
H. Wolbling and B. Steiger, Z. angew. Chem., 46, 279 (1933). s
BO n . TBBTB yOB METALS
^[ProcedveA drop of the test solution is mixed with 2 drops of the

reagent solution and stirred until the CCU evaporates. The residue is
again taken up with carbon tetrachloride. The green color of the dithizone
changes to orange when mercury is present.
Ldmit of Identifkation: 0.25 y mercury (as HgClj)
Concentration Limit: 1:200,000:
Reagent: Dithizone solution: 1 to 2 mg. dithizone" dissolved in
100 ml. carbon tetrachloride.
When other metals which react with dithizone are present, the test
must be modified by suitable means (complex salt formation, oxidation and
alteration of pH value). In acid solution the only interfering metals are
tin, antimony, bismuth, copper, gold, and the platinum metals.
Iron (III) and tin (II) salts may be oxidized; they then ao longer give
the color reaction. Antimony and bismuth complex salts with tartaric
acid do not react; in the presence of bismuth salts nitric acid should be
added. Gold salts can be reduced with sulfurous acid, and platinum metals
with copper or silver powder. In the presence of copper, the test solution
is neutralised and then treated with 95% formic acid until it is appreciably
acid; then the solution of dithiKOie in carbon tetrachloride is added. The
carbon tetrachloride layer is lig^t pink, which turns to bright yellow-orange
in the presence of mercury.
If not only copper, but also iron, cobalt, nickel, platinum, and gold
are present, the solution is treated with copper powder. Iron, cobalt, and
nickel remain in solution, but gold, platinum, and mercury are precipitated.
On treating the precipitate with dilute nitric acid, copper and mercury are
dissolved, and'mercury can be detected in the solution in the presence of
copper, as described.
In the absence of copper, the platiniun metals are precipitated
with silver powder, and meroury can be detected in the filtrate. Silver
does not interfere, as the silver reaction is prevented -by even low acid
concentrations. Thus, as little as 1 ^ of mercury in the presence of 100,000
times the amount of silver can be detected without difficulty when 1 drop
of .1 N sulfuric acid is added to the test solution.
3. Test with stannous chloride and aniline.'* Merouric salts are reduced
to metalUc meroury by stannous chloride in the presence of aziiline (com-
pare page 89). A grey or black fleck is formed on paper. The specificity
of the mercury test is affected by large amounts of silver salts, which are
also reduced by stannous chloride and aniline, to give metallic silver.
Bismuth salts, however, are without eifect, as they are only reduced by
alkaUne stannite solutions.
" For preparation, see E. Fischer, Ann., 190, 16, 118 (1878); E. Fischer and
E. Besthorn, ibid., 812,316 (1881).
'N. A. Tanaaaeft, Z. anorg. allgem. Chem., 136, 373 (1924); 140, 321 (1924).
MSBCDBT 51
IfProcednreA drop of the test solution is placed on test paper

followed by a drop of stannous chloride solution and a drop of aniline.
A black to brown color indicates mercury.
Limit of Identification: 1 y mercury
ConcerUiotion Limit: 1:50,000
Reagent: Freshly prepared stannous chloride solution.
4. Test with p-dimethylaminobemyUdene rhodanine.'* Mercury salts
give a red-violet precipitate in weekly acid solutions with an alcoholic or
acetone solution of p-dimethylaminobenzyUdene rhodanine (see page 43).
Large amounts of chlorides and also free hydrochloric acid hinder the
formation of the mercury rhodanine compound, as they reduce the normal
slight dissociation of mercury chloride, and also lead to the formation of the
complex HgCir~ ions. However, in acetate-buffered solutions, the mercury
gives a red color with the reagent even in the presence of excess chlorides.
In hydrochloric acid solutions, buffered with acetate, the intensity of the
red coloration bears no relation to the concentration of mercury and, even
in fairly concentrated solutions, only a relatively weak color develops.
Obviously, in the presence of chlorides, only a portion of the mercury reacts
with the rhodanine. i
Test in the absence of chlorides and large am,ounts of free adds
^ProcedureA drop of the weak nitric or sulfuric acid test solution
(the acidity should not be greater than 0.1 N) is mixed on the spot plate
with a drop of reagent solution. According to the amount of mercury, a
violet precipitate or pink color is formed. The reagent itself in acid solu-
tion is colorless or faintly yellow.
Test in the presence of chlorides and any amount of free adds
1[ProediireA drop of the acid test solution is mixed on the spot
plate with a drop of reagent and a few drops of sodium acetate. In the
presence of mercury there is a pink coloration. As the reagent itself is
colored yellow to orange with the addition of acetate, a parallel test should
be carried out with dilute hydrochloric or nitric acid.
Reagents: 1) Saturated alcoholic solution of p-dimethylaminobenzyl-
, idene rhqdanine
2) Saturated sodium acetate solution
Silver salts give a red-violet precipitate with the reagent under the
same conditions (see page 43) and must therefore be removed by precipita-
E. HeUer and P. Erumholz, Mikroehtmie, 7, 214 (1920).
tion with hydrochloric acid before the test. Copper salts give a dirty red
coloration only in solutions that are neutral or strongly buffered with
acetate. Under suitable conditions, however, mercury can be detected
in the presence of even considerable copper.
Test in the presence of copper
When an acid copper solution is treated with an excess of sodiiun
phosphate, insoluble Ught green copper phosphate is formed, which reacts
very slowly with rhodanine. The addition of phosphate also reduces the
acidity so much that the mercury present gives a red color with rhodanine,
which is clearly visible even in the presence of the green copper phosphate.
^ProcedureA drop of the acid test solution (of not more than 1 N
acidity) is mixed on the spot plate with 5 drops of sodium phosphate and
1 drop of rhodanine solution. In the presence of mercury a violet to pink
color is formed. When very small amounts of mercury are present a
blank test should be carried out, and, the result observed at once.
Limit of Identification: 1 y mercury Jin the presence of 450 times
Concentration Limit: 1:50,000 \the amount of copper
Reagents: 1) Saturated alcoholic solution of p-dimethylaminoben-
zylidene rhodanine
2) 10% solution of NasPO*
5. Test by catalytic acceleration of the reduction of tin(IV) salts.'" Tin
(IV) salts are reduced to tin (II) salts by hypbphosphites thus:
2 Sn+++++ HsPOr + 2 H2O = 2 Sn+++ P O r " + 6 H+ (jf)
This reduction is, however, both slow and incomplete, but it can be remark-
ably accelerated" by mercury (II) salts, which also react with hypophos-
phoric acid. It appears that the reaction {2) induces,^the reaction {!).
2Hg++ + HjPOr + 2H2O = 2Hg + POr"" + 6*H+ {2)

This induction effect takes place even with very small amounts of mercury
salts, so that the mercury can be detected by the formation of tin (II) salts,
which are identified by the cacotheline reaction (see page 87). The test
succeeds even with a solution of undissociated mercury cyanide, or of
complex sodium mercury iodide.
Pd, Au, and Cu salts must not be present, as they/are themselves
reduced by hypophosphite and then react with, oacotheline in the same
way as Sn(II) salts. Silver salts and, to a greater extent, osmium salts,
" F. Feigl and L. Badian, unpublished studies.
B. S. Evans, Analyst, 56, 177 (1931).
MERCURY 53
reduce the catalytic action of mercury.'^ Cu(II) salts are reduced by

hypophosphite to Cu(I) salts and in this state react with cacotheline in the
same way as Cu(II) salts.
l[ProcedureA drop of the test solution is mixed with a drop of the
reagent solution in a micro test tube, which is suspended for 15 seconds in
a boiling water bath. According to the amount of mercury present, the
yellow solution turns red or light pink. A blank should be carried out when
very small amounts of mercury are present.
Limit of Identification: 0.1 -y mercury
_ Reagents: 1) Ammonium chlorostannate
2) Sodium hypophosphite
3) Cacotheline (preparation see page 88)
Ten g. ammonium chlorostannate are dissolved in 80 ml. 2 N hydro-
chloric acid and filtered after 24 hours. This solution is mixed with 50 ml.
5% sodiiun hypophosphite solution and 8.ml. 1% cacotheline solution are
added.
6. Test by activation of aluminum. Contrary to the usual stability of
aluminum, aluminum-amalgam (which is easily formed by placing mercury
or mercury salts in contact with aluminum) is quickly converted into
alumina in moist air." The mercury thus liberated can amalgamate with
fresh aluminum, and the process is repeated, so that small amounts of
mercury, such as mercury electrolytically precipitated on aluminum, can
be detected by the formation of alumina.'* Mercury can easily be
electrically precipitated, from even one drop of solution, on to aluminum
foil. The small amounts of alumina formed can then be identified by the
lake formation with aUzarin (see page 143). In this way minimum amounts
of mercury may be detected.'^
In order to be able to use the alizarin test, the electrolytic precipi-
tation of mercury must take place from neutral solution, as acid or alkaline
solutions attack metallic aluminum sufficiently to give a strong reaction
\viih alizarin. When the test solution is neutral, the mercury can be
precipitated directly on to an aluminum cathode, and the alizarin test
carried out in situ. If, however, the test solution is acid or alkaline, the
mercury must be deposited on a platinum wire cathode, which, after wash-
ing with water, is connected as anode against a cathode of aluminum foil.
On passing the current, the mercury dissolves from the anode and is
deposited on the almnimun and forms an amalgam.
" I. M. Kolthoff and R. S. Livingstone, Ind. Eng. Chem., Anal. Ed., 7, 209
(1935).
" Regarding this method of detecting aluminum, see F. Cucuel, Mikrochemie,
13, 323 (1933).
'* E. Schmidt and E. Tornow, Chem.-Ztg., 56,187,206 (1932).
64 n . TESTS JOB HETALS
flVocednreWhea mercmy is to be detected in neutral solution, a

drop is placed in a stamped depr^sion in a piece of aluminum foil that has
been roughened by sand blasting. A mlcrodrop of dilute sodium sulfate
solution is added as conductor and a drop of quinone solution as depolarizer:
Then the tip of the platiniun wire, which is used as an anode, is immersed
(the aluminum foil being the cathode), and the current from, a flashlight
battery is passed through for 15 minutes (see Fig. 41). The solution is
then washed off the aliuninum foil with water and the moistened portion
dried with a clean cloth. After 5 minutes the almnina formed is moistened
with a drop of an acetic acid solution of alizarin, allowed to stand for 3
minutes, washed off with water, and again dried with the clean cloth;
another drop of alizarin solution is placed on the spot,
left for three minutes and then rinsed ten times in dis-
tilled water. K mercury is present, red dots of the
Fig. 41. Aluminum aluminum lake of alizarin stick to the aluminum foil.
foil for electrolytic For small amounts of mercury, a blank test must be car-
detection of mer- ried out with distilled water. A red color is also formed
cuiy (j actual size)
with alizarin, but it disappears on washing or drsring.
If an acid solution is to be examined, a drop
should be placed in the apparatus shown in Figure 42
and electrolyzed for 15 minutes with a platinum wire
as cathode. The mercury collects on the wire. This
is then washed and used asi anode agiunst the aluminum
Fig. 42. Set-up for foil as cathode, as described. On passing the current,
electrolytic deposi- the mercury goes anodically into solution, is then
tion of mercury deposited on the aluminum cathode, and can be identi-
(i actual size)
fied as described.
Limit qf Idenlificaiion: 0.007 y mercury "^
Concentration Limit: 1:7,143,(KX)
Reagents: 1) Sodium alizarin sulfonate: 0.2 g. of the salt is dissolved
> in 100 ml. water and 0.-5 ml. acetic acid is added.
2) Quinone solution: a cold saturated aqueous solution.
S) Sodiiun sulfate: 0.02 g. of the salt dissolved in 100 ml.
water.
The preceding test can be recommended when minimal quantities of
mercury are to be detected and, consequently, the tedious preparation and
testing of suitable aluminum foil will be justifiedir -A shorter but less
sensîve test follows." Aluminum foil is roughened with emery paper,
washed with water, and etched with concentrated alkali until a uniform
evolution of hydrogen occurs. After rinsing ^ t h water and rubbing with
< A. Longer, Chem. Litty, 83, 438 (1938); Chem. Ab$tracU, SS, 3717 (1939).
LEAD 55
a cloth moistened with dilute alkali, the foil is dried. A drop of the test
solution is placed on the prepared aluminum, allowed to react for 3 minutes,
and ihe liquid is then taken up with filter paper. If mereury is present,
white growths appear after about 6 minutes (Id". Limit: 0.1 y Hg). Con-
siderable quantities of acids, or of metals that form a precipitate with
alkalis, interfere w^th the test. '
7. Other tests for mercory. 1. Mercuric salts can be detected by the
reaction with Cujlj," in which Cu[Hgl4] is formed. The test is best
carriied out on Cujlj paper {Id". Ldmit: 0.03 y Hg). Easily reducible
substances, concentrations of Bi exceeding 500 mg. per 1., and a higher
acidity than 0.1 iV, interfere wilJi this test.
S. Mercuric and mercurous salts may be detected by the formation of
a brown or yellow precipitate with chromotropic acid.** The test is carried
out on filter paper {Id'. Ldmit: 0.1 mg. Hg). The presence of acids and
silver salts interfere with this reaction.
LEAD
1. Test with benzidine." Lead peroxide, in common with a number of
other oxidizing agents, can oxidize benzidine (I) to the so-called "benzidine
blue" (II). This is a meriquinoid oxidation product*" consisting of one mole-
cule of the amine, one molecule of the imine, and two equivalents of a
monovalent acid.
H.N<r J><^ V-NH,
HtN< >< >NH, 2HX
(i) (II)
Alkali and bromine water (alkali hypobromite) are recommended for
the conversion of the lead salt to PbOi, as the excess hypobromite can be
instantaneously destroyed by means of ammonia; 3 NaBrO + 2 NH =
3 NaBr -}- Nj + 3 HjO. This test for lead*' is interfered with by cerium,
manganic, bismuth, cobalt, nickel, silver, and thallium salts. Under the
same conditions, these metals also give higher oxides capable of oxidizing
benizidine to benzidine blue. If, however, the lead test is carried out in an
alkaline extract (plumbite solution), thallivun offers the only interference.
All other metal ions are precipitated as hydrous metal oxides and so do not
enter the alkaline extract. When only bismuth salts are present, it is
sufficient, before the addition of bromine water, simply to heat with the
' P. Artmann, Z. anal. Chem., 60, 81 (1921).
" E. A. Kocsis and G. Gelei, Z. anorg. allgem. Chem., 238, 202 (1937).
" G. DenigSs, Prieis de ckimie analytique. 4th ed., Paris, 1913, p. 72.
" Compare W. Schlenk, Ann., 363, 313 (1908).
" F. Feigl and A. Singer, Pharm. Presae, 6, 37 (1935). See also F. Feigl and
F. Neuber, Z. anal. Chem., 62, 371 (1923).
H. TESTS FOR METALS
alkali. BiO(OH) is formed, which is not converted by hypobromite into

the higher bismuth oxide. I
^ProcedureA drop of the test solution is placed! onfilterpaper and
treated successively with alkali and. bromine water. After the last drop
has soaked into the paper, 2 drops of a solution of ammonia are added,
allowed to spread, and the excess ammonia removed by waving the paper
over a small flame. The solution of benzidine is then added, and according
to the amount of lead present, a light to deep blue fleck is formed. The
blue color fades when very small amounts of lead are present.
Limit of Identification: 1 7 lead
Reagents: 1) 3 N sodium hydroxide
2) Saturated bromine water
S) Solution of benzidine in acetic acid
4) Solution of ammonia (I'.l)
Lead can be detected in even greater dilutions by the following:
The test solution is treated with 3 ml., 3 N alkali and 2 ml. bromine
water, boiled a few times, and filtered through a quantitative filter paper.
After washing with hot ammonia (1:1) followed by hot water, a drop of
an acetic acid solution of benzidine is placed on the paper. In the presence
of 10 7 of lead in 10 ml. test solution, which implies a dilution of 1:1,000,000,
there is an appreciable blue coloration.
2. Test with sodium rhodizonate.^* Sodium rhodizonate (I) produces
colored precipitates of basic lead rhodizonates from neutral or slightly acid
lead solutions. Violet Pb(CgOe) Pb(OH)j H2O is thrown down in neutral
solution, scarlet-red 2 Pb(C606)-Pb(OH)2-H20 is produced from weakly
acid solutions. The deep color of these lead salts probably arises from the
fact that lead rhodizonate functions as an inner complex salt (see II).
O O-
(1)
o
0=4
Na
ONa :<t> (11)
O 0-
Both reactions are so sensitive that positive results are given immediately
by even such slightly soluble materials as PbS, PbS04, PbCrO/, etc.
f ProcedureA drop of the test solution is-pJaced on filter paper.
After the liquid has been soaked up, the spot is touched with a drop of
sodium rhodizonate solution. A blue fleck or ring is formed if lead is
F. Feigl and H. A. Suter, Ind. Eng. Chem.,^nal. Ed., 14, 840 (1942). See
ftlso I. M. Kolthoff, Pharm. WeekUad, 62,1017 (1925).
LEAD 57
present. If an intense reaction occurs, the blue fleck is transformed to

scarlet by spotting with a drop of buffer solution.
Limit of Identification: 0.1 y lead
Reagents: ly 0.2% solution of sodium rhodizonate (freshly prepared)
2) Buffer solution (pH = 2.79) 1.9 g. sodium bitartrate
and 1,5 g. tartaric acid per 100 ml.
Detection of lead in the presence of other metals. Sodium rhodizonate,
at pH '^ 3, forms colored compounds also with T1+, Ag+, Cd++, Ba++, and
Sn++. The sensitivity of some of these reactions is less than that with
Pb++. Lead can be identified easily in the ordinary qualitative scheme,
if its chloride is present along with the chlorides of silver, univalent mercury,
and thallium.
The mixed precipitate produced by hydrochloric acid is not washed,
but is transferred directly to a crucible, dried by gentle warming, and then
carefully heated to redness. Any thallous and mercurous chloride are
thus removed by volatilization. The cold residue is digested with 4 drops
of strong ammonia water to dissolve any silver chloride. The contents of
the crucible are then evaporated to dryness. Three drops of buffer solution
and 1 drop of sodium rhodizonate are added. If the chloride precipitate
contains leatf, a red precipitate or coloration will appear. It is necessary
to dissolve the silver chloride in ammonia because this salt melts and
encloses lead chloride, which may thus be shielded from the sodium
rhodizonate.
This procedure, which can be used to detect lead in the presence of
all other metals, is far more sensitive than the customary method of extract-
ing lead chloride in hot water and then adding a suitable reagent. The
limiting proportion was detemiined in about 5 mg. of the mixed chlorides;
the value of Pb: Ag is 1:5000.
Detection of traces of lead in water, alkali salts, and sulfuric acid, see
p. 430.
Detection of lead in alloys, eXc, see page 428.
3. Test with dithizone (diphenylthiocarbazone).*' Dithizone (I) forms
a brick-red, inner-complex lead compound (II) with lead'"salts in neutral,
ammoniacal, alkaline, and cyanide solutions.
H H H
NNC.H. NNCHi.
( S=c( S=<^ >Pb/2 ("^
" H . Fischer, Z. angew. Chem., 42, 1026 (1929); Mikrochemie, 8, 319 (1930).
58 II. TESTS FOB H E T A L S
Dithizone reacts with numerous metal ions, asVell as ^ t h lead, to form

inner complex compounds which are soluble in oiânic liquids. However,
if the conditions given here are observed," the test for leald is specific.
IfProcednreÂ drop of the test solution is vigorously shaken m a
small test tube with a drop of a carbon tetrachloride solution of dithisone.
The green reagent assumes a brick-red color that is easily seen against
a white background.
Limit of IderUifiaîon: 0.04 y lead (in neutral solution)
Coneentration Limit: 1:1,250,000 s
Reagent: A soluticm of 1 to 2 mg. dithizone in 100 ml. carbon tetra-
chloride**
The fact that the reaction between lead salts and dithizone takes place
in the presence of considerable funounts of potassium cyanide and sodium
potassium tartrate, renders the test for lead specific among the hivy metals
TABUS 1
limit o( ForeSgn Potuntaa PfaportioB

Foreign meUl aalt lued identifica- Qrankk, 7 Otber HiU added, Ibnit^
metal, 7 iaOJKml. Pb: {oteifa
0.05 ml. inOASml. ia 0.05 ml. metal
AgNO. 0.2 11,600 10 1:58,000

CuS04-aq 0.1 1,800 9 18,000
NiS04-aq 0.1 1,600 10 16,000
ZnSOiaq 0.1 1,176 6 2 mg. NH4CI 11,760
Cd(C,H,0,)aq 0.1 1,600 10 2 mg. NHiCl 16,000
K antimony 1 tartrate.. 0.1 930 2.6 6 mg. Bochelle
salt 1: 9,300
which are "masked" by the addition of these salts. Table 1 gives the
limits of sensitivity and ccmcentration limits to be achieved under the
varying conditions.
4. Other tests for lead. 1. If a, drop of dilute sulfuric acid and a drop
of the test solution are placed successively on filter paper, the resulting
fleck of PbSO* can be washed with dilute sulfuric acid and water. When
spotted with a solution of CdSnIi containing iodide, the PbSO* is con-
verted into orange-red 2 Pblj-Snlj {Id\ Limit: 10 y lead).*'
S. Lead in neutral solutions, or as the hydroxide, can be detected
by the formation of a violet lake color on the addition of a 1% solution of
the blue oxaîne dyestuff, gallocyanine {Id". Limit: 0.3 y Pb).** When
other metals are present, PbSOi should be precipitated on theâper before
** Sometimes the'solution does not keep because the, glass container furnishes
traces of lead.
N. A. Tananaeff, Z. anorg. allgem. Chetn., 187, 81, 341 (1927). See also A.
5. Komarowsky and W. Owetschkin, Z. anal. Chem., 71,56 (1927).
F. Favelka, MikrochemU, 7, 3(8 (1929)^.
BISMUTH Sd
the treatment with gallocyaaiae. In tiiis way 2 to 3 Y Pb may be detected

in the presence of 10 to 15 times the amount of the foreign metal (Ag,
Bi, Cu, Cd).
S. Carminic acid (an oxyanthraquinone derivative of complex struc-
ture) also fonns a violet lake color with neutral solutions of lead salts,
or with Pb(OH),, in the presence of NH, (Id". Limit: 1 y Pb)." Under
certain conditions this test for lead can aiao be used in the presence of
small amounts of metals (A the HtS group.
BISMUTl^
1. Test wi& dndtoirine aad potaadam iodMe.^' Numerous organic
bases, among them cinchonine, form insoluble (and some colored) double
iodides of the general formula Bilt-B-HI (B = base molecule) with
weakly acid solutions of bismuth salts and potasiun iodide. The cincho-
nine double io<iide is orange-red.
^Procedure.Â piece of filter paper is impr^nated with the cincho-
nine solution, and a drop of the slightly acid test solution is placed on it.
An orange-red fleck indicates the presence of bismuth.^'
lAmit of Identification: 0.14 y bismuth
Reagent: Cinchonine solution. 1 g. cinchonine is dissolved by
warming in 100 ml. water containing a little nitric acid.
After cooling, 2 g. potassium iodide is added.
Test for bismuth in the -presence of other metals

Owing to the iodide content of the retênt solution, the bismuth
test is affected by the presence of copper (II), lead, and mercury salts.
Nevertheless, the test for bismuth may be carried out in the presence
of these interfering metal salts, since they diffuse at different rates through
the capillaries of the paper, and are fixed in different zones.
When a drop of test solution containing bismuth, coppa*, mercury
and lead is placed on filter paper impregnated with the reagent, four
different zones can be observed:
1. A white central ring, which contains the mercury. -
S. An orange-colored ring of the bismuth compound.
S. A yellow ring of lead iodide.
4. A brown ring of iodine, liberated by the cupric (II) salts.
The different rings or zones are wider or narrower according to the c<m-
centratibn of the different metals.
" F. Pavellm, loc. cit.
E. L6ger, Z. anal. Chem., 28, 374 (1889).
" F. Feigl and F. Neuber, Z. anal. Chtm., 6S, 373 (1923).
60 II. TESTS FOH METALS
The sensitivities of the bismuth test on filter paper, using capillary

separation from the other metals, are: I
a) Bismuth in the presence of lead '
Limit of Identification: 12 y bismuth I
Proportion Limit: BiiTh = 1:112
b) Bismvih in the presence of copper
Limit of Identification: 12 y bismuth
Proportion Limit: BiiGu. = 1:168
c) Bismuth in the presence of mercury
Proportion Limit: Bi:Hg = 1:100
d) Bismuth in the presence of cadmium
Cadmium does not affect the test. ,
Bismuth in the presence of copper, mercury, and had

Proportion Limit: Bi:Cu:Pb:Hg =1:84:53:30
2. Test with alkaline stannite solution with the addition of lead salts/"
Bismuth salts are reduced to metallic bismuth by means of alkaline
solutions of sodiiun or potassium stannite."
2 Bi(0H)3 + 3 NasSnOj = 2 Bi + 3 Na^SnO, + 3 HjO
Lead salts are only very slowly reduced by alkaline stannite solutions
at room temperatures. To test this, a drop of a 1% lead acetate solution
may be placed on the spot plate with a drop of the stannite solution; the
light brown coloration due to the separation of lead is visible only after
3 to 10 minutes.
This slow reaction:
Pb(0H)2 + NajSnOj = Pb + NajSnO., + HÔ
is tremendously accelerated by the simultaneous separation of bismuth."
Even such small amounts of bismuth as can no "longer be detected by
the reduction with stannite are effective. It appears that the induced
reduction of the lead by traces of bismuth is due to the fact that the bis-
muth acts as a crystaUizing center for the lead. This property affords
a test for very small amounts of bismuth.
" F. Fcigl and P. Krumholz, Ber., 62,1138 (1929). See_also C. Porlezza, Atli
soc. set. nat. toscatia, 37, 1 (1928). -' "
" L. Vanino and F. Treubert, Ber., 31, 1113 (1898).
" If for instance 1 ml. of a 1% Bi(NOs)s solution is poured into 25 ml. of 0.1 N
Pb(C!H|02)i solution, and then an excess of alkaline stannite added, lead sepa-
rates immediately. After a few minutes the filtrate gives no reaction for lead on
acidifying with nitric acid and testing with sulfuric acid.
BISMUTH 61
>
The test is specific for bismuth in the acid sulfide group, in the
absence of silver, copper and mercury. The interference of the last
two metals may be prevented as described below.
IfProcedure.A drop of the hydrochloric acid test solution, a drop of
a saturated solution of lead chloride, and 2 drops of stannite solution
are mixed and stirred on a spot plate. In the presence of large amounts
of bismuth, a precipitate of lead appears at once. Smaller amounts
require 1 to 3 minutes-before a definite brown appears, which gradually
intensifies until the lead is completely precipitated. As lead alone
although slowlyis also reduced, a blank test with a drop of hydrochloric
acid, lead chloride Solution, and 2 drops of stannite solution should be
carried out, if small amounts of bismuth are suspected.
Limit of Identification: 0.01 y bismuth
Reagents: 1) Saturated lead chloride solution
2) 25% sodium hydroxide
S) A solution of 5 g. stannous chloride in 5 ml. cone,
hydrochloric acid, diluted to 100 ml, with water.
The stannite solution is made up shortly before use
by mixing equal volumes of 2) and S).''
Test for bismuth in the presence of copper
Copper salts are slowly decomposed by stannite solutions with de-
position of cuprous oxide, and thus interfere with the detection of small
amounts of bismuth. By the addition of potassium cyanide, the copper
is converted iato K4Cu2(CN), which is quite stable to stannite. Thus
even very small amounts of bismuth may be detected in the presence of
much copper.
^ProcedureÂ drop of the test solution is mixed on the spot plate
with a drop of a saturated solution of lead chloride, a drop of 2 iV sodium
hydroxide, a drop of 5% potassium cyanide, and finally 2 drops of stannite,
and stirred. According to the bismuth content, either inmiediately or
after a few minutes, a brown to black coloration appears.
In this way 0.1 y bismuth in the presence of 1 mg. copper, that is in
the ratio of 1:10,000, can be clearly recognized in 1 drop, if a blank deter-
mination on a 1% copper solution is carried out.
Test for bismuth in the presence of mercury
Since stannite reduces mercury salts, and the free mercury makes it
impossible to see the liberated bismuth, the mercury must be removed
" A freshly prepared stannite solution is essential. On long standing, tin is
often precipitated from alkaline stannite solutions, the stannite being partly oxi-;
dized, partly reduced: 2 NajSnOj + Hrf) = NatSnO, -|- 2 NaOH H- Sn.
OS n . TESTS FOR METALS
before trying tiie stannite test. A drop of the test solution is evaporated
to dryness in a porcelain microcrucible, and carefuUy ignited to volatilize
the mercury. The residue is taken up in a drop of N hydrochloric acid
and tested for bismuth as jiist directed. In this way, 0.05 y bismuth can
be detected in the presence of 0.6 mg. mercury, which represents a ratio of
1:10,000.
3. Test by Inndnescaice of the hydrogen flame.'* Bismuth gives a
cornflower-blue coloration to the hydrogen flame. Extremely small
amounts of bismuth can be detected when the sample, mixed with alkaline
earth carbonate, is placed in the flame.
fProcedoreThe hydrcên is obtained from a Kipp's apparatus,
and is washed by passing through two wash bottles of water. After
testing for freedom from the explosive admixture of oxygen, the gas is lit
at a delivery tube of platinum or porcelain. Theflameshould be not more
than 0.5 cm. long. Pure calcium carbonate and water are mixed to a
thin paste, and a small amount is taken either with a loop of platinum
wire, a Wedekind magnesia rod, or a narrow strip of mica.
The calcium carbonate is gently ignited in the flame, then the not
more than slightly acid test solution of bismuth added by means of a second
platinum loop, and the ignition repeated. After cooling, the preparation
is repeatedly laid in the lower part of the hydrogen flame for a short time.
In the presence of bismuth, at the moment of lighting up the flame, a com-
fllower-blue color is perceptible. As soon as the lime begins to glow, the
luminescence disappears, being masked by the yellow glow.
Limit of Ideniifieation: 0.004 y bismuth
Only antimony and manganese compounds give analogous lumines-
cence reactions, the former green-blue, the latter yellow (see page 86)^
4. Test vi^ fotbaAma chromium thiocyanate.'' Bismuth salts react,
in solutions of mineral acids, with potassium chromium thiocyanate
K,Cr(CNS) as follows:
Bi+++ -I- Cr(CNS)r" = BiCr(CNS),
giving insoluble brick-red bismuth chromium thiocyanate.
Only mercury, silver, thallium, and lead salts also give prfscipitates
under these conditions, but they are pink or yellow.
1[IôcedareA droplet (0.012 ml.) of the test solution is placed on
filter pîer and dried over a warm asbestos plate, and treated with a drop
of an alcoholic solution ofliie reagent. After drying, a drop of sulfuric
acid is added. According to the bismuth content, a brick-red fleck or
rinig is formed.**
M J. Donau, Monat$h., S4, 949 (1913).
C. Mahr, Z. anorg. allgem. Chem., 808, 313 (1932).
coppnt OS
LimU of Identification: 0.4. y biamuth

Reagents: 1) 3% alcoholic solution'* of K,Cr(GNS)
2) Sulfuric acid 1:2
5. Other tests for iMsmath. 1. The stannite reductioa of bismuth solu-
tions containing lead (see page 60) can, obviously, also be carried out in
lead-free solutions, with reduced sensitivity however {Id". LimU: 1 7 Bi).
2. Instead of stannite, a solution of K4Mn(CN)i m^y be used as
reducing agent.*^ Black BiO and K|Mn(CN) are formed {Id". Limit:
10 7 Bi in a 0.01 ml. drop). This test is conaderably less sensitive than
the tests 1 to 4 just described, but it may, however, be carried out in the
presence of Hg, Ag, and Cu salts.
5. Bismuth may be detected by forming black Bilj and converting
this, by means of hot water, to red BiOI {Id". Limit: 26 7 Bi).
4. The orange-red double iodide of bismutii and the base, is precipi-
tated from nitric acid solutionis of bismuth salt by an alcoholic solution of
quinoline and potassium iodide" {Id". Limit: 1 7 Bi). Pb^^, Sb+++,
Hg^", and Ag+ ions give black precipitates. Interference of Cu++ and
Fe"*"^, due to liberation of iodine, may be prevented by placing a drop of a
solution of NaHSOj on the paper impregnated with the reagent.
5. A yellow-green color develops if paper impregnated with thio-
acetamide is spotted with the acidified bismuth solution." {Id". Limit:
7 7 Bi).
COPPER
1. Test by catalytic acceleration of the ferric-tfaiosidfate reaction."
When a solution of a ferric salt reacts with a solution of an alkali thiosulfate
a transient deep violet color results. The complete reaction can be ex-
2 Fe+++ + 2 S,Or" - 2 Fe++ -|- SiOT"

The intermediate color indicates that this equation is merely the net
representation of the stoichiometric consumption of the reactants, whereas
the real course of the reaction must be quite different. Actually, the
reaction occurs in two stages." In the first {1) the violet complex anion
" For preparation, see C. Mahr, loc, dl.
" N. A. Tananaefif, Z. dnal. Chem., 108, 419 (1936).
" G. Lochmann, Z. atud. Chem., 86, 241 (1931).
M . V. Gaptschenko and O. G. Scbeinziss, Chem. Abtiracit, 33, 1212 (1938).
" N. W. Wawilow, Chem. Abitracte, 82, 5725 (1938).
" F. L. Hahn and G. Leimbach, Ber., 66, 3070 (1922).
> J. Holluta and A. Martini, Z. anorg. allgem. Chem., 140, 208 (1924). See aUo
H. Schmidt, Z. phytik^Chem., A148, 321 (1930); Z. EltktrocKtm., 8S. 700 (1930).
64 n . TESTS FOR METALS
FeCSjOs)! is produced instantaneously, and it then reacts at a measurably

slow rate with, the Fe+++ ions (S). The summation of these partial reac-
tions gives the net equation of this redox reaction:
Fe+++ + 2 SjOr -* FeCSjOs)? (rapid) (1)
FeCSjOs)! + Fe+++ - 2 Fe++ -f S 4 0 r (slow) (3)
2 Fe^++ + 2 SjOr -* 2 Fe++ + SSr (slow) (1 + 2)
Copper salts accelerate the second partial reaction and therefore
speed up the total reaction.'* Consequently, the intermediate violet color
due to the Fe(S203)r ions disappears far more rapidly when copper ion's
are present. This effect ia probably due to an intermediate production of
Cu(I) salt, in that the complex ion does not react with ferric ions as shown
in (^), but rather with cupric ions as given in {4). The resulting Cu(I)
can then react very rapidly with Fe(III) as shown in (5) regenerating
Cu(II). The summation of (4) and (5) gives the partial reaction (2),
in which the catalyst does not appear as a reactant:
Fe(S203)r + Cu++ -> Cu+ + Fe++ + SiO?" (rapid) U)
Cu+ + Fe+++ - Cu++ + Fe++ (rapid) (5)
Fe(SsOa)7 + Fe+++ -* 2 Fe++ + S,Or (rapid) {4 + 5)
The reaction between Fe"''++ and SsOr" can be carried out in thei pres-
ence of an alkali thiocyanate. Under these conditions, the CNS~ acts
not only as indicator for the ferric salt, by producing the soluble red
Fe(CNS)3, but it also reduces the concentration of the Fe+++ ions, since
Fe(CNS)3 is only slightly dissociated. Consequently, the rate of the reac-
tion between Fe+++ and 8207" ions, and therefore the velocity of all the
partial reactions in which Fe+++ ions participate, is decreased. Accord-
ingly, the catalyzed acceleration due to copper salts is particularly evident
under these conditions. Therefore, extremely small amounts of coppir are
definitely revealed by the more rapid fading of the color that results from
the action of Na2S203 on Fe(CNS),.
The velocity of the Fe(CNS)3-Na2S203 reaction depends on variations
in the concentration ratios of iron:thiocyanate:thiosulfate, on the acid
content, and on the temperature. Alimainum, zinc, and nickel salts, and
especially arsenic, retard the reaction.
It must be noted that water and many reagents often contain traces
of copper that can introduce significant errors in comparative tests. Such
traces can be removed from water by shaking it_with CaF2 or talc and sepa-
rating the adsorbent by centrifuging." ' -
Compare also A. C. Oudemans, Z. anal. Chen,., 6, 129 (1867).
" F. Pavelka, Mikrochemie, 23, 202 (1937).
COPPER 65
UProcedurÂ drop of the test solution and a drop of distilled water

are placed in adjacent depressions of a spot plate. A drop of ferric thio-
cyanate solution and 3 drops of 0.1 N sodium thiosulfate solution are
added to each, and stirred with a glass rod. The time of decolorization of a
copper-free solution is 1| to 2 minates. The decolorization of the test
solution containing as little as 1 -y of copper is almost instantaneous. For
even very small amounts of copper, the difference in time as compared with
the blank test is appreciable.
Ldmit of Identification: 0.02 y copper
Reagents: 1) 0.1 N solution thiosulfate solution
2) Ferric thiocyanate solution. 1.5 g. ferric chloride and
2 g. potassium thiocyanate in 100 ml. water
2. Test with benzoin oxime." The so-called acyloin oxime compounds,
of the general formula R-CH(OH)-C(:NOH)-R', give, in neutral solu-
tions, insoluble flocculent green precipitates with solution of copper salts.
The green copper salt of benzoin oxime, C6H6-CH(OH)-C(:NOH)-C6H6,
is completely iiisoluble in dilute ammonia, and can therefore be used for the
detebtion of copper. The insolubility of the copper benzoin oxime in
ammonia is probably due to the saturation of the partial Valency field of
the copper by the two phenyl groups, forming an inner complex compound,
C,HsC CCH,
I II
O NO
in which the copper atom loses the capacity for adding ammonia molecules
and going into solution as a copper ammine salt.
If other metallic salts, that form precipitates with ammonia, are
present in such amount that they interfere with the recognition of the ben-
zoin oxime, then their precipitation can be prevented by the addition of
sodium potassium tartrate. The sensitivity of the copper test is, however,
somewhat reduced by considerable amounts of tartrate. Large amounts
of ammonium salts also prevent the precipitation of the benzoin oxime.
Thus, if solutions are strongly acid, or contain ammonium salts, a drop
should be evaporated and ignited. The benzoin oxime reaction is carried
out only after the residue has been taken up in a drop of dilute hydrochloric
acid.
liProcedureA drop of the weakly acid test solution is treated on
filter paper with a drop of benzoin oxime, and held over ammonia. A
green coloration indicates copper. In the presence of large amounts of
F. Feigl, Ber., 66, 2032 (1923); Mikrochemie, 1, 76 (1923). 6
86 n . TESTS roB METALS
other ions precipitated by ammonia, a drop of Rochelle salt is placed on

the filter paper before the addition of the oxime. j
The test may also be carried out on quantitative filter paper (S & S
No. 589) impregnated with a saturated solution of benzoin oxime.
Limit of Identification: 0.1 y copper
Reagents: 1) 5% alcoholic solution of benzoin oxime**
S) 10% Rochelle salt (sodium potassium tartrate)
If the test solution is strongly acid, a drop of ammonia is first placed
on the filter paper, then a drop of the test solution, and the paper left
for several minutes in a heated drying oven. In this way, 0.5 y copper
can be detected in the presence of 1000 times the amount of hydrochloric
acid.
The following procedure may also be used.*^ A quantitative filter
paper is impregnated with 5% alcohoUc solution of benzoin oxime, and,
after drying, it is cut into strips 1 mm. wide and 10 mm. long. One
of these strips is dipped into a warm drop of the test solution. After a
few minutes, a distinct green zone develops, which, on treatment with
ammonia, becomes stronger.
Limit of I'dentification: 0.05 y copper
The reaction is generally not interfered with by any other metallic
salts, but large amounts of neutral salts reduce the sensitivity somewhat.,
3. Test with salicylaMoxime.'' Salicylaldoxime (I) gives a yellow green-
l y precipitate of the inner complex copper salicylaldoxinie (II) with
acetic acid solutions of copper salts.
H
^ ^^ NOH
(II)
Most other metal ions give precipitates with salicylaldoxime only in
neutral or weakly alkaline solutions, although palladium and gold salts
in acetic acid solutions also give precipitates of Pd (CrHtOtNt)} and inetallic
gold, respectively.*'
IfPntcednreÂ drop of the test solution, previously neutralized and
then slightly acidified with acetic acid, is mixed in a micro test tube with
* For preparation, see A. Werner and P. Detscheff, Bet'., 38, 72 (1905).
" W. Geilmann and K. Brtlnger, OlatXeO^. Ber., 87, 329 (1929).
* F. Ephraim, Ber., 63. 1928 (1930).
H. Holier, Z. anal. Chem., 95,398 (1933).
COPPER 67
a drop of the reagent. According to the amount of copper present, a

yellow greenish white precipitate or opalescence appears.
Limit of Idenii^xxUion: 0.5 y copper
Reagent: 1 g. salicylaldoxime"' is dissolved in 5 ml. alcohol and
the solution poured drop by drop into 95 ml. water at
30''C. An oily suspension is formed that almost disappears
on gentle shaking. The solution is then filtered.
4. Test with o-tolidine and ammonium thiocyanate." When even very
dilute solutions of copper salts are united with benzidine and alkali cyanide
(see page 208) or alkali bromide, iodide, or thiocyanate, benzidine blue
(see page 73) is produced by oxidation. Since cupric salts, of themselves,
do not oxidize benzidine,J;his effect obviously involves a raising of the
oxidation potential oi Cu(II) salts by binding the Cu(I) salts, formed
during the oxidation, into complex or insoluble halides. Furthermore, it is
likely that complex Cu-benzidine"*^ ions are formed.
If, instead of benzidine, the homologous base o-tolidine is used, a
more sensitive test for copper results. o-Tolidine has the advantages
that its solutions are more stable and more easily oxidized by cupric salts.
Salts of silver, mercury (I), iron, thallium (III), cerium (IV) and
gold, and also chloroplatinic acid, interfere with the reaction. Silver salts
may be removed by precipitation as chloride, and the effect of iron salts
may be masked by the addition of alkali fluoride. The other strongly
oxidizing metal salts, which interfere with the test owing to their oxidation
of benzidine, may be reduced with bismuth amalgam and rendered harm-
less. Manganese salts only interfere when present in high concentrations,
and give a slight blue color with the reagent after a considerable time.
When this occurs it is advisable to carry out a blank test with a saturated
solution of manganese sulfate.
fProcedoreA drop of the reagent solution is placed on filter paper,
-followed by a drop of the neutral or slightly acid test solution. A light or
dark blue stain is formed according to the amount of copper present.
Limit of IdentifiaUion: 0.003 y copper (in 0.015 ml.)
Reagent: A solution of 0.1 g. o-tolidine and 0.5 g. NH^CNS in
5 ml. acetone
5. Test wifli phoqdiomolybdic acid." Molybdeniun in the coordinated
molybdenum trioxide molecules of phosphoniolybdic acid H1PO4 12M0. aq
is far more reactive than in free molybdic acid or in normal molybdates.
' For preparation, see L. Claisen and O. Eisleb, Ann., 401,99 (1913).
" L. Kul'berg, Mikrochemie, 20, 153 (1936).
" F. Feigl and F. Neuber, Z. anal. Chem., 62, 376 (1923).
68 II. TESTS FOR MKTALS
This increase in activity is due to the form of attachirient of the molyb-

denum trioxide molecules, and is shown by the fact that it is reduced by
certain organic and inorganic compounds that have Utile or no effect on
molybdic acid and normal molybdates. Potassium cuprocyanide, formed
from copper salts and potassium cyanide,
2 CuSO* + 6 KCN = KjCus(CN)4 + (CN)j + 2 K2SO4
is among the compounds which can reduce the molybdenum in phos-
phomolybdates to "molybdenum blue." This reaction is utiUzed as a
spot test.
[[ProcedureA drop of the test solution followed by one of potassium
cyanide and one of phosphomolybdic acid, and finally a drop of dilute
hydrochloric acid, are placed on filter paper. According to the amount of
copper present, a more or less deep blue color is formed, due to molybdenum
blue.
Liimit of Identification: 1.3 T copper
8) 1% phosphomolybdic acid solution (for preparation,
see page 85)
S) Dilute hydrochloric acid
Large amounts of nitric acid should not be present when carrying
out this test. The other metals of the second group affect the test for
copper either not at all, or only in a slight degree. Copper can be detected
in the presence of other metals in the following limiting proportions:
2.5 T copper in presence of
700 times the amount of mercury
2 . 5 7 copper in presence of
900 times the amount of lead
2.5 -y copper in presence of
400 times the amount of bismuth
4.0 -y copper in presence of
300 times the amount of mercury
SOO times the amount of lead
120 times the amount of bismuth
and 280 times the amount of cadmium
6. Test with l,2-diammoanthraqiunone-3-sulfoiuc acid." The red-violet

aqueous alkaline solution of l,2-diaminoanthraquinone-3-sulfonic acid (I)
turns deep blue on the addition of small amounts of copper salts. Larger
quantities produce a blue precipitate. In view of the constitution of the
reagent, this change probably .is due to the formation of a complex copper
salt in which the Cu atom is coordinated as shown in (II) arid (III).
" R . Uhlenhuth, Chem.-Ztg., 34, 887 (1910); H . " E . Ballaban, Mikrochemie
ver. Mikrochim. Ada, 27, 62 (1939).
COPPER 69
-NHj
>Cu
-NH,
(I) (II) (III)
When compounds of this type are isolated, however, their composi-

tion does not correspond to the formula given here.'* Most of the colored
material consists of hydrous cupric oxide. Consequently, this reaction
involves an adsorption of the reagent itself, or of small quantities of its
copper salt, on the CuO-xHjO. Such adsorption compounds are known
as color lakes.
In dilute solutions, cobalt and nickel salts give green-blue and dark
blue colorations, respectively; flocpulent precipitates of the same colors
separate from more concentrated solutions. Other metal ions do not pro-
duce colored products, but it should be noted that certain accompanying
materials may give precipitates because of the alkaline reaction medium.
If the precipitates are colorless, the copper reaction can indubitably be
recognized, because, when the reaction is positive, white precipitates as-
sume a uniform blue color. The blue of the complex copper salt can be
seen when colored precipitates such as Fe(0H)3 are present, if steps are
taken to coagulate the precipitate (warming, stirring, centrifuging). A
further procedure for detection by isolation of cuprous thiocyanate will be
discussed later.
Cyanides interfere with the reaction because they form stable com-
plex cuprous cyanide. Under these circumstances, the procedure must
include fuming with sulfuric acid or ignition. Tartrates, citrates, oxalates,
and phosphates do not interfere with the test.
1[ProcedureA drop of the neutral or acid test solution on a spot
plate, or in a microcrucible, is treated with a drop of the reagent and then
made alkaline with 1 N sodium hydroxide. If the color changes from red-
violet to cornflower blue, copper is present. If very small quantities of
copper are involved, a mixed color appears, and, in this case, it is best to
use not more than a microdrop of the reagent and to compare the color
with that obtained from a solution known to contain no copper.
' Filter paper impregnated with the reagent solution may also be used,
A drop of the neutral or extremely weak acid test solution is allowed to
" J. V. Dubsk^ and V. Benco, Z. anal. Chem., 94,19 (1933).
70 II- TESTS n>B HXTAUS
soak into the paper, and then is spotted with a drop of 1 AT sodium hy-
droxide. A blue fleck or ring, depending on the eoi^>er content, appears
on the red-violet reagent paper. The prepared paper is stable.
Limit of Identification: 0.02 y copper
Concentraiim Limit: 1:2,500,000
Reagent: A solution of 0.05 g. l,2-dianiinoanthraquinone-3-sulfonic
acid^' in 100 ml. water. The reagent solution is stable.
The following procedure is recommended when consderable quantities
of accompanying materials, particularly cobalt and nickel salts, are present.
A drop of the test solution is placed on filter paper and dried (drying oven).
Tlie spot is then treated with a drop of potassium ihiocyanate solution
containing sulfur dioxide, and dried again. This treatment produces
difficultly sduble cuprous thiocyanate, which remains fixed in the capil-
laries of the paper. Manganese, cobalt, nickel, or other heavy metal
salts can be removed by bathing the paper repeatedly in potassium thio-
cyanate solution and finally in distilled water. The dried paper is then
spotted with the alkaline reagent soluti(i.
Reagents: 1) ECNS solution containing SOj. A freshly prepared
mixture of 1 iVKCNS and HiSOiin the proportion2:l..
S) Alkaline reagent solutami: 0.05 g. 1,2-diaminoanthra-
quinone-3-sulfonic acid in 50 ml. distilled water pbu
50 ml. 1 iV^ NaOH.
7. Test with mbeapic add/* An alcoholic solution of rubeanic acid (I)
gives a black precipitate of copper rubeanate from ammoniacal or w e ^ y
acid solutions of copper salts. This precipitate has the constitution of tm
inner, complex salt of the di-imido form of rubeanic acid (II):
H,NCCNH, HN^ I I ^NH

B i s s
8 8 \ /
I cu
(I) (II)
For the mechanism of the salt formation, see page 118.

This precipitation of copper with rubeanic acid also takes place in
ammoniacal, tartrate-containing solutions, but not in alkaline cyanide
solutions. Only cobalt and nickel ions react under the same conditions, to
give brown and blue-red precipitates respectively. The test is extremely
sensitive, and imder suitable conditions (see p. 71) <ian also be carried out
in the presence of cobalt and nickel salts.
" For preparation, see R. Uhlenhuth, Chem. Zentr., 1911,1,6Q2; German Pat.
231,091; FnedUlnder, 10, 688 (1910-12).
' Pr. RAy and R. M. RAy, Quart. J. Indian Chem. Soc., 8,118 (1926); Pr. R4y,
Z. anal. Chem., 79.94 (1929).
CDPPBR 71
f Procedure-A drop of the solution, as near neutral as pooible, is

placed on filter paper, held over ammonia, and treated witii a drop of the
reagent solution. A black fleck or circle indicates copper.
Even the traces of copper sometimes present in distilled water give a
positive reaction. TTierefore, in testing for small amounts of copper, a
blank must be carried out with copper-free distilled water (see page 64).
The following figure are for the limit of identification using a micro-
drop (0.015ml.).
The sîsitivity of the reaction is reduced in the presaice of large
amounts of ammonium salts.
In the presence of 400 times the amount of iron or cadmiimi 0.48 y
of copper can be detected.
Limit of IderUification: 0.006 y copper
Concerdration Limit: 1:2,500,000
Redqents: 1) Ammonia
^) 1% alcoholic solution of rubeanic acid''
Test for copper in the presence of nickel and ccbaU by capillary separation''*
As already stated, cobalt and nickel, as well as copper, produce
colored rubeanates from neutral, ammoniacal or tartrate-containing solu-
tions. The copper salt, however, is the least soluble, and accordingly, has
the lowest solubility product. TTiis value is attained with even very small
amoimts of copper reacting with the slight, but adequate concentrations of
the di-imide form of rubeanic acid found in alcohol solutions of this reagent.
Nickel and cobalt are precipitated by rubeanic acid either sUghtiy, or not
at all, if the test solution contains free acetic acid. The conditioning factor
is the relative concentration of the acid and metal salt. Copper, on the
otêr hand, is precipitated quantitatively.
Since, in practice, the nickel or cobalt content of the test solution is
unknown, and therefore the correct amount of acetic acid cannot be added
exactly, this sensitive test for copper cannot be carried out in a test tube if
cobdt or nickel are present, as they may also be precipitated. When,
however, the test is carried out on filter paper, traces of copper can easily
be detected, even in the presence of large amounts of nickel or cobalt.
Capillary separation is employed.
^Procedure-A drop of the test solution, acidified with acetic acid,
is placed on filter paper impregnated with rubeanic acid. (Spot test paper
is best.) Two zones are formed of differing acetic acid content. In the
central zone the acid concentration is the greatest, and here only the copper
is precipitated in the form of an olive green or black circle. The nickel
" For prep&ffttioB, aee R. Wdliwr, / . prakt. Chtm., ^. 129 (18S4)..
" F. Feigl and H. J. KMWli^> Mikreehtmie, 8, 230 (1930).
72 II. TESTS FOR METALS
diffuses farther and forms a blue to violet ring afound the central zone.
This ring develops more towards the middle as the acetic acid evaporates.
In the presence of cobalt, the same process 'occurs, except that the
central zone is surrounded by a yellow-brown ring of cobalt rubeanate.
When both cobalt and nickel are present, the copper can still be detected
through capillary separation. The test solution should not contain more
than 2% cobalt and/or nickel.
Ldmit of Identification: 0.05 7 copper /in the presence of 20,000
Concentration Limit: 1:1,000,000 times the amount of nickel
in the presence of 2000
Limit of Identification: 0.25 y copper J times the amount of co-
Concentration Limit: 1:200,000 Ibalt (in acetic acid solu-
ition)
When the test is only concerned with the detection of copper in
the presence of cobalt, a drop of the neutral test solution may be placed
on the paper impregnated with rubeanic acid. The copper rubeanate
is formed in the central ring surrounded by a concentric brown-yellow
ring of cobalt rubeanate.
Limit of Identification: 0.05 7 copper fin the presence of 20,000
Concentration Limit: 1:1,000,000 |^times the amount of cobalt
8. Test with dithizone." Diphenylthiocarbazone (dithizone) (see page
57), with many of the heavy metals, forms insoluble colored inner com-
plex salts, that can easily be extracted with organic solvents. The cop-
per salt is yellow-brown. It is formed in solutions that are neutral,
ammoniacal, or that contain ammonium salts. When a dilute solution of
the reagent in carbon tetrachloride is used, and a small amount of this
is shaken with the test solution, copper can be detected in the presence
of large amounts of other heavy metals (with the exception of the noble
metals and mercury). The greater tendency for copper dithizone to be
formed than the other heavy metal dithizone salts leatls-toJts formation
by itself. ~
^ProcedureA drop of the neutral or weakly ammoniacal test solu-
tion is shaken with a drop of a solution of dithizone in carbon tetrachloride
in a stoppered micro test tube. The green color of the reagent changes
immediately to yellow-brown.
Limit of Identificaiion: 0.03 7 copper
Reagent: Solution of 1 to 2 mg. dithizone in 100 m|. carbon tetra-
chloride ^ ^
" H . Fischer, Mikrochemie, 8, 319 (1930); Z. angew. Chem., 42, 1025 (1929).
COPPER 73
The test can also be carried out on filter paper or on a spot plate;
a stronger reagent solution (about 10 mg. of dithizone in 100 ml. of carbon
tetrachloride) should be used. The limit of identification is then 0.2 y
copper.
Table 2 shows the sensitivity of the test in neutral copper solutions
in the presence of other heavy metals which react with dithizone.
9. Other tests for copper. 1. Filter paper is spotted successively with 1
drop of the test solution, 1 drop of 10% solution of benzidine in acetic
ester, and 1 drop of saturated KBr solution. A blue fleck appears'"
(/d". Umii: 0.6 y Cu).
2. The addition of (NH4)2Hg(CNS)4 to a solution containing both
Cu++ and Zn++ does not produce a mixed precipitate of white ZnHg(CNS)4
and yellow-green CuHg(CNS)4, but, instead, a violet precipitate." If
one drop of the test solution, one of 1% zinc acetate, and one of a solution
containing 8 g. HgCU and 9 g. NH4CNS in 100 ml. water are placed on
TABLE 2
Other metallic salt present Limit o{ identifica- Other metals pres- Proportion limit,
tion, -7 in 0.0s ml. ent, 7 in 0.05 ml. Cu: foreign metal
PbCCHiO-aq 0.05 13,700 1:246,000

ZnSOi-aq 0.07 2,000 1: 28,500
Cd(CjH,0,)-aq 0.05 7,200 1:144,000
NiS04-aq...... 0.1 4,000 1: 40,000
filter paper or a spot plate, a violet precipitate forms'^ (/d". Ldmit: 0.1 y
Cu). Nickel and cobalt interfere; iron must be masked by adding fluoride.
3. Dimethylaminobenzylidene rhodanine (see page 43) reacts with
cuprous salts (which behave in many ways similarly to Ag salts) to give
a red precipitate {Id". Limit: 0.6 7 Cu)." Cupric salts do not react, and
must therefore be reduced with HjSOj before testing.
4. A red stain is formed when a drop of an acetic acid solution of
8-hydroxyquinoline followed by a drop of the test solution and a drop
of a 25% KCN solution are placed on filter paper" {Id". Limit: 0.4 7
Cu). The test depends on the formation of the complex Cu (I) cyanide.
(CN)2 is also formed, and reacts with the hydroxyquinoline, giving a red
" F. Feigl and K. Lettmayr, unpublished studies. See also F. Feigl and F.
Neuber, Z. anal. Chem., 62, 375 (1923).
" R. Montequi, Chem. Abstracts, 81, 2858 (1927).
F. Feigl, Mikrochemie, 7, 6 (1929).
O. Funakoshi, Chem. Abstracts, 23, 4644 (1929).
A. S. Komarowsky and N. S. Poluektof, Z. anal. Chem., 96, 23 (1934).
74 II. TB8TS FOR ICETALS
1
color. Neither ondizing agents nor metallic ions giving colored oxine
compounds should be present.
5. A violet to dark brown color appears if 1 drop of the test solution
is treated with 1 drop of 25% HBr (/d. lAmit: 0.15t-y Cu). Ag+, Hg(I),
Pb-H-, Cd++, Fe(III), and CI" interfere.
6. At pB. 7 to 8, an orange coloration appears if a copper solution is
treated with a 1% water solution of 2-nitro8o-l-naphthol-4-8iilfonic acid**
(Id". Limit: 0.01 y Cu). Co"*^ and Fe(II) give similar reactions.
7. Traces of copper accelerate the oxidation of HCl-phenetidine by
hydrogen peroxide (violet color).*^ The test may be carried out as a drop
reaction in a microcrucible. ^
8. Diphenylcarbazone and its substitution products, in neutral or
slightly acid solution, may be used as sensitive but nonspecific reagents for
copper** (Id\ Limit: 0.002 y Cu or 0.05 r Cu in neutral or 0.1 N HCl
solution, respectively, with di-m-nitrophenylcarbazone).
CADMIUM
1. Test with ferroos dipyridyl iodide.** The organic base a,a'-dipyridyl
(a,a'-dip) produces an intense red in acid or neutral solutions of ferrous
salts. The color is due to the formation of the stable complex cations
Fe(a,a'-dip)j^ (see page 122). These complex cations combine with
anions that have a large atomic volume, forming slightly soluble, red crys-
talline compounds. The precipitation occurs, in part, in even very dilute
solution. Accordingly, complex anions, such as Hgli , Cdl* ,
Ni(CN)4, etc. in particular, and likewise considerable quantities of io-
dides, serve as precipitants for Fe{a,a'-dip)t* ions.
The formation of red Fe(a,a'-dip)-Cdl4 can be used for the detec-
tion of cadmium if a saturated water solution of Fe(a,a'-dip)|Ij containing
an excess of I~ ions is used as reagent. The ionic species in such a solution
then unite with Cd++ ions: ~
Fe(a,a'-dip)p- + 4 I" -j- Cd++ -> Fe(a,a'-dip),-Cdl4
A red-violet precipitate is obtained. This is characterized by the fact

that both its cationic and anionic constituents are complexes. This
accounts for the remarkable sensitivity and selectivity of the test for
cadmium.
f ProcedureThe reaction is carried out on thick filteft paper (S &
S 601). A drop of the weakly acid, neutral, or ammOniacal test solution is
" S. Augusti, Mikrochemie, 22, 139 (1937).
" L. A. Sarver, Ind. Eng. Chem., Anal. Ed., 10, 378 (1938).
' L. Szebell^dy and M. Ajtai, Chem. AbstracU,33, 4155 (1939).
" P. Krumholz and F. Hdnel, MtfcrocAim. AcUr, 2, 180 (1937).
F. Feigl and L. Miranda, Ind. Eng. Chem., Anal. Ed., 16,141 (1944).
QcADHnm 75
placed on the paper and is inunediately, before ike drop has been absorbed
by the paper, treated with a drop of the reagent. Reaction occurs at once
and, after the liquid has soaked in, the Cd precipitate is left as a red fleck
or ring, which, because of its intense color, stands out against the reagent
solution that has spread tiirough the paper. A blank is necessary only if
very small quantities of cadmium are to be detected.
The test solution and the reagent can also be brought together in a
centrifuge tube. In this case, it is best to place a drop of the reagent in
the tube and then introduce a drop of the test solution, and to centrifuge
without previously mixing the two. A red precipitate is produced in the
constricted end of the tube. It is rather striking that the sensitivity of the
test is considerably less if the drops are mixed before centrifuging.
Limit of Identification: 0.05 y cadmium
Ccmcentration Limit: 1:1,000,000
Reagent: 0.25 g. a,a'-dipyridyl and 0,146 g. FeS04-7H,0 are dis-
solved in 50 ml. water, 10 g. KI added, and after shaking
vigorously for 30 minutes the Fe(a,a'-dip)Ij is filtered off.
The resulting saturated solution of Fe(a,a'-dip)Ij contains
excess KI. The solution is stable; in case it becomes turbid
on long standing, it should be filtered before use.
Test for cadmium in the presence of oiher metals
The direct use of Fe(a,a'-dip)It as precipitant for cadmium is inter-
fered with by those metal ions that form slightly soluble or complex iodides.
Solutions of .Ag, Tl, or Pb salts may be precipitated by the iodide in the
reagent and the precipitates are made red by adsorption of Fe(a,a'-dip)r'"
ions. Cu++ ions in neutral or acid solution liberate iodine forming CujIj
that likewise combines with a,a'-dipyridyl forming colored addition
products.** Hg, Sn, Sb, and Bi salts form soluble complex iodides that
also form red precipitates by union with Fe(a,o'-dip)i^ ions, although
the sensitivity is less in these cases.
Despite the interference of ions that form iodides, the cadmium test
can be made almost specific if the test solution is treated with ammonia,
filtered, and the ammoniacal filtrate then tested with the reagent. The
Cd(NH)t* ions in the filtrate react promptly, whereas, .any .Cu(NH)J^
and ZnCNH*)*"^ ions are inactive. Only T1+ and AgCNHj)? ions, which
likewise enter the anmioniacal filtrate, can interfere, since they form Agl
and Til by combination with the iodide in the reagent. Consequently,
if cadmium is to be detected in the presence of silver and other ions that
form slightly soluble iodides, the foUoiving procedure should be used. The
test solution is treated first with dilute hydrochloric acid. Any precipitate
(AgCl, TICI, HgjClj, PbCl) is filtered off, the filtrate made ammoniacal,
0 Compare G. Tartarini, Gau. ehim. ital., 68,697 (1933).
76 n- TESTS FOR S E T A L S
I
refiltered if necessary, and the ammoniacal filtrate tested with the reagent.
All these operations can be accomplished with one or two drops of the test
solution in microcentrifuge tubes, in which any precipitates can easily be
separated by centrifuging.
The concentration limits of mixtures of cadmiimi and copper, and
cadmium and zinc, which are of practical importance, were determined by
preparing ammoniacal solutions of the respective mixtures. The following
quantities of cadmium could be detected in one drop:
0.08 7 cadmium in the presence of 5000 times this quantity of copper
0.01 7 cadmium in the presence of 5000 times this quantity of zinc
If the detection of about 0.2 7 Cd is adequate, still better limiting concen-
trations can be obtained.
2. Test with di-p-nitrophenylcarbazide." Numerous metal hydroxides,
including cadmium hydroxide, are colored by di-p-nitrophenylcarbazide
(I) and its oxidation product di-p-nitrophenylcarbazone (II).
H H ^ IT H
NNC,H,NO.(p) NNC.HiNOjCp)
0=0/ . o=c(^
NNC.H4N0,(p) N==NC.H,NO,(p)
H H
(I) (II)
The color is probably due to adsorption complexes (lakes). Cadmium

hydroxide precipitated in the presence of (I) is brown. On standing for
some time, the color changes to green-blue, because the carbazide is oxi-
dized to the carbazone (II). The color change is accelerated by formalde-
hyde ; the reason is as yet not known.
This fact can be used to test for cadmium, even though copper is
present. It is necessary to provide conditions which wifl permit the
precipitation of cadmium hydroxide, but not of copper hydroxide. The
divense behavior of the complex cyanides toward formaldehyde can be
utilized. Alkali cyanides react with formaldehyde to produce the salt of
glycolic nitrile, HjC^ ; cyanide ions are consumed (see p. 435).
\CN
The complex cyanides are slightly.dissociated as follows (omitting
the intermediate stages): f
Cd (CN)r" ^ Cd++ -f 4"CN- {1)
Cu,(CN)r ^ C u r -f 4 CN- ()
" K . Heller and P. Krumholz, Mikrochemie, 7, 217 (1929); P. Krumholz and
F. Honel, Mikrochim. Acta, 3,181 (1937). ^
CADMIUM 77
The concentration of the cyanide ion (/) is always sufficient to react with
formaldehyde, thus continually disturbing the equilibrium of the system,
so that sufficient cadmium ions are formed to exceed the solubility product
of cadmium hydroxide. The cadmium hydroxide formed under these
conditions seems to be especially suited for the formation of the absorption
color with the carbazide. Unlike the cadmium compound, the complex
potassium cuprous cyanide decomposes into cuprous cyanide only on
heating; in the cold, the solution remains quite clear.
IfProcedureA drop of the acid, neutral or ammoniacal test solution
is mixed on the spot plate with a drop of sodium hydroxide and one of
potassium cyanide; then a drop of the reagent and two drops of formalde-
hyde are added, with stirring. In the presence of cadmium, a blue-green
precipitate or coloration is formed. The reagent alone, which is red in
alkaline solution, is colored violet by formaldehyde. Thus, with small
amounts of cadmiima, the color should be compared with that of a blank
test.
Limit of Identification: 0.8 y cadmium
Reagents: 1) 10% sodium hydroxide
2) 10% potassium cyanide
S) 40% formaldehyde
4) 0.1% alcoholic solution of dihitrodiphenylcarbazide'*
Test for cadmium in the presence of other metals

In order to prevent the reaction between copper and dinitrodiphenyl-
carbazide, a sufficient excess of potassiima cyanide must be used.
^ProcedureA drop of the test solution, which should contain not
more than 4 g. copper in 100 ml., is stirred on the spot plate with a drop of
sodium hydroxide and 3 drops of potassium cyanide until the copper
hydroxide or cyanide is completely dissolved. Then 2 drops of reagent
and 3 drops of formaldehyde are mixed with the solution. By carrying
out a parallel test with a 15% solution of copper sulfate, the following
values are attained:
Limit of Identification: 4 y cadmium /in the presence of 400 times
If cadmium is to be detected in the presence of ions of Group (2),
then it is best to add ammonia to the test solution, centrifuge, and carry
out the test for cadmium on the supernatant liquid, containing the copper
and cadmium, as described.
" For preparation see P. Krumholz and F. Honel, Mikrockim. Acta, 2, 177
(1937).
The presence of large amounts of ammonium sialts somewhat reduces

the sensitivity. Nevertheless, if a blank test is carried out, 4 y cadmium
in the presence of 250 times the amount of copper, and 2 y cadmium in the
presence of 120 times the amount of copper, can be clearly detected.
3. Test with di^/S-naphthylcarbazone.'^ Di-/3-naphthylcarbazone like di-
p-nitrophenylcarbaaone produces a red adsorption compound with cadmium
hydroxide. Consequently, it is convenient to use the following test in
the same way as the one described ia 2 for the detection of cadmium in
the presence of copper. It should be noted that other metal hydroxides
likewise produce colored products with the reagent.
f ProcedureTwo drops of the neutral or slightly acid test solution
are mixed on a spot plate with 2 drops of the reagent and 1 drop of 2 AT
sodium hydroxide. If cadmium is present the red of the reagent turns to
violet.
hlmii of Identification: 02 y cadmium
Concentration Ldmit: 1:250,000
Reagent: 0.02% solution of di-/3-naphthylcarbazone in methanol*'
Test for cadmium in the presence of copper

Copper interferes with the test. This complication can be obviated
by the method described in 2, if Cd (OH)j is liberated from the cyanide com-
plex by adding formaldehyde. The presence of copper actually increases
the sensitivity of the cadmium test. The excess reagent is decolorized
by oxidationîn the presence of copper salts which obviously act as catalysts.
The reagent adsorbed on the Cd(OH)j retains its color.
^ProcedureTwo drops of the neutral or slightly acid test solutions,
which may contain a maximum of 0.5% copper, are mixed with 1 drop each
of 2 iV alkali and 10% KCN. After all the copper hydroxide has dissolved,
2 drops of the reagent and 2 drops of 40% formaldehyde are added. On
stirring, the color disappears almost entirely within several.minutes, if
cadmium is absent. If present, a more or less intense violet~precipitate
appears, which becomes distinctly visible as the color of the excess reagent
disappears.
Ldmit of Identification: 0.1 -y cadmium fin the presence of 5000 times
4. Other tests for cadmium. 1. Alcoholic solutions of diphenylcarbazide
can'Tie used for spot reactions.** Violet precipitates or colorations are
formed with neutral, ammoniacal, or acetate-buffeced cadmium solutions
(Id". Limit: 4 y Cd). Substituted diphenylcarbazides are better than the
" For preparation, see P. Krumholz and F. Hdnel, loc. cil. (see p. 76).
" F. Feigl and F. Neuber, Z. anal. Chem., 62, 378 (1923).
ABSENIC 79
parent substance with respect to greater selectivity and higher sensitivity

(see page 76).
S. p-Nitrodiazoaminoazobenzene forms a color lake with cadmium.
The reagent consists of a 0.02% solution in alcohol, which is also 0.02 N
with respect to KOH.** One drop of the reagent is placed on thick filter
paper and treated with 1 drop of the test solution that has been acidified
with acetic acid. One drop oi 2 N KOH is then added. If cadmium is
present, a bright pink circle surrounded by a violet-blue ring appears
(7d.'Limit: 0.025 y Cd). The interference by Cu, Ni, Fe, Cr, Co, and Mg
is prevented by adding tartrate. Only Ag, Hg, and NH4 will then inter-
fere. Silver is removed as iodide, mercury as sulfide.
-(6) Acid Sulfide Group
ARSENIC
1. Test with stannous chloride.*' Compounds of both tri- and pentavalent
arsenic are reduced by stannous chloride to elementary arsenic in solutions
strongly acidified with hydrochloric acid. The arsenic is precipitated as a
brownish black precipitate."
2 As-H-HH- + 5 Sn++ -* 2 As 4- 5 Sn++++
2 As+++ -f- 3 Sn++ -^ 2 As -f- 3 Sn++++
The reduction is accelerated by heating. It takes place only in strongly
acid solution, since only arsenic cations or undissociated arsenic halides
react with stannous chloride. In weakly acidified solutions, only arsenic
anions are present, but ho cations, since they undergo hydrolysis:
As*++ + 3 H,0 ? AsOr~ -f 6 H+
Pentavalent arsenic cations behave analogously.
Among the other metallic salts, only those of noble metals and mer-
cury (not, however, antimony salts) are reduced to the metallic state under
these conditions, so that this sensitive test for arsenic with stannous chloride
(the so-called Bettendorf test) is quite specific. To remove the interfering
mercury by simply igniting the sample is not feasible, since many arsenic
compounds (such as arsenic trioxide or arsenic halides) are also volatilized.
When, however, the arsenic is converted into the heat resistant pyro-
arsenate, then the arsenic can be detected in the presence of mercury.
The sensitivity of the test is decreased by the presence of colored
salts in the solution. Examples of these are chromium, cobalt, and nickel
" F. P. Dwyer, Australian Ghent. Inst. J. & Proc., 4, 26 (1937).
' A. Bettendorf, Z. anal. Chem., 9, 106 (1870).
" The precipitate always contains tin; see the detailed atudiea by K. Zwick-
nagel, Z. anorg. allgem. Chem., 161, 41 (1926).
gQ II. TESTS FOB METALS
in considerable excess. Copper salts, however, arei reduced by stannous

chloride to the colorless cuprous chloride, and do not interfere.
If arsenic is to be detected in the presence of large amounts of these
interferences, it is best to carry out the test on the mixture of sulfides
precipitated in acid solution. It must be noted, however, that when
arsenic is present in the pentavalent form, it is slowly and incompletely
precipitated by hydrogen sulfide in the cold. The precipitation can,
however, be remarkably accelerated by the addition of small amounts of
potassium iodide."
ProcedureA drop of the test solution is mixed in a microcrucible
with 1 or 2 drops of ammonia, 1 of hydrogen peroxide, and 1 of concentrated,
magnesium chloride solution. The mixture is evaporated slowly and then
strongly ignited. The arsenic, whether present as sulfide, or in alkaline
sulfide solution, is thus converted into heat resistant MgjAsjOr, while
the mercury salts are volatilized. The residue is then mixed with 1 or 2
drops of an acid stannous chloride solution, and warmed gently. The
formation of a brown-black precipitate or coloration indicates arsenic.
Limit of Identification: 1 y arsenic"
Reagents: 1) Ammonia
2) 10% hydrogen peroxide
S) 10% magnesium chloride
i) Stannous chloride solution (solution of SnCU in 35%
hydrochloric acid)
2. Test by reduction to arsenic hydride and decomposition with silver
nitrate"" or gold chloride.'"
I. With Silver Nitrate
When arsenic hydride is directed on to filter paper moistened with
silver nitrate solution, the wetted areas are colored. If a solution of one
part silver nitrate and one part water is used, arsenic hydride forms a
lemon-yellow fleck of AsAgj-AgNOs, which on treatment with water,
blackens with the deposition of metallic silver. Antimony hydride (SbQj)
colors the periphery of the moistened fleck dark red to black. A capillary
" Potassium iodide acts as a catalyst in that it reduces the arsenic acid thus:
2 A B O * + 4 I - + 4 H+ = 2 AsO, -|- 2 HjO -f- 2 Ij; the iodine liberated is again
changed to the ionic state by the hydrogen sulfide: Ij + HjS -> 2 H+ -I- 2 I~ + S.
" The test is somewhat more sensitive if the reduction with SnCU is carried
out in a micro test tube^ and then extraction done with ether. Very small amounts
of arsenic form distinct black flecks in the water-ether iftterface.
>"M. Gutzeit, Pharm. Ztg., 24, 263 (1879). See'also H. Beckurts, Pharm.
ZerUralhalh, 26, 197, 209, 223 (1884V
' L. W. Winkler, Z. angew. Chem., 30,114 (1917).
ABSENIC 81
separation between the reaction products of the two hydrides is thus

effected with silver nitrate. Filter paper that has been moistened with
more dilute silver nitrate solutions (e.g., in the ratio 1:4) or with am-
moniacal silver nitrate solutions, is blackened immediately by both gases.
Hydrogen sulfide and hydrogen phosphide give similar colorations (by
sulfide or phosphide formation) so that these hydrides must not be
present."^ Mercury salts interfere, as metaUic mercury is deposited on
the surface of the zinc, and this slows up or prevents the formation of
nascent hydrogen and consequently of AsHs."'
If ProcedureThe glass gas apparatus (described on page 31, Fig. 30)
is used. A drop of the test solution is mixed with a few grains of zinc and
dilute sulfuric acid. The apparatus is closed with the funnel with a flat
rim, on which is placed the filter paper moistened with silver nitrate solu-
tion. In the presence of arsenic, a gray fleck is formed.
Limit of Identification: 1 y arsenic
Reagents: 1) Metallic zinc in platelets
2) Dilute sulfuric acid
S) Silver nitrate solution (1:4)
II. With OoU Chloride

The decomposition of arsenic hydride by gold chloride is more sensitive
than by silver nitrate. The metallic gold formed by the reaction:
AsHs + AuCl, + 3 HjO = Au + 3 HCl + HAsO,
is clearly visible even in minute amounts, because it is very finely divided.
f ProcedureThe apparatus is charged with a piece of zinc (the size
of a small pea) and 3 drops of dilute sulfuric acid are added. The funnel
is covered with a piece of filter paper impregnated with gold chloride.
After 10 to 15 minutes in the dark, the filter paper is examined for any
stain that might appear, due to arsenic in the reagents. If the filter paper
remains bright yellow, it is moistened with a further drop of gold chloride,
and 4 more drops of sulfuric acid are placed in the bottom of the apparatus
followed by a drop of the test solution. The stopper is replaced at once.
In the presence of arsenic, a blue to blue-red fleck appears on the filter
paper after 10 to 15 minutes standing.
E. Dowxard, Proc. Chem. Soc, 17,92 (1901), and A. Gotthelf, Z. anal. Chem.,
24, 263 (1905), have suggested fixing HjS, PHi and SbHi by means of cotton wool
impregnated with CujClj, and then identifying the AsHi on mercuric chloride paper
by the formation of the yellow A8(HgCl)s. This procedure can be used as a spot
test.
<* J. Gangl and H. Dietorioh, Mikroehemie, 19, 263 (1936). ?
82 II- TESTS FOR MKTALS
Limit of IderUificcUion: 0.05 y arsenic ,

Concentraiion Limit: 1:100,000
Reagents: 1) 1% solution of HAuCU-21120 |
2) 2 N sulfuric acid (highest purity) I
S) Granular zinc (arsenic-free) I
3. Test with sUver nitrate. Soluble and insoluble arsenates form red-broMm
silver arsenate, insoluble in acetic acid:
MeÂ-sO* + 3 AgNOi = Ag3As04 + 3 MeNO,
If the arsenic is present in the fonh of arsenious acid, arsenite, sulfide,
alkali sulfoarsenite, or sulfoarsenate, it can be cbnverted into the arsenate
by treatment with ammonia and hydrogen peroxide. The test is only
specific in the absence of chromates and ferricyanides. These also give
colored silver salts, insoluble in acetic acid.
f ProcedureA drop of the test solution, or a few grains or more of
the solid sulfide, according to the expected a.rsenic content, are placed in a
microcrucible and warmed with a few drops of ammonia and hydrogen
peroxide. Sulfides must be completely dissolved, or made colorless. The
mixture is then acidified with acetic acid, and 1 or 2 drops of silver nitrate
solution is added. A red-brown precipitate' or coloration appears if
arsenic is preseat.
Limit of IdetUification: 6 y arsenious acid
Conceniraiion Limit: 1:8000
S) 1% silver nitrate solution
Test for alkali arsenites and arsenates in the presence of eadi other.
Arsenites can be detected in the presence of arsenates either by method
(a)or(&):
o) Redudion of iodine to iodide. The reaction of arsenious acid with
iodine, and of arsenic acid with iodides is reversible: ~~
AsjO, -H 2 1 , + 2 HjO ;r AsjO, + 4 I" '-f 4 H+
In alkaline bicarbonate or acetic acid solution the reaction proceeds from
left to right, consuming iodine. Thus, in the absence of other iodine
consuming substances, a decolorization of iodine is characteristic of
arsenious acid.
fProcedoreA drop of the test solution is mixed on,the spot plate
either with a drop of dilute sulfuric acid and a few mg. of sodium bicarbon-
ate, or else the solution is acidified with acetic"acid; then a drop of a
ANTMONT 83
starch-iodine eolution is added, K the blue color disappears on stirring

with a glass rod, arsenious acid is present.
Limit of Identification: 5 y arsenic fin the presence of any amount
Concentration Limit: 1:10,000 \of AftsOj
ReagerUs: 1) Dilute sulfuric or acetic acid
2) Sodium bicarbonate (solid)
S) Starch-iodide solution
h) Reduction of arsenious acid to arsine. In acid solutions, volatile
arsine is formed by the action of nascent hydrogen on either arsenic pentox-
ide or arsenic trioxide. The gas can be detected by the Gutzeit test (see
page 80). However, in alkaline solution, such as sodium hydroxide solu-
tion, only arsenites are reduced to arsine by metallic aluminum, while
arsenates remain unchanged.
Therefore the test for arsenic trioxide in the presence of arsenic
pentoxide can be carried out as described on page 81, except that the
Teduction in the reaction vessel is efiected -with aiuminxan ioii and sodium
hydroxide. i
4. Other tests for arsenic ^
1. As (III) can be detected in a drop of test solution on filter paper
on the addition of a drop of cone, hydrochloric acid, a drop of 0.5% kairine
(n-ethyl-o-hydroxytetrahydroquinoline) and a drop of 1% FeCl. The
filter paper is gently warmed and a red-brown stain is formed"* (/d".
Limit: 0.005 y As). As(V) compounds must be reduced beforehand with
hydroxylamine sulfate. Hg, Pb, and Cu salts interfere.
ANTIMONY
1. Test by reduction to antimony.''* Soluble and insoluble antimony
(III) and (V) compounds are reduced to antimony by nascent hydrogen.
If the reduction is carried out on a piece of platinum foil, or the lid of a
platiniun crucible, with zinc and hydrochloric acid (or tin and hydro-
chloric acid)"' the antimony is formed as a black precipitate or brown
stain on the platinum surface. It is always deposited first on any rough
portion of the platinum.
Arsenic compounds are mainly reduced to the gaseous arsine, although
small amounts of arsenic are deposited on the zinc or appeafasblack flecks
in the liquid. Tin compounds are reduced to metallic tin, which forms a
gray platinum-colored deposit on the platinum. The presence of tin does
" W. Reppmann, Z. anal. Chem., 99, 180 (1934).
" C. R. Fresenius, Z. anal. Chem., 1, 444 (1862).
" G. Denigfes, Chem. Zentr., 1901, II, 1214.
not interfere with the test for antimony, but rather increases the sensitivity
by providing nuclei for the deposition of small amounts of the metal.
IfProcedurer-A drop of the test solution, which must be free from
nitric acid, is mixed with a drop of concentrated hydrochloric acid. A
small piece of zinc is added, and the mixture is allowed to stand on a piece
of platinimi foil for 5 to 30 minutes, according to the amount of antimony
present. The test can also be carried out on a watch glass.'""' A small
piece of platinum wire is placed on top of the zinc, and a drop of the strongly
acid test solution is added so that the zinc and platinum remain in contact.
In the presence of antimony, the platinum begins to darken, and the anti-
mony separates, in the fonn of glittering plates, on the surface of the
platinum. Any tin present adheres in spongy form to the zinc.
Ldmit of Identification: 20 y antimony
Concentration Limit: 1:2500
The reduction on platinum foil is recommended for the detection of
antimony oxide or antimonic acid in solid metastannic acid. The test
sample is mixed with dilute hydrochloric acid on platinum foil, gently
warmed for a few minutes, and then a small piece of zinc is added. In the
presence of antimony, a black or brown fleck is visible on the platinum,
after the surface has been washed with water.
2. Test with phosphomolybdlc acid."' As described under copper (see
page 67), molybdenum, when in the form of the complex phosphomolybdic
acid, has an increased reactivity. It can be smoothly reduced to molyb-
denum-blue by certain substances that have little or no. effect on normal
molybdates. Sb(III) salts, when warmed, also have thi^ property, but
they only react with free phosphomolybdic acid or ;its soluble salts, and not
with insoluble phosphomolybdates (difference from stannous chloride,
see page 86).
In the absence of tin (II) salts, the following test is specific for anti-
mony. It is very useful, in the ordinary systematic analysis, to determine
whether SbjSj is present in the sulfides precipitated by mineral acids from
alkaline sulfo solutions, Tiiis test is carried out in the solution obtained
by warming the precipitated sulfides with hydrochloric acid (1:1). The
antimony is always present in this,solution as antimony trichloride, and
the tin as tin tetrachloride, which does not interfere with the test.
It is simpler to warm a little of the alkaline sulfo solution with concen-
trated sulfuric acid until a clear solution is obtained. The solution then
contains Sb(III) sulfate, Sn(IV) sulfate, and HsAsO^. '
IfProcedureA drop of the test solution is filped on filter paper
impregnated with phosphomolybdic acid, and held over steam. In a few
' E. Rupp, Ber. dent, pharm. Ges., 32. 334 (1923).
" F. Fejgl and F. Neuber, Z. anal. Chem., 62, 3^2 (1923).
ANTIMONY 85
minutes a blue coloration appears that is more or less intense according to
the amount of antimony present.
Limit of Identification: 0.2 y antimony
Reagent: 5% phosphomolybdic acidi"' solution.
3. Test with 9-methyl-2,3,7-trihydroxy-6-flaorone." Antimony (Hi)
salts, in acid solution, react with aromatic o-dihydroxy compounds (e.g.,
pyrocatechol, pyrogallol) to produce slightly soluble, white, or light yellow
crystalline precipitates. These can be formulated as cyclic esters of
antimonous acid."* 9-MethyI-2,3,7-trihydroxy-6-fluorone (I), which can
be viewed as a colored derivative of pyrocatechol, forms a red antimonous
compound (II).
SbOH
In neutral or weakly acid solution, the reagent also forms orange-red

or orange-brown precipitates or colorations with a mmiber of other heavy
metal ions; in strongly acid solution, however, it acts only with antimony
(III) salts and maj'', therefore, be termed a specific reagent.
If antimony (V) is present, a preliminary reduction to antimony (III),
by means of metallic magnesium, is necessary. Ferric salts, which also
give a color reaction in acid solution (phenol reaction of the reagent), can
be masked by phosphoric acid or alkali fluoride.
UProcedureA drop of the test solution, whose acidity is brought to a
pH of about 4 by a tartrate buffer, is placed in a microcrucible or on a spot
plate. A drop of the reagent solution is added, and the mixture is warmed
gently if necessary. A red precipitate appears if antimony is present.
Limit of Identification: 0.2 y antimony
Reagent: 0.5% solution of 9-methyl-2,3,7-trihydroxy-6-fluorone in
alcohol."'
""For preparation, see H. Hundeshagen,Z. anal. Chem.,2S, 144 (1889). See
also A. Linz, Ind. Eng. Chem., Anal.'Ed., 15, 459 (1943).
"P. Wenger and C. P. Blanopain, Helv. Chim. Acta, 20, 1427 (1937).
' " F. Feigl, Mikrochemie, 1,74 (1923). See also F. Feigl and H. Ordelt, Z. anal.
Chem., 64, 41 (1924).
" ' For preparation, see C. Liebermann and S. Lindenbaum, Ber., 37, 1177,
2728 (1904).
86 K- TESTS FOR METAIiS
4. Test with rhodamine B." If antimony (V) salts are 'added to aqueous
solutions of xanthone dyestuffs, which are usually red, the color is changed
to violet or blue. Finely divided precipitates are deposited at the same
time. The composition of these precipitates is not yet known. The
dyestuff, rhoclamine B (tetraethylrhodamine):
^N(C.H.).
c,H..c( ;o
^^ NN(C.H.).
is the most suitable reagent for antimony, especially in testing for small
amounts in the presence of large amounts of tin. In the course of sys-
tematic analysis, antimony (III) chloride is always formed together with tin
(IV) chloride, when the acid sulfides precipitated from alkaline sulfo solu-
tions are dissolved in hydrochloric acid (1:1). Hence oxidation to anti-
mony (V) is necessary. This is easily carried out by adding sodium nitrite.
Small amounts of iron do not interfere with the test. Mercury, gold,
.and thallium chlorides, and any basic bismuth chloride, precipitated by
hydrolysis, likewise molybdates and tungstates in acid solution, give color
reactions with rhodamine B similar to those given by antimony salts.
^[Procedure1 ml. of the dyestuff solution is treated on a spot plate
with 1 drop of the test solution, which should be made strongly acid with
hydrochloric acid, and also oxidized beforehand, if necessary, by sodimn
nitrite. In the presence of antimony, the bright red (fluorescent) dye
solution changes to violet.
Limit of Identification: 0.5 y antimony /in the presence of 12,500
Concentration Ldmit: 1; 100,000 \times the amount of tin
Reagent: Rhodamine B solution (0.01 g. dyestuff in 100 ml. water)
5. Test by luminescence in the hydrogen flame.'^^ Antimony salts give
a green-blue luminescence to the hydrogen flame. Extremely small
amounts of antimony can be detected by this effect. The sample fs mixed
with alkaline earth carbonate, ignited gently, and touched with the hydro-
gen flame under suitable conditions. For the method of carrying out
luminescence tests, see page 62.
TIN
1. Test with ammonium pfaocfphomolylidate."' Stannous chloride reduces
not only molybdates to the colored lower oxides,"' but also reacts with
"> E. Eegriwe, Z. anal. Chem., 70, 400 (1927).
"J. Donau, Monatsh., 34, 949 (1913).
' F. Feigl and F. Neuber, Z. arud. Chem., 62, 382 (1923).
"' Compare C. Zenghelis, Z. physik. chem. Unterricht, 24. 137 (1911).
TIN 87
phosphomolybdic acid and its salts. "Molybdenum blue" results. It is

an important fact, especially for the detection of tin (II) in the presence
of antimony (III) salts, that stannous chloride will reduce not only the
soluble phosphomolybdates as does antimony trichloride, but also the
insoluble phosphomolybdates {e.g., the potassium or ammonium salt).
^ProcedureFilter paper, impregnated with a solution of phos-
phomolybdic acid, is held for a short time over ammonia to form yellow,
insoluble ammonium phosphomolybdate, and then dried. This paper will
keep in the dark, in well stoppered bottles.
When a drop of the solution to be tested for stannous salt is placed on
this paper, a more or less, deep blue coloration forms, according to the
amount of tin present.
lAmit of Identification: 0.03 y tin
Concentration lAmit: 1:1,670,000
Reagents: 1) Phosphomolybdic acid (for preparation, see page 85)
S) Ammonia
Test for tin in the presence of antimony
Where the tin occurs originally in the divalent condition, the test
may be carried out as described, and antimony salts do not interfere.
If, however, tetravalent tin is present, it must first be reduced to stannous
chloride. This can be done by placing 1 or 2 drops of the test solution in a
small porcelain crucible, and warming with either a small strip of magnesium
ribbon or a small piece of zinc, and a few drops of cone, hydrochloric acid,
until the metal dissolves. A drop of this solution is placed on ammonium
phosphomolybdate paper. Any metallic antimony, which is formed as a
black powder, does not interfere with the test for tin.
2. Test with cacotheline.'" Aqueous solutions of cacotheline, when
treated with acid tin (II) solutions, give a violet color due to the formation
of a reduction product of cacotheline. The latter is a nitro compound of
brucine, of unknown constitution."' Some other reducing compounds
such as hydrogen sulfide, sulfites, thiosulfates, and Sb(III) salts, react with
cacotheline."' Iron (II) salts (in the absence of fluorides and phosphates,
do not react with cacotheline, so.that a tin solution, reduced with iron wire,
can be used for the test. Colored metallic salts interfere, if present in
considerable quantity. Ti(III),U(IV),Rh(III),Nb (III) salts.and lower
" ' G. Gutzeit, Helv. Chim. Ada, 12, 720 (1929).
" According to N. Moufang and J. Tafel, Ann., 304, 47 (1898), cacotheline is
the nitrate of the bisdimethylmononitrobrucine hydrate, and has the empirical
formula C I H M ( O H ) I ( N O , ) N , 0 , - H N O , .
" Compare I. L. Newell and co-workers, Ind. Eng. Chem., Anal. Ed., T,
26 (1935).
88 II- TESTS FOR METALS
oxides of Mo and W"" also interfere. A violet coloration is given by

compounds of As, Sb, and Te in the presence of metallic zinc and acids.
When carried out as a spot test, the test is more sensitive than in a
teiJt tube (test tube limit of identification: 30 T Sn in 3 ml.).
^ProcedureFilter paper is impregnated with a saturated aqueous
solution of cacotheline. A drop of the test solution is added before the
paper is quite dry. According to the amoimt of tin present, a red circle
or ring is formed on the yellow paper, surrounded by a colorless zone.
Limit of Identification: 0.2 7 tin
Reagent: Saturated aqueous solution of cacotheline"'
Detection of tin in metals, minerals, etc., see page 432.
3. Test by flame color.''" When hydrogen is evolved from zinc and
hydrochloric acid in the presence of soluble or insoluble tin compounds, it
gives a characteristic blue color in the nonluminous flame of a Bunsen
burner. The reason for this phenomenon is not known; it is not, however,
due to the formation of tin hydride, as was first assumed,.'*'
A portion of the test solid or liquid is mixed with a considerable
amount of cone, hydrochloric acid in a porcelain dish, and a few granules
of pure stick zinc is added. The mixture is then stirred with a test tube
filled with cold water. If the portion of the test tube, which has been
dipped in the mixture, is held in a nonluminous Bunsen flame, a character-
istic blue flame mantle forms around the test lube, reveahng the presence
of even very small quantities of tin. This flame color is specific for tin,
and may be carried out on a single drop of the teat solution, for which the
reducing power of the gases of the flame is suflScient.'** The presence of
arsenic, if more than equivalent to the amount of tin, causes this very
characteristic reaction to fail. Sn02 prepared in the wet way, and ignited,
responds decisively to this test, but tinstone does not. Tinstone must
first be opened up with KNaCOj {e.g., by fusion in a loop of platinum wire).
^ProcedureA drop of the test solution is placed on a magnesia rod
and evaporated by holding it about 0.5 cm. away from a very small Bunsen
flame. The residue is moistened with a drop of cone, hydrochloric acid,
and held in the reducing portion of a microflame.. In the presence of tin,
a blue flame mantle forms around the stick of magnesia. If the amount
of tin present exceeds 0.25 7, the flame color will reappear several times
on moistening the residue with cone, hydrochloric acid each time.
' G. Beck, Mikrochim. Ada, 2, 287 (1937).
".For preparation, see N. Moufang and J. Taf-eh Inn., 304, 47 (1898).
' H. Meissner, Z. anal.Chem., 80, 247 (1930). See also 0 . Schmatolla, Chem.-
Ztg., 26, 468 (1901) and F. L. Hahn, Z. anal. Chem., 82,113 (1930).
" ' Private communication from F. L. Hahn.
"* Experiments with H . J . Kapulitzas.
GEHMANItTM 89
lAmit of Identification: 0.03 T tin

Reagents: 1) Metallic zinc
2) Cone, hydrochloric acid
4. Other tests for tin. 1. Sn(II) salts can be detected by their reducing
action on Fe(III) salts."' The red precipitate with dimethylglyoxime
serves to identify the Fe(II) salt formed {Id". Limit: 0.04 -y Sn). a,a'-
Dipyridyl can be used in place of dimethylglyoxine to detect the Fe(II)
produced.
2. The blue azo dyestuff, diazine green S(K), is reduced by Sn(II)
salts, giving a violet to red color^" (7d". Limit: 2 y Sn).
3. Filter paper impregnated with the green photo product of 2-ben-
zylpyridine, is turned red on treatment with a hydrochloric acid solution
of SnCy" (/rfn. umit: 1.3 7 Sn in 0.01 ml.). As(III) and Sb(III) salts
do not interfere, but the same color change is effected by sulfites.
4. Tin may be detected"' by placing a drop of the solution, which has
been reduced, if necessary, with metallic magnesium, on filter paper
impregnated with mercuric chloride. The spot is then alkalinized with
aniline. Only tin (II), but not antimony (HI), is thus reduced to metal.
(Brown fleck.) (/d. Limit: 0.6 y Sn.)
5. One drop of the hydrochloric acid solution containing Sn(IV) is
treated on a spot plate with 1 drop of 0.1% solution of 1,2,7-trihydroxy-
anthraquinone in methyl alcohol. The mixture is first made alkaline with
ammonia and then acidified with 33% acetic acid."' The orange colora-
tion is due to the formation of tin lakes (Zd". Limit: 0.2 y Sn). Ti, Zr, AI,
Fe, and Cr salts produce colorations, Bi"'"'"*' and MoOT" colored precipi-
tates.
6. The red solution of anthraquinone-l-azo-4-dimethyIaniline hydro-
chloride gives a blue-violet precipitate, (Cs2Hi70sN3)2-H2SnCl6, with
Sn(IV) salts."" Acid stannic solutions produce violet flecks on filter
paper impregnated with the reagent {Id". Limit: 0.01 y Sn). Zn, Cd, and
Hg salts react similarly; Sb(III), U, Mo, Ir, Te, and Ga salts, in consider-
able quantities, produce violet colorations.
GERMANIUM
1. Test by the formation of a complex with mannite,'" Germanic acid,
like boric acid, is able to form complex compounds with the polyvalent
F. Feigl, Chem.-Ztg., 43, 861 (1919).
" ' E. Eegriwe, Z. anal. Chem., 74, 223 (1928).
' " H. Freytag, Ber., 67, 1477 (.1934).
" N. A. Tananaeff, Z. anorg. allgem. Chem., 133, 372 (1924).
" ' E. Eegriwe, Z. anal. Chem., 120, 81 (1940).
" V. J. Kuznetsov, Chem. Abstracts, 36. 3190 (1941).
' " N. S. Poluektoff, Mikrochemie, 18, 48 (1935).
90 n. TESTS FOE METALS
alcohols, such as glycerol, mannite, glucose. The Compounds ifonned

are strong monobasic acids, which may be titrated with alkaU or iodo-
metrically."' Therefore, on mixing a germanate solution or GeOjwith
alkali and mannite, a decrease in pH indicates the presence of germanium.
This reaction is specific for germanium, in the absence of boron.
^[ProcedureA drop of the slightly acid germanate solution is mixed
with a drop of phenolphthalein solution, and 0.01 N sodium hydroxide
is added until the red color appears. On the addition of mannite (solid)
the red color is either partly or completely discharged.
Ldmit of Identification: 2.5 7 germanium
Reagents: 1) 0.01 iV sodium hydroxide
2) Phenolphthalein solution
3) Mannite (soUd)
2. Test with anunonium molybdate and benzidine.'^^ In solutions con-
taining mineral acids, germanates react with molybdates to form the
water-insoluble germanium molybdic acid H8Ge(Mo207), which, Hke the
analogous complex compounds of arsenic; phosphorus and silica with
molybdic acid, shows an increased capacity for oxidizing certain organic
and inorganic compounds. When benzidine is treated with an acid solution
of germanium molybdic acid, buffered with sodium acetate or ammonia,
lower molybdeniun oxides are formed (molybdenum blue, see page 84) and
a blue oxidation product of benzidine (benzidine blue, see page 55). Under
carefully controlled conditions, this reaction affords a sensitive and specific
test for germaniimi.
^ProcedureA drop of' the alkaline or slightly acid test solution is
treated, either on the spot plate or on filter paper, with a drop of the molyb-
date solution, then with a drop of benzidine solution, and then buffered with
a few drops of a saturated solution of sodium acetate, or, when the test is
carried out on filter paper, treated with ammonia gas. A" hghtôj dark
blue stain is formed, according to the amount of germanium present.
lAmit of Identification: 0.25 7 germanium (in 0.025 ml.)
Reagents: 1) Ammonium molybdate solution. 1 g. (NH4)jMo04 dis-
solved in 10 ml. water and 10 ml, cone. HNOi added
2) 0.1% acetic acid solution of benzidine
3) Saturated solution of ammonimn acetate
This method for the detection of germanium is only decisive in the
absence of certain other materials. Apart from compounds which reduce
molybdates .directlye.g., Sn(II), Fe(II)i As(III), and Se(IV)arsenic
" A. Tschakirian, Compt. rend., 187,229 (1928).
"A. S. Komarowaky and N. S. Poluektoff, Mikrochemie, 18, 66 (1935).
GERUA.NIUM 91
acid, phosphoric acid, and silicic acid should not be present, as they also
can form heteropoly acids of molydeniun, which react with benzidine.
In the presence of these acids, the gennanium can be distilled out of
hydrochloric acid solution (3.5-4.0 N) as GeCU. The molybdate-
benzidine test is carried out with the distillate.
UProcednreIn the small glass beaker (4 ml. capacity) of the appa-
ratus shown in Figure 43,1 or 2 drops of the sUghtly alkaline test solution
are evaporated, and, after cooling, 2 or 3 drops of 4 N hydrochloric acid
are added. The beakel- is covered with the small water-filled bulb and
gently heated over a wire gauze. The GeCU vapor condenses on the glass
knob of the condenser. When the drop is large enough, the heating is
discontinued, and the drop is carefully transferred to a spot plate. The
test is then carried out using, however, 5 or 6 drops of saturated sodium
acetate solution.
Limit of Identification: 2 y germanium
The distillation from hydrochloric acid solution
does not effect a complete separation from all inter-
fering substances. Trivalent arsenic and tetravalent
selenium are also volatilized, and these considerably
reduce the sensitivity of the germanium test. Further,
As(V) may be reduced to As (III) in the process of dis-
tillation from hydrochloric acid solution, and so get
into the distillate as AsCU- The test for germanium
Fig. 43. Micro- ^ *^ presence of selenivun and arsenic can only be
beaker fitted with successfully carried out if the interfering elements
water-filled biilb a^j.g converted to the higher oxides beforehand by
giê) evaporation with 30% hydrogen peroxide and 1 or
2 drops of ammonia. The dry residue is then treated
with a small crystal of potassium permanganate and 2 drops of 4 iV hydro-
chloric acid. The germanium can then be distilled, and the test carried
out on a drop of the distillate. Any free chlorine present is destroyed
by means of a drop of a 6% NajSOs solution, after the addition of the
molybdate reagent. In this way, 10 y germanium may be detected in the
presence of 1000 times the amount of seleniimi (as SeOs), or 800 times the
amount of arsenic. .
3. Other tests for gennanium. The similarity between boric acid and
germanic acid (see page 89) is also shown in the reaction with hydroxy-
anthraquinones, which give a color change in sulfuric acid solution with
boric acid (see page 257). Germanium dioxide or germanic acid also react.
In this way, 5 Y Ge (1:10,000) may be detected."* The dyestuff p-nitro-
N. 8. Poluektoff, Mikrochemie, 18,49 (1935).
92 n- TESTS FOR METALS
!
benzeneazochromotropic acid behaves similarly, but the reaction is less
sensitive.
MOLYBDENUM
1. Test with potassium thiocyanate and stannous chloride.'" Solutions
of molybdates are colored yellow by the addition of potassium thiocyanate
and hydrochloric acid. If a little zinc or another reducing agent is added,
pentavalent molybdenum is produced along with red, soluble H3M0O-
{CNS)6. The latter is quite soluble in ether, and so can be extracted by
this solvent.
When iron is present, it is advisable to add several drops of phosphoric
acid (d = 1.76) after the reduction; colorless ferric phosphate is formed.
The presence of iron is revealed by the red color that immediately appears
on adding potassium thiocyanate.
If phosphates, organic acids (oxalic and tartaric, etc.) as well as
phosphoric acid, are present in the original solution, these also give stable
complex compounds with molybdates, and the molybdate reaction may be
completely inhibited or its sensitivity greatly reduced. Regard should
also be paid to the presence of mercury salts and nitrites, which, under the
conditions of the experiment, consume thiocyanateby formation of the
slightly dissociated mercury thiocyanate and soluble red nitrosyl thiocya-
nate (NOCNS), respectively. Tungstates form insoluble blue lower
tungsten oxides, which decrease the sensitivity and,specificity of the test.
This interference may be decreased by using capillary separation.
Titanium, vanadium and uranium do not interfere with the reaction;
only tungsten, as stated, gives a blue fleck of the lower tungsten oxides.
This interference is prevented if a drop of hydrochloric acid is placed on
the test paper; the insoluble tungstic acid is held back in the paper, while
the molybdate diffuses through the capillaries to the edge of the drop, and
can be identified there. The presence of formic or phosphoric acids reduces
the sensitivity of the test.""
The test can be carried out on filter paper, using either stannous
chloride or sodium thiosulfate as the reducing agent."^
"jfProcedoreA drop of the test solution and a drop of a potassium
thiocyanate solution are placed on filter paper previously moistened with
hydrochloric acid. In the presence of iron, a red fleck appears, which dis-
appears on adding stannous chloride or sodium thiosulfate;/ In its place,
a brick-red fleck of HjMoO(CNS)8 appears, if molybdate is present.
C. D. Braun, Z. anal. Ghent., 2,36 (1863); F. C. Krauskopf and C. E. Swarte,
J. Am. Chm. Soc., 48, 3021 (1926); Y. Uzumasa and K. Doi, Bull. Chem. Soc. Japan,
14, 337 (1939); Chem. AbsiracU, 84, 959 (1940).
" J. Sterba-Behni and J. VostrSbal, Z. anprg. allgem. Chem., 110, 82 (1920).
" ' N . A. Tananaeff and G. A. Pantechenko, Chem. AhstracU, 84,566 (1930).
MOLYBDENTJM 93
Limit of Identification: 0.1 y molybdenum

Reagents: 1) Hydrochloric acid (1:1)
S) Potassium, thiocyanate solution
5) Stannous chloride or sodium thiosulfate solution
2. Test with potassium xanthate."' In solutions containing mineral
acids, a deep red-blue coloration is formed by the combination of molyb-
dates with potassium ethyl xanthate SC(SK)OC2H6); with large amounts
of molybdenum, there is a separation of almost black, oily drops. The
product is the complex compound, MoOj- [SC(SH)(0CjH6)]j," which is
soluble in organic Uquids, such as benzene, chloroform, carbon bisulfide.
To an extent, it is an organic analogue of Mo08'2HCl,** which likewise
dissolves, without decomposition in organic solvents. This very sensitive
color reaction is quite specific for molybdates, although those organic acids,
which give complex compounds with molybdates (oxalic, tartaric or citric
acid), decrease the sensitivity, if present in considerable quantities.
IfProcedureA drop of the nearly neutral or slightly acid test solution
is mixed on a spot plate with a grain of solid potassium xanthate and treated
with 2 drops of 2 iV HCl. A pink to violet color develops, depending on
the quantity of molybdate present.
Limit of Identification: 0.04 7 molybdenum
Reagents: 1) Potassium xanthate (solid)
S) 2 N hydrochloric acid
The use of filter paper impregnated with Zn or Cd xanthate can be
recoixmiended highly. A red fleck or ring appears when a drop of the
acid test solution is applied (Id". Limit: 0.02 y Mo). The reagent paper
is prepared by immersing filter paper in ZnSO^ or CdS04 solution, drjong,
" ' S . Malowan, Z. anerg. allgem. Ckem., 108, 73 (1914); Z. anal. Chem., 79,
202 (1929); J. Koppel, Chem.-Ztg., 43, 777 (1919).
" M. Siewert, ^ . anal. Chem., 60,464 (1921); Z. ges. Naturw., 23, 5 (1864). See
also J. Koppel, loc. cit.
"This compound was first prepared by C. Debray, Compt. rend., 46, 1101
(1858). F. Ephraim, Inorganic Chemistry, 3rd English ed., Nordeman, New York,
1939, p. 493, assigns the structure (I) to it. The xanthate compound probably has
the analogous structure (II). This assumption is supported Ky the fact that, as
stated by Malowan (loc. cit.), the ethyl xanthate acid ethyl ester SC(SCjHi)(OCiH)
does not react with molybdic acid. R. Montequi [Chem. Abstracts, 24, 3722 (1930))
assumes that the xanthate reaction involves a pentavalent molybdenum compound.
" (OH,)' r (OH),

MoO MoO
. CI, _ L [aCS(OC,H,)l
(I) (II)
94 II. TS8TS FOR METALS
and bathing in potassiuna xanthate solution. After washing with water,

and drying, the paper is stable.
Test for molybdenum in ores, etc., see page 433. j
3. Test with phenylhydrazine.'^^ Molybdates in acid i solution give a
blood-red coloration or red precipitate with phenylhydrazine. At high
dilutions, a pink color appears. The phenylhydrazine is oxidized by am-
moniiun molybdate to the diazonium salt, and this couples with the excess
phenylhydrazine and molybdate.
^Procedure**'o) A drop of the test solution and of the reag^t
solution are mixed on the spot plate. A more or less deep red coloration
appears according to the amount of molybdeniun present. A blank should
be carried out for small amounts.
6) A drop of the reagent solution is placed on spot paper, and, before
it has soaked in, a drop of the test solution is added. A red ring forms
around the spot after a few minutes, if molybdenimi is present.
7- -i J. Tj ^.e . /0.32 7- molybdenum (on the spot plate)
Limit of IdenttncaiKm: <, ,,, / , \
1^0.13 y molybdenum (on spot paper)
r^..w,-o (I'A
Voncentration7-vv.
L/imit: ; '-:60,000 (on th^spot plate)
\ l : 300,000 (on spot paper)
Reagent: Solution of phenylhydrazine in glacial acetic acid (1:2)
4. Other tests for molydenum. 1. On mixing molybdate and a tincture
of cochmeal, at pH 5.7 to 6.2, a flame-red fluorescence results. .The test
is carried out in capillary tubes (7d". Limit: 0.02 y MoO).'*' Boric acid
gives a yellow fluorescence. With reference to interference of other ions,
see the original papers.
2. Molybdates react with a,a'-dipyridyl, followed by SnClj, to give
a violet color*** (Id". Limit: 0.4 y Mo). Any interference due to tungstates
can be prevented by complex salt formation with tartaric acid.
S. Molybdate solutions containing mineral acid give a violet color
with diphenylcarbazide."' The reaction is due to the carbazone formed
by oxidation (Zd*. Limit: 2.5 y Mo). The test is more sensitive if di-;9-
naphthylcarbazone is used"* {Id". Limit: 0.3 y Mo). Chromates inter-
fere because of an analogous color reaction with carbazone (see page 128).
TUNGSTEN
1. Test with staonons chloride. Tun^tates are reduced by stannous
chloride in strongly acid solutions to the blue, lower tungsten oxide.
"> L. Spiegel and Th. Maass, Ber., 36, 512 (1903); E. Montignie, Bvll. toe. chim.
France, [4], 47,128 (1930).
" Experimenta with H. J. Kapulitzas.
" L. 8sebÛ6dy and J. 36n&B, MikrocMm. Acta, 1,46 (1937).
" A. S. Komarowsky and N. S. Poluektoff, Mikrochim. Acta, 1,264 (1937).
E. Lecocq, Bull. toe. chim. Bplg., 17, 412 (1903); Chem. Zentr., 1904,1, 836.
" P. Krumholi! and F. Hdnel, Mikrochim. Acta, 2rl77 (1937).
TUNGSTEN 95
This compound, in contrast to "molybdenum blue," which forms under

similar conditions, is sparingly soluble, and is stable in the presence of
excess stannous chloride.
IfProcedure1 or 2 drops of the test solution are mixed on the
spot plate with 3 to 5 drops of stannous chloride. In the presence of
tungsten,, a blue precipitate or coloration appears at once, or after a short
time.
Limit of Identification: 5 y tungsten
Reagent: 26% solution of stannous chloride in cone. HCl
Test in the presence of molybdenum
The test for tungsten in the presence of molybdenum can be carried
out as a spot test."' ^
IfProcedureA drop of hydrochloric acid is placed on filter paper, and
a drop of the test solution placed in the middle of the moist fleck. A
bright yellow fleck of tungsten trioxide appears. If this is treated with
potassium thiocyanate and stannous chloride (see page 92) the yellow
fleck changes to blue, due to formation of lower tungsten oxides. Under
these conditions, ipolybdenum gives a red fleck [of K3Mo(CNS)6], which
disappears on the addition of cone, hydrochloric acid, and hence does not
interfere with the tungsten reaction.
Ldmit of Identification: 4 y tungsten
Reagents: The same as in the molybdenimi test, page 93
Ignited tungsten trioxide can be brought into solution by means
of sodium peroxide, and detected as described. Similarly, tungsten in
minerals can be detected after fusion with 5 times the amount of sodium
potassium carbonate.
Phosphoric acid and organic hydroxy acids, such as tartaric and
citric acids, which form complex compounds with tungstic acid, hinder
the precipitation of tungsten trioxide with mineral acids; certain other
organic acids also impair the reaction to some extent.
2. Test by catalysis of the Ti(in)-malacliite green reaction."' Many
dyes, including malachite green, a triphenyhnethane dye, are reduced
rapidly to the corresponding colorless leuco compounds by titanium tri-
chloride in warm neutral solution. The reduction is usually slow at room
temperature and in acid solution. The slow reaction:
Ti(III) + malachite green > Ti(IV) + leuco malachite green
is catalytically accelerated by tungstate. This serves as the basis of a
sensitive test for tungsten.
" ' N. A. Tananaeff and G. A. Pantschenko, Chem. Abstracts, 24, 567 (1930).
" E . B. Sandell, Ind. Eng. Chem., Anal. Ed., 10, 667 (1938).
96 n . TESTS FOB METALS
The catalysis is due to the fact that W(VI) is reduced rapidly by

Ti(III) to W(V), which quickly reduces malachite green to the colorless
leuco base. Consequently, this is an intermediate reaction catalysis involv-
ing two rapid partial reactions in which the catalyst (tungsten) participates.
The summation of the partial reactions (1) and (2) gives the net catalyzed
reaction (S) in which the catalyst does not appear.
Ti(III) + W(VI) -* Ti(IV) + W(V) . . . (rapid) (/)
W(V) + malachite green -* W(VI)
+ leuco malachite green . . .(rapid)
Ti(in) + malachite green -* TI(IV)
+ leuco malachite green . . . (rapid)
The catalytic action of W(VI) is highly specific; only molybdenum
reacts analogously, but the effect is less pronounced. Other metal ions
that can be reduced by Ti(III) have no such effect on the malachite green
reduction.
Despite the specific catalytic action, consideration must be given,
however, to the presence of accompanying materials. First of all, metal
ions interfere if they are reduced to lower valence stages or to the free
metal, or if they form slightly soluble chlorides. TiCU is consumed by
these reductions, or the visibility of the reaction is impaired by the pre-
cipitated metal or chloride.
Alkali chlorides and chlorides of metals, which are not reduced by
Ti(III), do not interfere seriously, but the time of a blank reaction is, in
general, decreased. Alkali sulfates and magnesium sulfate markedly
increase the speed of reaction between malachite green and Ti(III) in the
absence of tungsten, and consequently decrease the catalytic effect of this
element. Nitrates and fluorides must be absent. The former are reduced
by Ti(III); fluorides form stable complex salts with W(VI) and thus
inhibit the catalysis.
Although molybdenum catalyzes the reaction, its effect is much less
pronounced than that of tungsten, so that, in small amounts, it hardly
interferes. Moreover, the presence of molybdenum is revealed by the
appearance of a yellow-brown color, which fades rapidly when Ti(III)
is added to 0.01 N HCl solution containing this element. When molyb-
denum and phosphate are both present, a permanent dark red-brown
appears on adding Ti(III) to the acid solution. However, the reduction of
malaclHte green hardly proceeds more rapidly than J n the absence of
phosphate. '' -
IfProcednreOne drop of the test solution which may be neutral or
0.1 N with respect to HCl, and free from interfering substances, is treated
VANADIxm QM
on a spot plate with a microdrop of TiCIj and 1 microdrop of a -wate i

tion of malachite green. Depending on the concentration of tungstej^ ^.u
solution becomes colorless (very pale violet) more or less rapidly.
Limit of Identification: 0.1 7 tungsten
Reagents: 1) 1% solution of TiCU
2) 0.005% aqueous solution of malachite green
3. Test with diphenyline."' It is well known that benzidine (I) pre-
cipitates the white benzidine tungstate from solutions of alkali tungstates.
This reaction is unsuitable for the detection of tungsten, especially in
the presence of molybdenum, as molybdates react similarly, and further,
sulfates are precipitated as benzidine sulfate. If, however, instead of
benzidine, its isomer, diphenylihe (II) is used.
H.N<^^ ^~^\ ^NH. H.N<^^ ^<^ y
NH,
, (I) (II)
then sulfates are not precipitated, and mftlybdates are only precipitated
from solutions more concentrated than 10%. Tungsten, however, is
precipitated quantitatively as diphenyline tungstate.
^[ProcedureA drop of the test solution is mixed with a drop of
diphenyline hydrochloride in a micro test tube. A precipitate, or cloudi-
ness, indicates the presence of tungstate. For very small amounts, a
blank test should be carried out and compared with the test, after both
have stood for 15 minutes.
Limit of Jdentification: 6 y tungsten
Reagent: 1% solution of diphenyline hydrochloride^"" in 2 JV HCl
VANADIUM
1. Test with hydrogen peroxide."* A solution of vanadium containing
sulfuric acid turns red-brown to blood-red, or, in. very dilute solution,
pale brown-pink, on the addition of hydrogen peroxide. Excess hydrogen
peroxide causes partial decoloration. The reaction depends on the forma-
tion of the colored peroxovanadium salt (I) which, in the presence of
excess hydrogen peroxide, reacts:
F. Feigl, Rec. irav. chim., B8, 471 (1939).
" For preparation, see H. Schmidt and G. Schultz, Ann., 2ffl, 330 (1881).
"1 G. Werther, J. prakt. C/wm., 83,195 (1861). 8
98 !! TESTS FOR METALS
H,0. ~~ I
(viO.csOl), + 6H,o ;::" 2 (V:O,)(OH), + 3HJSO,
(J) ^'^*^* (II)
and is converted into yellow orthoperoxyvanadic acid (II).">^ An excess of
hydrogen peroxide and sulfuric acid is consequently to be avoided. The
interference due to the color of iron (III) salts can be prevented by the
addition of phosphoric acid or fliioride (formation of the colorless
Fe(P04)j or FeFT ions). Titanium salts, which give a yellow per-
compound under these conditions (see page 150), can be converted into
complex titanium fluoride by the addition of alkali fluorides.
Cerium salts, molybdates, chromates, iodides, and bromides, as
well as large amounts of colored metaUic salts, reduce the sensitivity
of this test for vanadium.
^ProcedureA drop of the solution is mixed with a drop of sulfuric
acid, either on a spot plate or in a porcelain microcrucible. After waiting
for a few minutes, a drop of 1% hydrogen peroxide solution is added,
A further drop of peroxide may be necessary.
According to the amount of vanadiumpresent, a red to pink colora-
tion appears. ,
lAmit of Identification: 2.5 y vanadium
Reagents: 1) 15-20% sulfuric acid
2. Test by formation of iron (II) dimethylglyoxime.^'^ The reaction
V(IV) + Fe(III) ^ V(V) + Fe(II) proceeds from left to right in alka-
line solution and in the reverse direction in acid solution. As iron (II)
salts give a deep red coloration with dimethylglyoxime in the presence
of ammonia (see page 125), vanadates, when reduced beforehand to vana-
dium (IV) salts, may be detected by applying thi sensitive reactioUj, The
reduction is carried out by heating vanadates with concentrated hydro-
chloric acid:
VJOB + 10 HCl = 2 VCI4 -1- 5 Hb -f CI2
IfProcedureA drop of the test solution along with 2 drops of cone,
hydrochloric acid is carefully evaporated to a little more than half the orig-
inal volume in a microcrucible. After cooling, a drop of a ferric chloride
solution and 3 drops of a dimethylglyoxime solution are added and the mix-
ture rendered alkaUne with ammonia. According to the^vanadium content,
a cherry-red to brown color is formed. In order to reveal the color that
" J. Meyer and A. Pawletta, Z. anal. Chem., 69,16 (1926).
" F. Ephraim, Helv. Chirn. Acta, 14,1266 (1931)^
VANADIUM 99
is hidden in the precipitated ferric hydroxide, a strip of filter paper should

be dipped in the solution. The ferric hydroxide precipitate remains be-
hind, and the red solution of iron (II) dimethylglyoxime diffuses up the
capillaries.
lAmit of Ideniification: 1 r/ vanadium
Reagents: 1) Cone, hydrochloric acid
2) 1% ferric chloride solution
8) 1% alcoholic solution of dimethylglyoxime
4) Ammonia
3. Test with cacotheline.^'^ Vanadium (III) salts react with cacotheline
similarly to tin (II) salts. They reduce aqueous solutions of the com-
pound, forming a violet solution (see page 87). Vanadates can be de-
tected by means of this color reaction, if reduced by metallic zinc and
hydrochloric acid in the presence of cacotheline.
Molybdates and tungstates interfere with the test by forming blue
reduction products. Iron (II) salts interfere only in tie presence of
phosphates or fluorides, since in this case the ferrous salts are able to
reduce cacotheline. Tin salts must not be present.
IfProcediireÂ drop of the test solution is mixed on a spot plate with
a small piece of granulated zinc and a drop of cone, hydrochloric acid, and
the cacotheline solution added, According to the vanadium content, a
violet to red color is formed.
lAmit of Identification: 2 y vanadium
Reagents: 1) Granulated zinc
3) Aqueous solution of cacotheline (see page 88)
4. Other tests for vanadinm. 1. The well-known catalytic oxidation of
aniline to aniline black'*' by vanadium salts may be applied as a test for
vanadium"' (/d". Limit: 3 y V). This test, which is carried out on filter
paper, in acid solution, is only applicable in the absence of other oxidizing
agents.
2. The oxine test may be carried out in a microcrucible by adding
a drop of an acetic acid solution of oxine to the hot test solution, which
has been treated with sodium tartrate (Id". Limit: 0.27 T V in 0.04 ml.).'"'
3. Vanadium (IV) may also be detected with phosphomolybdic acid
by the formation of molybdenmn blue'" (Id". Limit: 0.4 7 V in 0.04 ml.),
' " Studies with H. Kappelmacher.
" ' J. Lightfoot, Jahresb. Fdrtsch. Chem., 86, 1076 (1872); A. Guyard, BvU. toe.
cWm., [2], 26, 58(1876).
" N. A. Tananaeff and G. A. Pantsohenko, Chem. Abstract, 2i, 567 (1930).
"A. 8. KomarowBky and N. S. Poluektoff, Chem. Zenir., UU, 1,3773.
in the absence of Ce(III), Co, Sn(II), Fe(III) and chron|ates. Vanadium

(V) salts must be reduced with oxalic acid before carrying out the test.
J^. 8-Hydroxyquinoline (oxine) in acetic acid solution reacts with
V2O6.'*' A blue-black, metallo-organic compound results. It may be
extracted with chloroform in a micro test tube (Id". Liniit: 0.1 7 V).
GOLD
1. Test with dimethylaminobenzylidene rhodanine.^" Gold salts give
a red-violet precipitate with p-dimethylaminobenzylidene rhodanine
in neutral and weakly acid solutions.
Silver, mercury, and palladium salts must be absent as they also
react with this reagent to give colored insoluble products (see pages 43, 51,
and 107).
IJProcedureA drop of the neutral or weakly acid test solution is
placed on rhodanine-impregnated paper. In the presence of gold, a violet
fleck or ring is formed.
Limit of Identification: 0.1 7 gold
Reagent: Spot paper (S & S No. 601) is impregnated with a satu-
rated alcoholic solution of p-dimethylaminobenzylidene
rhodanine, and dried. For preparation of reagent, see
page 44
2. Test with benzidine."" Gold (III) salts oxidize acetic acid solutions
of benzidine, an organic base, to a blue quinone-imine type of dyestuff,
benzidine blue. Colored, gold hydrosols are produced at the same time.
Considerable quantities of heavy metals or alkali salts prevent the forma-
tion of the sols and consequently impair the test.
^Procedure*"A drop of both the test solution and an acetic acid
solution of benzidine are placed onfilterpaper. A blue color indicates gold.
Limit of Identification: 0.02 -y gold in 0.001 ml.
Reagent: 0.05% solution of benzidine in 10% acetic acid
3. Test by reduction to metallic gold."^ Gold salts like those of other
noble metals, are reduced to the free metal by evaporating their solutions
and heating the residue. These processes may be carried out in a glass
capillaiy, when, if the glass has been sufficiently heated, the reduced gold
is enclosed by the molten glass or forms a colloidal solution in it. After
" R. Montequi and M. Gallego, Chem. Abstracts, 28, 3409, (1934).
" H. Holzer, Mikrochemie, 8, 275 (1930); see also F.-Feigl, P. Krumholz, and
E. Rajmann, ibid., 166 (1931).
" G. Malatesta and E. di Nola, Chem. Abstracts, 8,1397 (1914).
" N. A. Tananaeff and K. A. Dolgow, Chem. Abstracts, 84, 1313 (1930).
" C. Duval and P. Fauconnier, Mikrochim. Acta^ 3, 30 (1938).
GOLD 101
cooling, the glass acts as a lens, and this magnification makes it possible to
detect the small flakes of gold. For amounts of gold of less than 1 y
in the drop, no particles of gold are formed but, instead, a red colloidal
dispersion of the gold in the glass, that is easy to see against a dark back-
ground. The only other metal that reacts similarly is copper, but the two
metals may be distinguished by the behavior on diluting the test solution.
IJProcedureA drop of the solution of the gold salt, which may either
be acid or alkaline in reaction, is sucked up into the fine capillary end
of a glass tube fitted with a rubber cap. A small space is left between
the drop and the end- of the capillary. The drop is carefully evaporated
by heating over a microbumer; the rubber cap is then removed. The glass
is then heated until the particles of gold are enveloped in a ball of melted
glass, which later serves as a lens.
lAmit of Identification: 1 y gold
Gold solutions containing less than 1 y gold in a drop give a reddish
thread in the glass. This is easy to distinguish against a dark background.
As little as 0.05 y gold may be detected by this means.
The procedure is applicable in the qualitative analysis of gold alloys,
colloidal gold solutions, toning and fixing baths, etc.
4. Other tests for gold. 1. A reagent paper is prepared by impregnating
filter paper with a reducing substance (such as SnCU, HgzCla, benzidine,
pyrogallol, etc.) and dried at not more than 40 C. in 2 hours. On adding
a drop of a solution containing gold, a colored stain of metallic gold forms."'
By comparing this with the fleck obtained from a gold solution of known
concentration, the test may be made semiquantitative.
Platinum Metals
Catalxjtic tests for platinum metals
a) By condensation of hydrogen on thefinelydivided metoZ*'*
Iridium, palladium, platinum, and rhodium are able to condense gases
on their surface by adsorption. In so far as these gases react with oxygen
of the air, the heat liberated will be taken up by the metal and can ignite
inflammable gases. Finely divided platiniun metals are especially reactive
owing to their large free surface. When a drop of a solution of a platiniun
metal is placed on a strip of asbestos paper, and the moistened portion
strongly ignited, finely divided metal is deposited. When cool, the strip is
held in a stream of gas (ordinary coal gas or hydrogen). The spotted por-
tion begins to glow, and if suflBcient metal is present, the gas catches fire.
" R. N. CoBteanu, Z. anal. Chem., 104, 351 (1936).
"* C. R. Presenius, Qualitative Analysis. 17th ed. Translated by C. A.
Mitchell, Wiley, New York, 1921, p. 314. See also L. J. Curtmann and P. Roth-
berg, J. Am. Chem. Soc., 33, 718 (1911).
The procedure used by Hahn"' is recommended in carrying out the

test.
^[ProcedureA strip of asbestos paper ( 2 x 6 'cm.) about 0.5 mm.
thick is well moistened at one end and a depression malde in the paper with
a rounded glass rod. This is best done on a cork, provided with a depres-
sion of the required depth. A point is made in the middle of the depression
of the paper with a drawn-out end of a glass rod. If the asbestos is slightly
pierced at this point or tip, no harm results.
The asbestos is then strongly ignited in a reducing ,Bunsen flame and a
drop of the test solution is placed precisely on the asbestos tip, which is
ignited again. Before the asbestos is quite cold, it is held with the concave
side of the depression over the mouth of a tube emitting a stream of hydro-
gen. By moving the strip slightly up and down, it is easy to discover
the position at which the glowing is strongest. This indicates the presence
of platinum metals.
The hydrogen is generated in a Kipp's apparatus from purest zinc
and hydrochloric acid, and passed through a tube containing fine grained
soda lime. It is then led upward through a capillary tube which is drawn
so that the flame is only 5-10 mm. high. The size of the opening must be
determined by trial.
The intensity of the glowing depends mainly on the concentration of
the solution, and only slightly on the drop size. A large volume of Uquid
is spread over a large surface, all of which glows after heating and treating
with hydrogen. A small voliune of the same solution, however, placed
exactly on the tip oi the po'mt, gives an almost point-siised glowing area
which is very easy to see; owing to the contrast with the surrounding area.
When using a microdrop (1 mm.') of a solution of platinic chloride,
the following observations may be made:
Concentration of the solution of
platinum/(nim.>) Kesalt
1-10~' The hydrogen ignites "^ -^ . ^
1-10"* The speck glows very brightly^
8-10~' The speck glows very brightly-
6-10~' The speck glows clearly
4-10~ The speck glows weakly
2-10~' The speck glows only at times
I 10~ The speck does not glow at all '
Accordingly, the following sensitivity data hold for platinum:
Ldmit of Identification: 0.04 7 platinum
Concentration Ldmit: 1:250,000 /
Palladium, and also iridium and rhodium can.^be defected by this
catalytic reaction.'"* The identification limits are: 0.18 7 Ir; 0.02 y Rh;
0.01 7 Pd.
F. L. Hahn, Mikrochtmie, 8, 77 (1930).
" L. J. Curtmann and P. Rothberg, / . Am. Ohem. Soc, 33, 718 (1911).
PLATINUM METALS 103
This test for the platmum metals is remarkably indifferent to the

presence of foreign elements. Iron, uranium, copper, molybdenum,
nickel, and cobalt salts do not interfere with the detection of platinum
even when present 1000 times in excess. Although arsenic poisons the
catalysis, 0.07 7 of platinum can still be detected in the presence of 50
times the amoimt of arsenic (as arsenic trioxide).
b) By induced redxiction of nickel salts^"
Sodium hypophosphite acts only very slowly on aqueous solutions
of nickel salts to give metallic nickel (with varying nickel phosphide
content): Ni++ + H^jOr + 2 HjO -> Ni + 2 P O " + 6 H+. This
reaction is remarkably accelerated by small amounts of palladium (or other
platinmn metals)."' As palladium solutions are rapidly reduced by
hypophosphite to metallic palladium, the action may be due to colloidal
palladium, on whose surface the hypophosphite is decomposed with libera-
tion of hydrogen. Apparently, the reduction effect on the nickel salts is
due to the hydrogen being present in the nascent state or else in an adsorbed
form.*" This may also be the reason why anhydrous chromium (III)
chloride, in neutral or acid solution, is more rapidly dissolved in the pres-
ence of small amounts of palladium salts.
^[ProcedureTwo cleaned test tubes, which have been rinsed mth
alcohol and ether to remove traces of fat, are charged with 10 ml. 1%
nickel acetate solution, and 1 ml. saturated sodium hypophosphite solu-
tion. In one test tube is placed 1 ml. of the neutral or weakly acid test
solution, and in the other 1 ml. water. The test tubes are then stood in a
beaker containing boiling water. In a few minutes, hydrogen begins to
appear in generous amounts, and in 2 to 30 minutes, according to the con-
tent of palladium, nickel is deposited, partly as a black powder and partly
as a metallic mirror. The blank test remains green, and nickel is only
deposited after much longer warming.
Limit of Identification: 0.0025 7 palladium (in 1 ml.)
Reagents: 1) 1% nickel acetate solution
S) Saturated sodium hypophosphite solution
The addition of potassium iodide, which iorms insoluble Pdlj with
Pd++, completely inhibits the catalytic acceleration of the nickel reduction.
A saturated water solution of Pdlj has no action, in contrast with a satu-
rated solution of palladiimi dimethylglyoxime, of which one drop has a
distinct effect.
" F. Feigl and E. Fr&nkel, Ber., 66, 540 (1932).
" C. Paal and L. Friederici, Ber., 64, 1766, 2661 (1931); see also R. Scholder
and H. L. Haken, ibid., 64, 2870 (1931).
" C. Paal and L. Friederici, Ber., 66, 640 (1932).
Salts of Pt, Os, and Ru behave similarly to pallkdium, but with less
sensitivity. A slight content of palladium may bei responsible for the
action in these cases. J
Limit of Identification: 1.5 -y platinum, 0.5 y o s m i ^ , 0.5 y ruthenium
[l: 6,600,000 platinum
Concentration Limit: j 1:20,000,000 osmium
[1:20,000,000 ruthenium
PLATINUM
Test with stannous chloride, in presence of other noble metals."" Plati-
num salts, like those of gold, palladium, and osmium, in acid solution,
are reduced to the metal by stannous chloride. The platinum can be de-
tected even in the presence of these noble metals by a spot reaction. It
is fixed on filter paper by converting it into insoluble ammonia-resistant
thallium platinum chloride, TljPtCU. The fleck is then spotted with an
acid solution of staimous chloride.
^ProcedureÂ drop of thallium nitrate is placed on filter paper,
followed by a drop of the test solution, and another drop of thallium
nitrate. The paper is washed with aminonia. Any double salts of gold
or palladium go into solution, and are washed away, while T^PtCU
remains behind. On treatment with a drop of stannous chloride solu-
tion in strong hydrochloric acid, a yellow to t)range-red stain is formed,
according to the amoimt of platinum present.
Limit of Identification: 0.025 y platinum (in 0.002 ml.)
Reagents: 1) Saturated solution of thalliunS nitrate
2) Stannous chloride solution
PALLADIUM
1. Test with stannous chloride in the presence of gold and platinum.^"
Palladium salts, like gold and platinum salts, are reduced to the metal
by stannous chloride in acid solution. In order to detect palladium by a
spot test in the presence of these two metals, use vis made of the fact that
palladium salts are precipitated by mercuric cyanide, to give insoluble
palladium cyanide, whereas gold and platinum salts form soluble complex
cyanides. Palladium cyanide reacts with stannous chloride.
^[ProcedureOne drop of a mercuric cyanide solution, followed by a
drop of the test solution, and a further drop of mercuric cyanide solution,
are placed on filter paper. The palladium is precipitated as palladous
cyanide in the middle of the fleck, whereas the gold and platinum diffuse
"N.A.Tananaeff andG.T.Michaltachiachin.Z. anal. Chem., 94, 188 (1933).
"N. A. Tananaeff and K. A. Dolgow, Chem. Abstracts, 24,1313 (1930).
PALLADIUM 105
outwards, and can be completely washed away with several drops of

water. Stannous chloride is then placed on the middle of the fleck.
A dark orange to yellow-gold color appears if palladiiun is present.
Limit of Identification: 0.04 y palladium (in 0.002 ml.)
Reagents: 1) Saturated mercuric cyanide solution
2) Stannous chloride solution
2. Test by catalysis of the reduction of phosphomolybdates by carbon
monoxide."* Carbon monoxide and hydrogen reduce acid molybdate
auad phosphomolybdate solutions only very slowly. In the presence
of metallic platinum and palladium, which act as catalysts, the reduction"'
(especially of phosphomolybdates) takes place quickly. A lower molyb-
denum oxide, "molybdenum blue" results. In contrast to hydrogen,
carbon monoxide can reduce only acid palladium solutions to metallic
palladium. The latter, owing to its finely divided condition, has a very
marked catalytic action on the reduction of phosphomolybdic acid by car-
bon monoxide. Probably the acceleration of the reaction byfinelydivided
palladium is due to its adsorption of the carbon monoxide molecules,
which effects not only a condensation of the gas but also changes the linkage
in the carbon monoxide molecules, so that the adsorbed gas is more reactive.
As very small amounts of metallic palladium are sufficient to increase
appreciably the reduction of phosphomolybdic acid with carbon monoxide,
the reaction with activated CO affords a very sensitive and specific test for
palladium.
f ProcedureTwo drops of the slightly acid test solution are mixed
with a drop of phosphomolybdic acid in a microcentrifuge tube. The tube
is gently warmed and a rapid stream of carbon monoxide passed through
the mixture by means of a fine capillary. According to the palladium
content, a more or less intense blue color appears, either at once, or in 1 to
2 minutes. For very small amounts of palladium, a blank on pure phos-
phomolybdic acid should be carried out, in order to compare the colors
Limit of Ideniification: 0.025 y palladiiun
Reagents: 10% phosphomolybdic acid (for preparation, see page 87).
The carbon monoxide for reduction is best prepared by
dropping cone, formic acid into concentrated sulfuric acid
at about 100 C.
Large amounts of ruthenium and osmium, owing to their own intense
color, interfere with the test for small amounts of palladium. This inter-
ference is overcome if, after passing carbon monoxide through, the solu-
" ' F. Feigl and P. Krumholz, Ber., 63, 1917 (1930).
"' C. Zenghelis, Z. anal. Chem., 49, 729 (1910).
106 n.- TBBTs roB HBTALS
HOD. is shaken witii a few drops of amyl alcohol, in which the molybdeniun
blue is soluble. In this way 0.12 y palladium can be detected in the pres-
ence of 1000 times the amount of osmium. ,I
Iron (III), mercury, and gold salts reduce the sensitivity of the test.
Other metallic salts do not interfere appreciably so long as their concen-
tration does not exceed 0.25 to 1%.
If platinum salts are to be tested for palladium, the test solution
should contain not more than 0.1% platinum, as larger amounts of platinum
reduce the sensitivity of the test for palladium.
Arsenites and arsenates affect the test, when their concentration
exceeds 0.05%. Arsenites have a reducing action; arsenates accelerate
the carbon monoxide reduction of phosphomolybdic acid, even in the ab-
sence of palladium.
3. Test mib nickd dimethylglyoxime.''* If a suspension of red nickel
dimethylglyoxime (see page 114) in water is treated with a neutral or acetic
acid solution of a palladium salt, acid-insoluble, yellow palladium dimethyl-
glyoxime and a soluble nickel salt are produced almost immediately
(DH = dimethylglyoxime radical): ^
Ni(DH)j + Pd++ -> Pd(DH)2 + Ni++
A sensitive and sure test for palladium is based on this reaction in
combination with the protective layer effect. If filter paper is impregnated,
with nickel dimethylglyoxime and the red paper is treated with 1 drop of a
neutral or acetic acid solution of a palladium salt, the Pd++ ions react with
the nickel salt distributed in the capillaries of the paper. When sufficient
quantities of palladium are present, the fleck turns from red to yellow.
Small quantities give no change in color since only the outer parts of the
solid nickel dimethylglyoxime are consumed, while the greater part of
tiie red nickel compound remains unchanged. If the reagent paper that
has been spotted with dilute palladium solution, and which seemingly has
not been altered, is dipped into dilute hydrochloric acid, the free nickel
dimethylglyoxime is dissolved almost immediately and the red paper
becomes white. However, an invisible minute quantity of the acid-stable
palladium dimethylglyoxime is present at the site of the fleck. It protects
the underlying red nickel dimethylgloxime from attack by the acid; a red
fleck is Ipft. The detection of palladimn on nickel dimethylglyoxime paper
by means of the protective layer effect is not only very sensitive but also
absolutely specific, since no other metal ion reacts thus' under these con-
ditions.
^ProcedureA drop of neutral or acetic acid" test solution is placed
on nickel dimethylgloxime paper and almost dried by gentle warming
"*F. Feigl, Chemialry & Induttry, 67, 1161 (1938).
OSUITTM AND BTJTHENIUM 107
(waving over a flame or in a blast of heated air). The red paper is then
bathed in dilute hydrochloric acid until the surface surrounding the fleck
becomes white. The paper is then washed in cold water. A pink to red
spot remains, depending on the quantity of palladium present.
Limit of Identification: 0.05 y palladium
Reagent: Nickel dimethylglyoxime paper. Filter paper (S&S 589g)
is bathed in cold saturated alcohol solution of dimethyl-
glyoxime. After drying, the paper is placed in a solution of
2 N Ni(N03)s that has been made barely ammoniacal;
nickel dimethylglyoxime precipitates. After thorough
washing with water, the paper is bathed briefly in alcohol,
and dried. -
4. Other tests for palladiiiin. 1. An orange-yellow fleck is produced by
spotting the test solution on filter paper with an alcohol solution of naph-
thalene-4-sulfonic acid-l-azo-5-ortho-8-hydroxy(Juinoline"' (Id". Limit:
2 y Pd).
2. A red-violet fleck results if filter paper impregnated with p-di-
methylaminobenzylidene rhodanine is spotted with the acidified test
solution"' (Id". Limit: 0.004 y Pd). Special measures are required when
Au, Pt, Ag, and Hg salts are present, as they give analogous reactions.
3. Palladium may be detected by means of ^ neutral or slightly acidi-
fied solution of mercuric cyanide containing diphenylcarbazide.'" The
colorless solution turns violet because insoluble white Pd(CN)2 and Hg^-^
ions are formed; the latter then react with the diphenylcarbazide (see
page 48). The test is carried out on a spot plate {Id". Limit: 0.5 y Pd).
Considerable quantities of chloride impede the reaction.
OSMIUM AND RUTHENIUM
1. Test by activation of chlorate solutions."'' Alkali chlorate solutions
which are neutral or weakly acid have only a very sUght oxidizing action.
On the other hand, chlorates are strong oxidants in highly acidified solu-
tions. Alkah chlorate solutions are activated by the addition of osmium
tetroxide or ruthenium hydroxide, so that they give up their oxygen rapidly
to organic and inorganic compounds with reduction to chloride.'" For
instance, iodine can be liberated from potassium iodide in weakly acid
* G. Gutzeit and R. Monnier, Helv. Chim. Acta, 16, 233 (1933).
" F. Feigl, p . Krumholz, and E. Rajmann, Mikfochemie, 9, 165 (1931).
' " F. Feigl, unpublished studies.
' " F. Feigl, studies with S. Pickholz.
' K. A. Hofmann, Ber., 46, 3329 (1912); K. A. Sofmann, O. Ehrhart, and 0 .
Schneider, ibid., 46, 1657 (1913).
lbs II. TESTS FOR METALS
solutions, when merely a trace of osmium tetroxide is present.*" The

action of the osmium tetroxide is due to the formation of a complex com-
pound between chlorate and osmium tetroxide. The action of osmium
tetroxide itself on potassium iodide solution is: ,
Os04 + 4 KI + 2 H2SO4 = OsOs + 2 KjSO* + 2 H2O + 2 I2
This accompanying reaction, however, is only of importance when larger
amounts of osmium tetroxide are present. In any case it is best to dilute
the osmium test solution so that the reaction with potassium iodide does
not proceed.
This test for osmium and ruthenium is decisive in the absence of other
oxidizing compounds and colored ions.
^ProcedureA drop of potassium chlorate-potassium iodide solu-
tion, acidified with, a drop of dilute sulfuric acid, is placed on a spot plate.
Then, a drop of a starch solution and a drop of the neutral test solution
are added. According to the osmimn and ruthenium content, blue starch-
iodine is formed, either at once or in a short time. A blank test should
be carried out for small amounts of osmium tetroxide.
Limit of Identification: 0,005 y osmium tetroxide
When the test and blank are allowed to stand for several hours and
compared, OsO* can be detected in a dilution of 1:50,000,000.
Reagents: 1) Solution of 1 g. potassium chlorate and 1 g. potassium
iodide in 100 ml. water
2) Dilute sulfuric acid (1:1,000)
S) Starch solution (1%)
This test for osmium may be made specific by utilizing the volatility
of O8O4. The acidified test solution is gently warmed in the apparatus
shown in Figure 27 (page 31) and the volatile OSO4 is taken, up in a drop
of water hanging on the glass knob. The reaction with potassium'chlorate
and potassium iodide is carried out, on a spot plate, using this drop.
Limit of Identification: 0.01 y osmium
2. Test for rutheniain with rubeanic acid.''' Rubeanic acid (I) reacts
in ammoniacal solution in its aci-form (II)
" ' For strongly acid alkali chlorate solutions various oaUlyats are known,
e.g., vanadic acid [R. Luther, Z. Elektrochem., 13, 437, (1907)] and <ranadyl salts
[R. Luther and T. F. Ruttner, Z. anal. Chem., 46, 521 (1901)]. The reduction of
HClOj by KI, which does,not take place in dilute solutions, is, however, catalysed
both by Fe(II) and Fe(III) salts. [See C, F, Schonbein, / . prakt. Chem., [I], 75,109
(1868); W. F. Green, J. Phys. Chem., 12, 389 (1908).]
' " H. Wolbling and B. Steiger, Mikrochemie, 16,295 (1934).
COBAW 109
S=CNH, HSC-=NH S=CNH,
S=CNHj HSCNH HN==CS

(I) (II) (III)
with copper, cobalt, and nickel salts giving insoluble colored compounds
(see page 118). In strong mineral acid solutions, rubeanic acid reacts only.
with certain elements of the platinum group. With palladium and plat-
inum salts, red crystalline precipitates are obtained, which are inner
complex salts (III) of a semi-aci-form of rubeanic acid. Ruthenium salts
give a soluble blue compound, whose structure is not yet known. It is
remarkable that osmium, which in its other reactions is so similar to ru-
theniiun, does not react with rubeanic acid, so that this reagent can be used
for the detection of ruthenium in the presence of osmium. The reaction
can also he used to detect ruthenium in the presence of palladium and plati-
mmi. The insoluble compound is either filtered or centrifuged off, and
the blue color of the clarified solution observed.
^ProcedureA drop of the hydrochloric acid test solution is mixed
in a microcrucible with 1 or 2 drops of a solution of rubeanic acid in glacial
acetic acid, and the mixtiire gently warmed over a microbumer. According
to the amount of ruthenimn present, a more or less deep blue color appears.
Limit of Identification: 0.2 y ruthenium
Concentration Limit: 1:250,0(X)
Reagent: 0.2% solution of rubeanic acid''' in glacial acetic acid
3. Other tests for osmium. l.A blue or green stain is formed on paper by
the reaction between osmiiun and a saturated solution of benzidine acetate
or K4Fe(CN)ei" {Id". Limit: 0.01 7 Os in 0.001 ml.). For the detection
of still smaller amounts, OSO4 is volatilized in a glass tube drawn out to a
capillary, and the gas directed on to paper impregnated with the reagent
{Id". Limit: 0.008 7 Os in 0.001 ml.).
B. AMMONIUM SULFIDE GROUP

COBALT
1. Test with nitrosonaphthol.'^^ a-Nitroso-(8-naphthol (I) and other
aromatic o-nitrosophenols react, in their tautomeric isonitroso-oxime forms
(II), with cobalt and certain other metals to form colored precipitates.
Cobalt salts in acetic acid, neutral, or ammoniacal solution give red-brown
precipitates, which, once formed, are not soluble even in mineral acids.
" For preparation, see R. Wollner, / . prakt. Chem., 29,129 (1884).
" N. A. Tananaeff and A. N. Romanjuk, Z. anal. Chem., 108, 30 (1937).
" M. Ilinsky, Ber., 17, 2692 (1884); see also F. Peigl and R. Stern, Z. anal.
Chem., 60, 31 (1921).
110 n. TESTS FOE METALS
The precipitate is an inner complex Co (III) salt, whode structure is shown

in (III). I
NO 0=NH iO==N Co/3
-OH ^ f >=0 +Co-H-^
OJ (I)
The conversion of Co (II) into Co (III) is due to the reagent itself. I t
acts as an oxidizing agent because it is an orthoquinoid compound and a
derivative of nitrous acid.
Ferric, uranyl, copper, and palladium salts also give insoluble colored
compounds with nitrosonaphthol. Under suitable conditions, however,
the test for cobalt can be carried out successfully even in the presence of
considerable amounts of iron, uranium, and copper.
IfProcedureA drop of the neutral or weakly acid test solution and
a drop of the nitrosonaphthol solution are placed successively on filter
paper. A brown stain indicates the presence of cobalt.
If the test solution is strongly acid, it should be held over an ammonia
bottle after placing on filter paper, to neutralize the acid. Then, after the
addition of the reagent solution, the fleck is treated with a drop of dilute
sulfuric acid.
Limit of Identification: 0.05 y cobalt
Reagents: 1) Nitrosonaphthol solution. 1 g. a-nitroso-)3-naphthol is
dissolved in 50 ml. glacial acetic acid and diluted
with water to 100 ml.
2) 2 N sulfuric acid
As little as 0.006 T cobalt can be detected in a drop of 0.01 ml.>"
when instead of an acetic acid solution, an alkaline reagent solution is
used."' This is prepared as follows: 0.1 g. a-nitroso-/3-naphthol is dis-
solved by warming in 20 ml. water containing 1 ml. dilute alkali; the mix-
ture is filtered and the clear filtrate diluted to 200 ml. <If the isomeric
j8-nitroso-a-naphthol is used in place of a-nitroso-/3-naphthol, still smaller,
about one-tenth, quantities of cobalt can be detected.'*'
Test for cobalt in the presence of iron
Ferric salts form brown compounds with nitrosonaphthol and thus
interfere with the test for cobalt. Although iron (III) nitrosonaphthol
" W. BSttger, Mikrochemie {Emich Festschrift), 1930, p. 28.
F. W. Atack, J. Soc. Chem. Ind., 34,641 (1915).
"T Compare B. N. Cacciapnoti and F. Feria, Ann. chim. apvUcata, 29,166
(1939). ^
COBAIrt> 111
is soluble in acids, the precipitate dissolves quite slowly when it is deposited

in the pores of the filter paper. In the presence of iron, it is best to pre-
cipitate it together with the cobalt on the filter paper as FeP04 and
Co(P04)s, and then to add the reagent. The yelldW-white ferric phosphate
does not react with nitrosonaphthol, whereas cobalt phosphate reacts
instantaneously.
Limit of Identification: 0.21 y cobalt /in the presence of 1860
Concentration Limit: 1:240,000 1 times the amount of iron
Limit of Identification: 0.84 y cobalt fin the presence of 2100
Concentration Limit: 1:59,500 \times the amount of iron
When the test solution is acid the following procedure should be
used.
lIProcednreÂ drop of the acid test solution is mixed on a spot plate
with a drop of nitrosonaphthol and a few drops of sodium phosphate.
In the presence of cobalt, a brown coloration appears, which should be
compared with a blank when testing for small amounts.
Limit of Identification: 0.5 y cobalt fin the presence of 1000
Concentration Idmit: 1:100,000 \time8 the amount of iron
Reagents: 1) 1% solution of a-nitroso-/S-naphthol in acetone
2) 10% solution of sodium phosphate '
Test for cobalt in the -presence of uranium
Uranyl salts react with a-nitroso-;8-naphthol and form a yellow
precipitate. It is therefore necessary to take precautions in the presence
of uranium, especially when testing for small amounts of cobalt. Like
iron, uranium may be converted into the nonreacting phosphate, by treat-
ment with ammonium phosphate. The test is then carried out as in the
presence of iron salts.
T u ofr Identtficatton:
Limit Tj t f noe u li fiî
0.25 y cobalt J,. the presence
,f of . 1000 ,
{times the amount of
Concentration Limit: 1:200,000 i
uranium
V
Test for edbdU in the presence of copper

Copper (II) salts react with a-nitroso-/S-naphthol in the same way as
cobalt salts, and thus interfere with a decisive test. By means of potas-
sium iodide, copper is converted into cuprous iodide, which does not react
with nitrosonaphthol, and thus cobalt may be detected even LQ the presence
of large amoimts of copper. The free iodine developed:
2 Cu-H- + 4 I- = CuJi -t- I,
Cm be removed by sodium sulfite. The white insoluble cuprous iodide
does not interfere with the recognition of cobaltic nitrcônaphthol.
f ProcedureA drop of the acid test solution, a drop of 2 ^ hydro-
112 n . TESTS FOH METALS
chloric acid, and one of potassium iodide, together with a little solid sodium
sulfite are mixed on a spot plate. Then a drop of nitrosonaphthol solution
and a few drops of sodium acetate are added. In the presence of cobalt, a
more or less deep brown color appears. '
Limit of Identification: 0.2 7 cobalt Jin the presence of 2500
Concentration Limit: 1:250,000 \times the amount of copper
Reagents: 1) 10% potassium iodide solution
5) Solid sodium sulfite
8) 1% solution of nitrosonaphthol in acetone
6) 2iV hydrochloric acid
2. Test with rabeanic acid.'^' Cobalt is quantitatively precipitated as
a yellow-brown amorphous salt by an alcoholic solution of rubeanic acid
(diamide of dithio-oxalic acid) in the presence of ammonia or sodium
acetate. The compound formed is an inner complex salt of the acid
di-imido form of rubeanic acid. Once formed, the salt is insoluble in
dilute mineral acids. (For the mechanism of the salt formation, see page
118.)
Nickel and copper also react under the same conditions, giving blue
and black precipitates, respectively.
^ProcedureA drop of the test solution is placed on filter paper, held
over an ammonia bottle, and then spotted with a drop of the reagent
solution. In the presence of cobalt, a brown fleck or ring is formed.
A large excess oi- ammoniimi salts reduces the sensitivity.
Limit of Identification: 0.03 y cobalt
2) 1% alcohol solution of rubeanic acid"'
3. Test with ammoniiun thiocyanate and acetone."" Cobalt salts give a
deep blue color"* with thiocyanates in acid solution in the presence of
alcohols, aldehydes, and ketones, probably due to a solvate formation
of cobalt thiocyanate or the complex cobalt thiocyanates, such as K2C0-
(CNS), with the organic compound. It is interesting to note that the
absorption spectrum of the potassium compoimd in many alcohols and
ketones is imaffected by the nature of the solvent.\'' Nickel salts inter-
"Pr. RAy and R. M. R&y, Quart. J. Indian Chem. Soc, 3. 118 (1926); Pr.
R4y, Z. anal. Chem., 79, 94 (1929).
For preparation, see page 71. ,
" H . Ditz, Chem.-Ztg., 26. 110 (1901); 46, 121 (1922); Z. anorg. allgsm. Chem.,
219,97 (1934). I. M. Kolthoff, Mikrochemie, 8,176 (1930).- '2'
" Compare H. W. Vogel, Ber., 12, 2313 (1879); A. Rosenheim and co-workers,
ibid., 33.1113 (1900); Z. anorg. allgem. Chem.,21,289 (1901); 49.28 (1906).
J. V. Zawidflki, Chem. AbstraUs, 5, 424 (1911).
coBAi/r 113
fere only if present in considerable amounts; they produce a light blue

coloration. Ferric salts give the familiar deep red [Fe (CNS)3 or Fe (CNS)!"
etc ]. Since the product is soluble in the same organic liquids as Co(CNS)2,
the blue due to small amounts of cobalt may be hidden. However, cobalt
can be detected in the presence of large amounts of iron by taking the
proper measures.
Copper salts, which give a red-brown coloration or precipitate of
Cu(CNS)2, should be removed as cuprous thiocyanate.
^ProcedureA drop of the test solution is mixed with 5 drops of an
acetone solution of ammonium thiocyanate on a spot plate. According
to the cobalt content, a green to blue color appears.
Ldmit of Identification: 0.5 7 cobalt
Reagent: A saturated solution of ammonium thiocyanate in acetone
When nickel salts are to be tested for their cobalt content, the strength
of the solution should not exceed 0.2% nickel. A solution of this strength
when it contains nickel alone, only gives a yellowish green color with ace-
tone solution of thiocyanate. If as little as 0.5 y cobalt is present in a
drop (corresponding to a proportion Co:Ni = 1:200), a definite blue-green
color develops on addition of thiocyanate.
Test for cobaU in the presence of iron^^^
Ferric salts are converted by alkali fluorides into fairly insoluble
colorless complex iron fluorides of the general formula MsFeFi. The
stability of these complexes is so great that an aqueous solution contains
only very few iron ions, which are insufi&cient to give the red ferric thio-
cyanate reaction. Since the cobalt reaction, however, is not hindered by
the presence offluorides,cobalt can be detected in the presence of much iron,
if the latter is masked in this way.
^[ProcedureOne ox two drops of the slightly acid test solution is
mixed with a few mg. ammonium fluoride on a spot plate; then 5 drops
ammonium thiocyanate solution in acetone is added. In this way, X y
cobalt in 3 drops of a cobalt solution (1:50,000) can be detected by the
blue color in the presence of 1000 times the amount of iron.
Reagents: 1) Ammonium fluoride, solid
2) 10% solution of ammonium thiocyanate in acetone
4. Other tests for cobalt. 1. Cobalt can be detected (in the presence of
1000 times as much nickel) by means of 1% water solution of 2-nitroso-l-
naphthol-4-sulfonic acid at pH 7-8."* Red coloration {Id". Limit: 0.01
y Co). Copper and ferrous salts also give color reactions (pp. 74 and 128).
"I. M. Kolthoff, Mikrochamie, 8,176 (1930).
" L. A. Sarver, Ind. Eng. Chem., Anal. Ed., 10, 378 (1938).
114 n . TESTS FOR HETALS
NICKEL - J
1. Test with dimethylglyoxime."' Dimethylglyoximei (diacetyldioxiine),
CH,C(NOH)C(NOH)CHs, as well as a large number of other d-dioximes
of the general formula RC(NOH)C(NOH)R, gives a bright red
insoluble salt with nickel salts in neutral, acetic acid, or ammoniacal
solutions. For dimethylglyoxime the inner complex compound formed haa
the structure:
HaCC=N N=CCH,
V
/
H,C-C=N N=C-CH,
I II
OH O
The precipitation of nickel may be prevented by the presence of
large amounts of oxidizing substances (hydrogen peroxide, halogens,
nitrates, etc). A red color develops (see page 117). Palladixmi and plati-
num give yellow, acid-insoluble, inner complex salts, whose structure is
analogous to that of the nickel salt. Ferrous salts, in ammoniacal solu-
tions containing tartrate, produce a red coloration (see page 126). Cobalt
salts react with dimethylglyoxime to give soluble complex compounds of,
di- and trivalent cobalt. The dimethylglyoxime is thus consumed (see
also page 434), and so the sensitivity of the nickel test is very much reduced
in the presence of considerable amounts of cobalt. In this case a special
procedure is used (see page 435). Copper salts in ammoniacal solution,
give violet, soluble complex compounds with dimethylglyoxime.
When the test for nickel is to be carried out in ammoniacal solution,
and other metals, precipitated by ammonia, are present, the hydrous oxide
precipitation must be masked by the addition of citrates or tartrates. Care
must be taken that both iron (III) and cobalt salts are not present, as
although either of these metals alone is not precipitated by dimethyl-
glyoxime from ammoniacal, tartrate solutions, yet when they are together,
a red-brown precipitate is formed."^ Special attention must be given to
this possibility (see page 116).
UProcedureA drop of the test solution and of an alcoholic dimethyl-
glyoxime solution are placed either on filter paper and held over ammonia,
or on a spot plate and a small drop of dilute ammonia added.. The forma-
tion of a red fleck or circle on paper, or of a precipitate or color on the
spot plate, indicates the presence of nickel.
"5L. Tschugaeff, Ber., 38, 2520 (1905); O. Brunck, Z. angew. Chem., 20, 1844
(1907); 27, 315 (1914).
" I. G. Weeldenburg, Rec. trav. Mm., 43, 46M1924).
NICKEL 115
Limit of IdentificcUion: 0.16 y nickel

Reagent: 1% solution of dimethylglyoxime in alcohol
The test is considerably more sensitive when a drop of the test
solution is placed on dried filter paper impregnated with the reagent.
The impregnation is best carried out using a warm saturated solution
of the reagent in acetone. In this way 0.015 y nickel {concentration
limit 1:3,330,000) can be detected."'
^ Test in the presence of iron
Nickel can be identified by dimethylglyoxime in the presence of
considerable amounts of iron (III) salts.
IfProcedureA drop of the test solution, a drop of a saturated sodium
tartrate solution, 2 drops of a saturated sodium carbonate solution, and
finally, a drop of alcoholic dimethylglyoxime, are successively placed on
a spot plate. The red nickel dimethylgloxime precipitate is formed at
the edge and surface of the liquid, owing to the low surface tension of
the alcohol.
T . .^ , , , , . . ^. n_ . , , fin the presence of 1000 times
Limit of Idenltncation: 0.5 y nickel \^, x - 7-
_ , , T ; ^^.^cM^l\r^n U h c a m o u n t of irOU VO. 2 N
Concentratton Limit: 1:100,000 i, , , , . ., , ,.
(hydrochloric acid solution
Test in the presence of cobalt, copper, andmanganese
a) On the spot plate.
When as much as 50 times the amount of cobalt is present in ammoni-
acal solution, the detection of 2 Y of nickel becomes difficult. If still
larger proportions of cobalt are present, the test is impossible, as dimethyl-
glyoxime is consumed by the cobalt (see page 434); furthermore small
quantities of nickel glyoxime are soluble in solutions of he cobalt dioxime
compound.
When, however, cobalt is converted to the trivalent form before addi-
tion of the dimethylglyoxime, nickel can be detected in the presence of 200
times the amount of cobalt.
^[ProcedureA drop of the acid test solution, a drop of 3% hydrogen
peroxide, and a drop of a saturated solution of sodium carbonate are
placed, in turn, on a spot plate. When large amounts of cobalt are present
a green precipitate is formed. (It slowly darkens as it finally forms cobaltic
oxide.) Smaller amounts given a green coloration. If a drop of the 1%
alcoholic dimethylglyoxime solution is then added, red nickel dimethyl-
glyoxime is formed, and slowly rises to the surface of the liquid, owing to
the lower surface tension of the alcohol.
Limit of Identification: 1.25 y nickel fin the presence of 200 times
Concentration Limit: 1:40,000 \the amount of cobalt
' " F. Feigl and H. J. Kapulitzas, Mikrochcmie, 8, 244 (1930).
When both cobalt and manganese are present, the same procedure
may be used, although the sensitivity is reduced, owing to the formation
of manganese dioxide. Nevertheless, 2.5 7 nickel may' readily be detected
in the presence of 80 times the amount of cobalt and manganese.
b) On impregnated paper.
The procedure described on page 116 for testing for nickel on paper
impregnated with dimethylglyoxime can be used for the detection of small
amounts of nickel in the presence of much cobalt and copper, or manganese.
^ProcedureA drop of the test solution is placed on paper impreg-
nated with dimethylglyoxime. The paper is then immersed in a bath of
dilute ammonia, and kept gently in motion. The colored dimethylglyoxime
compounds of both cobalt and copper are dissolved; the red fleck due to
nickel remains on the white paper.
Limit of Identification: 0.8 7 nickel fin the presence of 1260 times
Concentration Limit: 1:62,500 1 the amount of cobalt
Limit of Identificaiion: 1.7 7 nickel Jin the presence of 590 times
The procedure is not applicable in the presence of manganese, owing
to the formation of manganese dioxide. If, however, ammonium carbonate
is used as the bath liquid, manganese dioxide is not formed. As the copper
and cobalt dimethylglyoxime compounds are not completely dissolved
out, the procedure is only advisable when testing for nickel in the pres-
ence of manganese.
Limit of Identificaiion: 0.1 7 nickel /in the presence of 10,000 times
Concentration Limit: 1:500,000 \the amount of manganese
Teat for traces of nickel in cobalt salts, see page 434.
Test for small amounis of nickel in the presence of cobalt and iron saife"'
Neither cobalt nor iron (HI) salts alone give insoluble compounds with
dimethylglyoxime, but together they, give a red-brown precipitate. This
is a complex compound of iron, cobalt, and dimethylglyoxime,*" The
formation of this compound can interfere with the detection of small
amounts of nickel. This interference can be inhibited by carrying out the
test under special conditions (for mechanism see page 435).
^[ProcedureOne or two drops of the test solution are placed in an
Emich centrifuge tube and warmed with a little saturated potassium
cyanide solution until the initial precipitate is dissolved. A few mg. of
Bolid dimethyl^yoxime and a few drops of formaldehyde are added; the
mixture is stirred with afineglass rod, and then.centrifuged. The deposited
w F. Feigl and H. J. Kaipulitzas, Mikrochemie (Emich Festschrift), 19S0,
p. 128.
" I . G. Weeldenburg, Bee. Irav. chim., 43,465 (1924).
NICKEL 117
dimetiiylglyoxime is colored red with nickel dimethylglyoxime, if nickel

is presents
2. Test with dimethylglyoxiine in the presence of oxidizing agents.'"" In
the presence of large amounts of nitrates and other oxidizing agents, small
amounts of nickel are not precipitated by dimethylglyoxime. Red to
orange colored solutions are formed instead. If sufficient oxidizing agent
is present, the precipitation of even large amounts of nickel is prevented.
The red solutions contain complex compounds of tetravalent nickel
probably with the complex cation.
OHj i
DHNNI;; DH CH,C(NO)
DH = I
' OH," . CH,CNOH
The formation of this colored nickel (IV) salt renders it possible to

increase the sensitivity of the dimethylglyoxime test. The discernibility
of the colored compound requires a lower ionization product, and accord-
ingly a smaller concentration of nickel than is required for the precipitation
of the normal insoluble nickel dimethylglyoxime. In agreement with this
is the fact that the compound of tetravalent nickel is stable in the presence
of potassium cyanide, whereas nickel dimethylglyoxime dissolves reaxlily.
The following test for nickel can, therefore, also be carried out in the
presence of cyanides.
IfProcedureA drop of the test solution is mixed on a spot plate with
1 or 2 drops of bromine water,2"' and rendered alkaline (disappearance of
the bromine color) with excess ammonia. Then a drop of dimethyl-
glyoxime solution is added. The oxidation by the hypobromite formed is
complete in 1 to 2 minutes. A red or orange colored solution remains in
the presence of nickel.
Limit of Identification: 0.12 y nickel
Reagents: 1) Saturated bromine water
2) Ammonia
S) 1% solution dimethylglyoxime in alcohol
3. Test with rubeanic add.'"' Rubeanic acid, the diamide of dithio-
" F. Feigl, Ber., 67, 758 (1924); see also A. P. RoUet, Compt. rend., US. 212
(1926).
*M Instead of bromine -water, persulfate (with the addition of a amall amount
of silver nitrate) may be used as the oxidizing agent (Communication from F. L.
Hahn).
" Pr. RAy and R. M. RAy, Quart. J. Indian Chem. Soe., S, 118 (1926); Pr. R4y,
Z. anat. Chem., 79, 95 (1930).
oxalic acid, forms, in solution, an equilibrium mixture with its tautomeric

(aci) di-imido form
SCNHj HSC=NH "SC=NH'
^ 1 ^ 2H+ + i
SCNH, HSC=NH LSG==NH
The acid form combines with nickel, cobalt, and copper salts to give
colorless, insoluble inner complex salts of the constitution
i S S
\ /
i Me
where Me = copper, cobalt, or nickel atom.^"* These complex salts are
formed when the concentration of the aci-form of rubeanic acid is large
enough to exceed the solubility product of the riibeanate in question. This
condition is attained by decreasing the number of hydrogen ions formed
according to the above equation by the addition of alkali acetate, ammonia,
or alkaU. The copper, cobalt, and nickel compounds, which are quantita-
tively precipitated from strongly ammoniacal solutions, once precipitated,
are also insoluble in dilute mineral acids. This is in accord with the theory
that they are inner complex salts. Their stability is only exceeded by that
of the cyanide complex salts of these metals, as is shown by the fact that the
rubeanates are soluble in potassium cyanide and are not precipitated from
alkaline cyanide solution.
llProcedureA drop of the test solution is placed on filter paper, held
over ammonia, and then treated with a drop of the reagent solution.
According to the nickel content, a blue to blue-violet stain forms.
Limit of Identification: 0.012 y nickel (in 0.016 ml.)
Concentration Limit: 1:1,250,000 ^^ ^
2) 1% alcoholic solution of rubeanic acid (see page 70)
It must be noted that the presence of much ammonium salt consider-
ably reduces the sensitivity of the test.
Test for nickel in the presence of cobalt, iron, or copper by capillary separation
of the ammine salts.^"*
As stated, rubeanic acid reacts, not only with nickel, but also with
cobalt and copper salts, to give colored complex compounds. None the
" ' The semi-aci-form ol rubeanic acid, in acid solution, produces colored
precipitates with Pt"*^ and Pd^^ ions. Soluble colored compounds are formed with
Ru'H- ions (compare, page 108).
" P. Feigl and H. J. Kapulitzas, Mikrochemie, 8, 239 (1930).
THALUTTM 119
less, in certain concentration limits, nickel can be detected in the presence

of ihsa& metals. Use is made of the different diffusion velocities of the
metal ammine salts in thin filter paper, the diffusion velocity for nickel
being most rapid. When a drop of an anunoniacal solution of copper,
cobalt, and nickel salts is placed on paper, or a drop of a neutral solution
on paper is held over ammonia, the nickel accumulates in the outer zone
of the spot. When a drop of the alcoholic reagent solution is then placed
at the side, as the drops coalesce, a blue ring of nickel rubeanate forms
around the brown to green or brown circle due to the cobalt and copper
compounds.
A drop (0.015 ml.) of a solution containing 1% cobalt and 0.0021%
nickel still shows a recognizable blue friiige round the yellow-brown
precipitation zone of the cobalt compoimd. This corresponds to a limit
of identification of 0.32 y nickel in a limiting proportion of Ni: Co = 1:480.
In the same way 0.032 y nickel can be detected in the presence of
4800 times the amount of iron. The iron is fixed in the center of the fleck
as Fe(OH), while the nickel ammine salt diffuses outward and reacts with
rubeanic acid in a separate zone.
THALLIUM
1. Test with potassium iodide. Potassium iodide precipitates the bright
yellow thallous iodide from acid solutions of thallous salts. The test is
affected by the presence of other metals giving insoluble iodides, that is by
mercury, silver, and lead. In the presence of mercury, thallimn can be
detected by using a laiê excess of potassium iodide, whereby the mercuric
iodide goes into solution as the complex KsHgl4. At the same time, by
the law of mass action, the solubility of the thallous iodide is reduced. In
the presence of silver and lead,">* it is best to digest with sodium thiosulfate
after precipitating the thallous iodide, or else to carry out the precipitation
in the presence of a large amount of tiiiosulfate. Silver and lead iodides
are thus dissolved as complex thiosulfates, and thallous iodide remains
unchanged.
IfProccdureA drop of the weakly acid test solution is mixed with a
drop of potassium iodide on a watch glass placed on a black background.
When a precipitate appears, a drop of sodium thiosulfate is added. A
yellow precipitate, insoluble in sodiiun thiosulfate, indicates tliallium.
Limit of Identification: 0.6 y thallium
Reagents: 1) 10% potassium iodide solution
2) 2% sodium thiosulfate
2. Test with benzidine.ô' When thallium is present as a thallic compound*
E . A. Werner, Chem. Newt, 58,61 (1886).
F. Fcigl, Chem.-Zig., 44, 689 (1920).
120 ^ - TESTS K)B METALS
it can be detected after conversion into Tl(OH)s by the'oxidation of benzi,

dine to "benzidine blue" (see page 55). Thallous salts, if present, must be
oxidized beforehand with aqua regia. '
It is necessary that manganese, cobalt, cerium, or silver salts should
not be present, nor any other oxidizing agent that would give the benzidine
color under the same conditions.
UProcedureA drop of ammonia is placed on spot paper, and a drop
of the test solution is added, followed by a drop of benzidine solution.
According to the amount of thallium present, a bluefleckor ring is formed.
Limit of Identificaiion: 0.3 y thaUium
IS) Benzidine solution. Benzidine is dissolved by heating
with dilute acetic acid, the solution allowed to cool, and
filtered
3. Test with phosphomolybdic acid and hydrobromic acid.'" A yellow
precipitate of thallivun (I) phosphomolybdate is formed by the interaction
of thallous salts and phosphomolybdic acid. When this precipitate is
treated with cone, bromine water, molybdenum blue and thaUium (III)
bromide are formed.
It appears that the phosphomolybdic acid is activated by its combi-
nation with thallium, as it normally reacts very slowly with hydrobromic
acid. Possibly the capacity of the bromide ion to cany the positive charge
from Mo (VI) to T1(I) is connected with the proximity in space of these
metals in the T1(.I) phosphomolybdate molecule.'"' This very singular
chemical reaction affords a means of testing for thallium (I) salts, but care
should be taken that no reducing substances are present, such as copper (I),
tin (II), antimony (III), iron (II), and mercurous salts. These are able
to reduce phosphomolybdate to molybdenum blue.
^ProcedureA drop of a saturated solution of phosphomolybdic acid
is placed on filter paper, and the test solution is nm from a capillary into
the middle of the spot. A drop of hydrobromic acid is then added. A
dark or light blue stain is formed, according to the amount of thallium
present.
Limit of Identification: 0.13 y thallium (in 0.025 ml.)
Reagents: 1) Phosphomolybdic acid (see page 85).
2) 50% hydrobromic acid '
' N. S. Poluektoff, Chem. Zentr., 1934,1, 3240, ' ' ^
' " T h i s hypothesis is supported by the observation that the foimatipn of
molybdenum blue is much slower when a mixture of phosphomolybdic and hydro-
bromic acid is treated on filter paper with a drop of a Gallium (I) salt.
THALLTOM - 121
4. Test with dipicrylamine.'"' Dipicrylamine (I), or a solution of its

sodiuiu salt, reacts in neutral solutions witli thallous salts. The red crystal-
line precipitate of thallium dipicrylamine (II), when once precipitated,
does not dissolve in dilute mineral acids. (The mechanism of the salt
formation is discussed on page 178.) -r
NO, TIONO
NO. j j I NO. JL
0%^<(~~\^<r \NO, 0JN<^^~ \N==/^ \N0J
NO, I NO, NO,
(II)
Thallium can be detected with dipicrylamine by the procedure used
for potassium (page 180). A drop of the neutral test solution is placed on
sodimn dipicrylamine paper. Thallium dipicrylamine is formed. If the
spotted paper is bathed in 0.1 N nitric acid, the unchanged orange-red
sodimn dipicrylamine is decomposed, forming bright yellow dipicrylamine,
whereas the red thallimn dipicrylamine remains unaltered. In this way,
20 y thallium can be detected in 1 drop.
Since the detection of thallium with dipicrylamine exhibits a sensi-
tivity that is relatively low for a spot reaction, and since, furthermore,
potassium and ammonium salts, as well as considerable quantities of
magnesium and sodium salts, interfere, it is better to use the dipicrylamine
reaction merely to identify thallium within the chloride group of the quali-
tative scheme. In other words, the element should be isolated as thallous
chloride, which is only slightly soluble in water. Any AgCl, PbCU, and
HgjClj that may have been precipitated with the TlCl do not react with
sodium dipicrylamine, whereas TlCl produces red thallium dipicrylamine
when spotted with the reagent.
.IfProcednreOne or two ml. of test solution is treated with dilute
hydrochloric acid at room temperature. The precipitate is collected on a
filter paper and washed free of acid with alcohol. The paper is then spread
on a glass or porcelain plate, spotted with 1 drop of sodium dipicrylamine
solution and then dried in a blast of heated air. 1 or 2 drops of 0.1 N
nitric acid are applied. If a red color develops, TlCl is present.
Reagent: Solution of sodium dipicrylamine. 0.2 g. dipicrylamine is
dissolved in 2 ml. 2 N sodium carbonate, then diluted
with 75 ml. water, and filtered
5. Other tests for thallium. Metal ions that form insoluble sulfides can,
with a single exception, also be precipitated as carbonates or basic
carbonates by adding an alkali carbonate. The exception is T1+ ion,
" F. Feigl and P. E. Barbosa, Rev. soc. brasil quim., 10, 137 (1941).
122 n- TESTS FOB METALS
whose carbonate is quite soluble ia water. Consequently, thallium can be

separated from other metals by treating the test solution with an eicess of
sodium carbonate and then filtering. If a drop of the filtrate is placed on
thick filter paper (S & S 601) and the fleck held over an open ammonium
sulfide bottle, a black-brown spot or ring (TljS) appears', according to the
quantity of thallium present {Id". Limit: 0.5 Y TI). If considerable
quantities of metal ions that are precipitated by sodium carbonate are
present, it must be remembered that smaU amounts of thallous carbonate
may be retained through adsorption. Furthermore, the carbonate precipi-
tation of Fe, Pb, and other heavy metal ions may be partially prevented if
organic hydroxy compounds that form complexes are present. In this
case, the filtrate will contain other metals that react with hydrogen sulfide.
IRON
1. Test with potassium ferrocyanlde. Potassiiun ferrocyanide forms
Prussian blue, Fe4[Fe(CN)6]3, with ferric salts in acid solution. This
compound, like Tumbull's blue Fe3[Fe(CN)6]2, is reduced to white ferro-
ferrocyanideî" by strong reducing agents such as Na2S204.
IfProcedureThe test can be carried''out by placing a drop of the
test solution and of potassium ferrocyanide solution together on filter
paper or on a spot plate.
Limit of Identification: 0.1 -r iron (on paper)
0.05 7 iron (on the spot plate)
Concentration Limit: 1:500,000 (on paper)
1:1,000,000 (on the spot plate)
In the presence of large proportions of other metal salts which give colorwl
precipitates with potassium ferrocyanide or that form complexes with the
Fe(III) ion (fluorides, oxalates,^" etc.), the Prussian blue reaction may be
either masked or completely prevented. In such cases it is best to use
test 2.
2. Test with o,o'-dipyridyl.2" Iron (II) salts in solutions of mineral acids
react with the organic base a,a'-dipyridyl (I) to give a soluble deep red
complex cation. This is very stable and possesses the coordination
formula (JI).
"O Fe
/<Z>'
"d) (I)
""C^/J
(II). - r ^
. M. Kohn, Z. anorg. Chem., 49, 443 (1906).
M. Kohn, Monaish.,'i3, 373 (1922); 44. 97 (1923).
F. Blau, Motxatsh., 19,647 (1898). F. Feigl andH. Hamburg, Z. anal. Chem.,
86, 7 (1931). ,
IRON 123
Iron (III) salts do not react under these conditions, so that very
small amounts of iron (II) salts can be detected in the presence of large
proportions of iron (III) as will be seen. Iron in the trivalent form, after
reduction, can also be detected by means of a,a'-dipyridyl.
Other ammine-forming, metallic ions in acid solution also react with
a,a'-dipyridyl, but only give weak colors, so that when sufficient reagent
is used they do not interfere with the test for iron. Large amounts of
halides, sulfates, etc. reduce the solubility of the ferrodipyridyl compound
in water, so that a red precipitate is sometimes formed. However, this
does not interfere with the test.
The a,a'-dipyridyl test for iron is especially useful when compounds
are present which interfere with the usual thiocyanate test (page 124).
The cheaper base a,a'-phenanthroline can be substituted for a,a'-
dipyridyl.
^ProcedureA drop of the test solution is treated with a drop of the
reagent solution on a spot plate, or a drop of the test solution is placed on
filter paper (S & S 589) which has been impregnated with an alcoholic
solution of the reagent, and dried. According to the amount of iron
present, a red or pink colored circle is formed.
lAmit of Identification: 0.03 y iron
Concentration Ldmit: 1:1,666,000
Reagent: 2% solution of a, a'-dipyridyl-" in alcohol
Test for iron {II) in the presence of iron {III) salts
Large amounts of iron (II) salts can be detected by the normal
procedure (as described) in the presence of iron (III) salts, since the pink
color of iron (II) dipyridyl is easily visible, even in the presence of the
yellow color of iron (III) salts. When, however, traces of iron (II) are
being detected, the slight pink coloration may easily be blanketed by the
yellow color of a concentrated ferric salt solution. In this case, it is best
to convert the Fe+++ ion into the colorless FeFi ion by the addition of
potassium fluoride. The pale coloration due to the traces of ferrous salts
can then easily be seen.
fProcedureA drop of the acid test solution is placed in a porcelain
microcrucible lined with paraffin. The yellow solution is decolorized by a
few crystals of potassium fluoride, and then a drop of the reagent solution
is added. In the presence of iron (II) salts, a red or pink coloration
appears. In the absence of ferrous salts, the solution remains colorless, or
iron (complex fluoride) may separate out.
Test for traces of iron salts in fluorides and mercury salts, see pages 437
and 438.
" For preparation, see F. Hein and W. Retter, Ber., 61, 1790 (1928); see also
J. P. Wibaut and H. D. Tjecnk Willink, Jr., Rec. trav. chim., 64, 278 (1935).
3. Test with 8-hydroxyquinoline-7-iodo-5-sulfonic add."* Acid solutions

of iron (III) salts react with water soluble 8-hydr6xyquinoIine-7-iodo-5-
sulfonic acid (I) producing a green color due to the fbrmation of the inner
complex compound (II). '
HO,S-
<^ NFe/3 <' NFe/3
(I) (II) (III)
The parent compound of the reagent, namely, 8-hydroxyquinoline,

which is difficultly soluble in water, forms an insoluble green-black inner
complex ferrip salt. Its coordination formula is given in (III). Conse-
quently, the SO3H group, which confers increased solubility in so many
other cases, brings about the formation of an inner complex anion, with
retention of the inner complex binding of the iron atom.
The test for iron (11^) with 8-hydroxyquinoline-7-iodo-5-sulfonic
acid (ferron) is specific. The only interference arises from the presence
of considerable quantities of colored ions or of strong oxidizing agents that
partially destroy the reagent. It is important to maintain the acidity at
pH 2 to 3.5. Consequently, if stronger, or less acid solutions are involved,
they must be buffered or acidified until a distinct acid reaction is obtained
toward methyl orange paper (pH = 3.5).
f ProcedureOne drop of the acid test solution (pH = 3.5) is treated
on a spot plate with 1 drop of the orange-yellow water solution of the
reagent. A green color indicates the presence of iron (III).
Limit of Identification: 0.5 y iron
Reagent: 0.1% solution in water of 8-hydroxyquinoline-7-iodo-5-
sulfonic acid.'i'
4. Test with potassium thiocyanate. Iron (III) ions combine with thio-
cyanate ions in acid solution [Fe+++ + 6 CNS- "= [Fe(CNS)6]] to give
the deep red soluble complex iron (III) thiocyanate ion"* or its alkali salts.
These compounds are quite soluble in ether and can be extracted from water
solutions by shaking them with ether. Phosphates, arsenates, oxalates,
tartrates, and other organic hydroxyl compounds, fluorides, and many
"* J. H. Yoe, J. Am. Chem. Soc, 64, 4139 (1932)
" ' For preparation, see A. Claus, Friedldnder, 3, 964 (1890-94); Oerman Pat.
72, 942, .
" H. .r. Schlesinger and H. B. van Valkenburgh, / . Am. Chem. Soc, 63, 1212
(1931).
/ ^
moN 125
compounds which give stable complex salts with iron (III), according to
the proportion present, can so reduce the concentration of ferric ions that
the ionic product necessary for the reaction is not reached, and even then
considerable amounts of iron may fail to be detected by the sensitive thio-
cyanate reaction. The same interference occurs when conaderable
amounts of mercury salts are present, as they form slightly dissociated
mercuric thiocyanate or double thiocyanates, i.e., K!!Hg(CNS)4, and thus
consume the thiocyanate ions. In such cases of interference, the test
described under 2 should be used.
The presence of nitrites is to be avoided, as in acid solution they form
nitrosylthiocyanate NO-CNS (anhydride of both nitrous acid and thio-
cyanic acid). This gives a red color (which will disappear on heating)
very similar to that of the iron thiocyanate.'"
IfProcedureA drop of the test solution is mixed on the spot plate
with a drop of 1% potassium thiocyanate solution, and a more or less deep
red color appears in the presence of iron.
Cmcentraiim lAmit: 1:200,000
Cobalt, nickel, chrpmium, and copper salts reduce the sensitivity of
the iron test owing to the color of their ions, or their reaction with thio-
cyanates. However, by the spot test, 1.25 y iron can be detected in the
presence of 320 times the amount of cobalt or chromium, and 0.025 y iron
in the presence of 640 times the amount of nickel or copper.'*'
5. Test with dimethylglroxime.'" Ferrous salts form a soluble red
inner complex compoimd with dimethylglyoxime in ammoniacal solution
or in the presence of organic bases:
O
I
H,CC=Nv
1 /Fe(am).
H,CC=N''^
I
OH
(where am = NH,, CjIiiN, or primary aliphatic amine and x = 2 or 3).
Their constitution, with respect to the inner molecular rings, is analogous
to that of the insoluble nickel dimethylglyoxime. If ferric iron is involved
it must be reduced with hydroxylamine hydrochloride or sulfurous acid
beforehand.
The presence of nickel interferes with the test, as the precipitation
of the red insoluble nickel dimethylglyoxime renders it diflBcult to see the
" G. Nadler, / . prakt. Chem., 99,188 (1866).
" K. Heller and P. Krumholz, Mikroehemie, 7, 2l9 (1929).
" L . Tschugaeff and B. Orelkin, Z. anorg. allgem- Chem., 89,-401 (1914); P.
Slawilc, Chem.-Ztg., 86.54 (1912); P. Feigl, Chem.-Ztg., 43. 861 (1919).
red color of the solution. If, however, potassium cyanide is added, the
nickel dimethylglyoxime dissolves, and only the ferrous salt remains, as
it is stable in the presence of potassium cyanide. 1
Cobalt and copper salts combine with dimethylglyoxime to give
soluble brown complex salts, and thus interfere when present in large
proportions.
To test for ferrous salts with dimethylglyoxime in the presence of
ferric salts, the solution is treated with tartrate. It gives a soluble ferric
complex compound that is stable in the presence of ammonia.
tProcedureA drop of the test solution (previously reduced, if
tecessary) is mixed with a crystal of tartaric acid, and then a drop of
alcoholic dimethylglyoxime is added, followed by a little ammonia. Ac-
cording to the iron content, a more or less intense red coloration appears.
It fades on standing in the air, owing to the oxidation of the ferrous complex.
Ldmit of Identification: 0.04 -yiron
Reagents: 1) 1% alcoholic dimethylglyoxime solution
S) Tartaric acid (solid)
3) Ammonia
6. Test with disodium l,2-diliydroxybenzene-3,5-distdfoMate.'2'' Di-
sodium l,2-dihydroxybenzene-3,5-disulfonate (I) produces water-soluble,
colored compounds with ferric salts. The iron atom is incorporated in an
inner complex anion. In solutions whose pH is less than 5, the complex
(II) is deep blue. The cautious addition of base to the blue solution results
in a sharp change to violet (III) at pH 5.7 to 6.5; at pH 7 the color changes
to red (IV). The structural formulas (II) and (IV) have been established
for the blue and red complex salts, respectively, through their analogy to
the like-colored complex iron salts of pyrocatechol, which were isolated
quite some time ago.''' There is little doubt that (III) correctly represents
the violet complex salt.
These complex salts are so stable that they are formed even in the
presence of fluoride, tartrate, and other materials that also form complexes
with iron (III). Consequently, this reaction succeeds under conditions at
which color reactions for ferric iron are ordinarily greatly impaired or
prevented. A further advantage is that the reagent can be applied as a
colorless water solution.
It should be noted that even minute quantities of titanimn salts give
an orange color with this reagent; copper salts produce a green-yellow.
The yellow developed by considerable amounts ormolybdenum impairs
the test for iron.
J. H. Yoe and A. L. Jones, Ind. Eng. Chem., Anal. Ed., 16, 111 (1944).
" H. Reihlen, Z. anorg. Chfm., 123, 173 (1922)^R. Weinland and E. Walter,
Z. anorg. allgem. Chem., 126,148 (1923). P. Karrer, Organic Chemistry, translated
by A. J. Mee, Nordeman, New York, 1938, p. 397.
IRON 127
NaO,&( Y~^^ NaO,s/\Ov / SO.Na
U-OH J n / I Na
SO,Na
SO,Na SOsNa
(I) (11)
Reagent Blue complex
-SOsNa
-O'^/'No-
L,r O 6
SO,Na
L
SO,Na Na,
SOsNa
SO.Na
(III)
Violet complex
NaO.S SO.Na
Na,
SO.Na
(IV)
Red complex
IfProcedureA drop of the test solution is treated in a depression of a
spot plate with a drop of the reagent solution and a drop of buffer solution.
A red to pink appears, depending on the amount of iron present.
Concentration lAntit: 1:1,000,000
Reagents: 1) 0.0113 g. disodium l,2-dihydroxybenzene-3,5-disulfo-
nate in 100 ml. water
2) Buffer solution (pH = 9.8) 1 g. NaHCOj and 0.5 g.
Na2CG3 in 100 ml. water
7. Other tests for iron. 1. A purple-red color is produced in ammoniacal
solution by the action of thioglycolic acid with iron (II) and iron (III)
salts."' One drop each of the test solution, of 6 iV^ ammonia, and of thio-
M E. Lyons, J. Am. Ckem. Soc., 49,1916 (1927).
128 TESTS FOB METALS
glycolic acid are mixed on a spot plate {Id". Limit: 0.01 y Fe). Sulfites
interfere; zinc salts decrease the sensitivity.
S. Ferric salts spotted on paper soaked with 0.2% quercetin or
quercitrin produce an olive-green ring*" (Id". Limit: 3 y Fe). Uranium
salts form rust-brown flecks (see page 169). i
S. Iron (II) may be detected by spotting with 1% aqueous solution
of 2-nitroso-l-naphthol-4-sulfonic acid at pH = S.*** Green color {Id".
Limit: 0.01 y Fe). Cu and Co salts also give color reactions.
CHROMIUM
1. Test with diphenylcarbazide, after conversion into chromate.*** Solu-
tions of chromates in mineral acids react with diphenylcarbazide (see page
48), to give soluble violet compounds of unknown composition.
As chromium (III) salts can easily be converted into chromates by
oxidation in acid or alkaline solution, or by oxidizing fusion, the diphenyl-
carbazide reaction can be utilized as a sensitive test for chromium.
(o) Oxidation in alkaline solviion
A suitable oxidizing agent is alkaline bromine water (hypobromite)
which rapidly converts chromium (III) salts to chromates:
2 Cr+-H- + 3 BrO- -1- 10 OH- == 2 CrQ -f- 3 Br- -f- 5 HtO
An excess of bromine can be rendered inactive by the addition of phenol,
which converts it into tribromophenol.
^[ProcedureA drop of the test solution acidified with mineral acid
is treated on a spot plate with a drop of saturated bromine water, and then
2 or 3 drops of 2 iV potassium hydroxide are added (the solution must
react definitely alkaline to litmus). After thorough mixing, a crystal of
phenol and a drop of diphenylcarbazide are added, and finally 2 N sulfuric
acid, drop by drop, until the disappearance of the red color produced by the
alkaline diphenylcarbazide.
In the presence of chromates, a blue-violet color remains. _
Limit of Identification: 0.25 y chromium
Cobalt and manganese salts interfere, as dark precipitates of hydrous
Co(III) and Mn(IV) oxide are formed. Nickel and copper salts interfere,
owing to the color of the precipitated hydroxide or oxide. In such cases,
a blank test is carried out, and the precipitated oxides are allowed to settle.
Then 1 y chromium (dilution 1:50,000) can be detected in the presence of
320 times the amount of cobalt, nickel, copper, and,ianganese.
'" E. A. Koceie, Mikrochemie, 26,13 (1938).
' " L. A. Sarver, Ind. Eng. Chem., Anal. Ed., 10, 378 (1938).
" P. Cazeneuve, Compt. rend., 131, 346 (1900).
CHROMIUM 129
Reagents: 1) 1% alcoholic diphenylcarbazide solution (see page 49)

2) Saturated bromine water
S) 2 iV sodium or potassium hydroxide
4) 2 N sulfuric acid
5) Phenol (sohd)
The conversion of chromium salts into chromates for the diphenyl
carbazide test can also be carried out as follows :^^^
^ProcedureA drop of the test solution is taken up in a loop of
platinum wire and carefully evaporated to dryness over a very small flame.
The platinum wire is then heated to redness and dipped in a mixture of
equal parts of sodium potassium carbonate and sodiima peroxide, and a
bead is made by heating repeatedly in the flame. All the chromium is
thus oxidized to chromate. The cold bead is dissolved in 1 or 2 drops
of sulfuric acid (1:1) on a spot plate, and 1 or 2 drops of an alcoholic di-
phenlycarbazide solution are added. A violet color indicates chromium.
Liimit of Identification: 0.5 y chromium
Evaporation on platinum wire, and subsequent ignition in the flame,
always results in the loss of small amounts of material by spattering.
Therefore, when very small amounts of chromium are to be detected,it is
preferable to carry out the evaporation, fusion, solution in sulfuric acid,
and finally the addition of the diphenylcarbazide, in a porcelain micro-
crucible. Then 0.02 y chromium in a drop can easily be detected. {Con-
centration limit: 1:2,500,000.)
Reagents: 1) Sodium potassium carbonate, sodium peroxide mixture
(1:1)
2) Sulfuric acid (1:1)
S) 1% alcoholic diphenylcarbazide solution
(6) Oxidation imacid solution
Chromium (III) salts can be oxidized to chromates by heating with
potassium persulfate in acid solution thus:
2 Cr+++ + 3 SjOi"" + 8 H2O = 2 CrOr" + 6 SO?" + 16 H+
This reaction is greatly accelerated by the presence of soluble silver salts,^^^
probably owing to the intermediate formation of silver (II) compounds
(see page 132). In a few minutes sufficient chromate is formed,''^' at room
temperature, for the diphenylcarbazide reaction.
When carrying out this test, large amounts of haHdes should not be
Studies with R. Novdcek.
' " F. Ibbotson and R. Howden, Chem. News, 90, 320 (1904).
" F. Feigl, Z. angew. Chem., 44, 741 (1931).
130 n . TESTS FOB METALS '
present, as they stop the catalytic action^bf the silver ions by forming
insoluble silver halides.
Under these conditions, manganese salts are oxidized to permanga-
nate, whose violet color may mask the chromate reaction. In this case,
however, sodium azide is added, which completely reduces permanganates,
but affects chromates only slightly (see page 262).
IfProcedureA drop of the test solution is mixed on a spot plate with
a drop of a saturated solution of potassium persulfate and a drop of a 2%
silver nitrate solution, and allowed to stand for 2 or 3 minutes. On adding
a drop of an alcoholic diphenylcarbazide solution, a violet to red color is
formed; this fades on long standing.
Concentration lAmit: 1:625,000
Reagents: 1) Saturated potassium persulfate solution
2) 2% silver nitrate solution
Test for chromium in the presence of mercury and molybdenum^*

Mercury salts, molybdates, and also vanadates, give blue to violet
compounds with diphenylcarbazide in acid solution, and can therefore
interfere with the chromium test. The interference can be prevented by
the addition of suitable compounds that reduce the ionic concentration of
the interfering elements below that required for the diphenylcarbazide
reaction. For mercury, it is sufficient to add an excess of hydrochloric
acid or alkali chloride; the usual low dissociation of mercury chloride is
thus even further reduced. (The formation of the complex HgCir~ ions
also helps to lower the ionic concentration of mercury.) When chromium
is to be detected in the presence of mercury, hydrochloric acid is used to
acidify the alkaline chromate solution. In this way, 0.25 y chromium is
easily detected by a spot reaction in the presence of 2:5 mg. mercury
(ratio 1:10,000).
In order to avoid the interference of molybdates, the simplest
method is to form the complex molybdenum oxalic acid Hj [Mo03(Cs04) ].
The molybdate concentration is so reduced that, neither the diphenylcarba-
zide, nor any other sensitive molybdate reaction takes place. Thei oxalic
acid (1 drop of saturated solution) must be added to the test solution
before the addition of diphenylcarbazide. Otherwise the molybdic acid
is partly reduced by reaction with diphenylcarbazide forming molybdenum
blue, and this is stable toward oxalic acid. This procedure will reveal 0.5 y
CrOj in the presence of 20 mg. M0O3.
" F. Feigl and P. Krumholz, Mikrochemie (Pregl FestcArt/t), 1929, p. 80.
CHKOMIXrai 131
2. Test with benzidine after conversion into du-qmate.'^ô Chromates

oxidize'benzidine in acetic acid solution to a blue quinoid compound (see
page 56). As all chromium. (Ill) salts are easily oxidized to chromates
with sodium peroxide, and the benzidine-chromate reaction is very sensi-
tive, a simple and definite test for chromium is available.
^ProcedureA drop of a moderately concentrated sodium peroxide
solution and a drop of the test solution are successively placed on filter
paper. The resulting chromate diffuses through the fibers of the paper
into the outer zone of the moist fleck. It can be identified there by spotting
with a drop of an acetic acid-benzidine solution. A blue ring (benzidine
blue) is formed.'"
Reagents: 1) Acetic acid-benzidine solution (see page 135)
2) Sodium peroxide solution (freshly prepared)
Test for chromium in the presence of other metals
The test just described is definite for chromium in the absence of
vanadates which also oxidize benzidine. It can be carried out in the
presence of lead, cobalt, silver, and copper salts (which give the blue color
with benzidine under the same conditions) owing to the capillary migration
of the chromates. It is necessary to vary the conditions only in the
presence of manganese, whose higher oxides react with benzidine (see page
134). The manganese dioxide is formed in a highly dispersed form, which
partly diffuses to the outer zone, and although invisible there, it reacts with
the benzidine in the same way as chromates. This interference can be
avoided by using a special method of precipitation so as to cause complete
aggregation of the manganese dioxide, before carrying out the spot test.
^ProcedureA drop of the solution which may contain cations of all
the groups, is mixed on a watch glass with an excess of sodium peroxide,
and stirred mth a glass rod while it is gently heated. A portion of the
suspension is transferred to filter paper with the aid of a capillary tube.
The precipitate forms a fleck on the paper, and the filtrate, which for
small amounts of chromium is almost colorless, forms a colorless zone
outside. If the paper is moistened from the outside of the wet spot with
a drop of an acetic acid solution of benzidine, a blue ring is formed when
it reaches the colorless zone and slowly extends to the center of the spot.
The following procedure may also be used: A small strip of filter
" N. A. Tananaeff, Z. anorg. allgem. Chem., 140, 327 (1924).
" According to L. Kul'berg, Mikrochemie, 20,244 (1936), the sensitivity of this
test for chromates with benzidine may be doubled by using a freshly prepared mix-
ture of equal parts of a 1% alcoholic solution of benzidine and 20% HjOj.
132 n- TESTS FOB METALS
paper (about 1 cm. wide) is folded over twice, andi put on a glass plate
with the folded portibns lying above each other. The precipitate and
solution from the watch glass are then brought ori to the filter paper.
When the undermost layer becomes moist, most of the precipitate remains
on the topmost strip. The second layer allows very little through, and
the third section is often free, and the fourth always free from the precipi-
tate. If the last, precipitate-free layer of filter paper is'treated with
benzidine, the development of a blue color indicates the presence of
chromate.
Detection of chromium in rodts, steels, etc., see page 438.
3. Other tests for chromium. 1. Acid alizarin RC forms an orange lake
color with chromium (III) salts^" when the test is carried out on filter
paper; the color is stable toward both acids and ammonia {Id". Limit:
0.6 7 Cr). Although the test may be carried out in the presence of not
too large amounts of the other elements of the (NH4)2S group, it is, never-
theless, advisable to carry out the simple conversion to chromate.
2. Chromates, in the absence of interfering ions, can be detected by
a spot reaction through the formation of red Ag2Cr04, or yellow PbCr04
{Id". Limit: 6 7 Cr).
MANGANESE
1. Test by catalytic oxidation to permanganate in acid solution.^^^ Manga-
nous salts do ' not react in the cold with persulfates, for example,
(NH4)2S208. On heating, part of the manganese separates as manganese
dioxide hydrate. In the presence of small amounts of soluble silver
salts, the oxidation proceeds to permanganate, so that instead of a pre-
cipitate, a violet coloration forms. The oxidation proceeds:
2 Mn++ -f 5 S2OF- -I- 8 H2O = 2 MnOr + 10 807" + 16 H+
Silver salts act as catalysts in this reaction, as well as in other oxidation
reactions of persulfates,'" probably by the intermediate formation of
silver (II) persulfate.'"
The test goes best when small amounts of inanganese and silver are
present from the beginning; otherwise, together with the red coloration,
there will be solne separation of manganese dioxide and silver peroxide.
'" F.^Feigl and R. Stern, Z. anal. Chem., 60, 28 (1921).
" H. Marshall, Z. anal. Chem., 43,418 (1904).
"* Compare H. Marshall, Z. physik. Chem., 37, 255 (1901).
"5 Compare G. A. Barbieri, Ber., 60, 2424 (1927); A.JTravers, Compt. rend.,
182, 972 (1926), assumes that the compound SAgjOz-AgNDj-formed from the silver
nitrate and persulfate, acts as an oxygen carrier. According to A. Pinkus and L.
Ramakers, Chem. Abstracts, 27, 2108 (1933), the oxidation proceeds in two stages:
2Ag+-[-Sj08+ 2'HsO = Aga02 + 2 S O r + 4 H+and 2 Mn++-1-5 A g . 0 , + 4 H + =
2 MnOr + 10 Ag+ -1- 2 HjO.
MANGANESE 133
Chlorides should be absent, or present only in small amounts, as the

catalytic silver ions are removed as silver chloride. The same holds for
bromides, iodides, or other salts that precipitate silver. It should be
noted that Cr(III) salts are oxidized under these same conditions forming
chromate. See page 262 regarding the detection of permanganate in the
presence of chromate.
^[ProcediireA drop of the test solution is mixed with a drop of
concentrated sulfuric acid in a microcrucible. A drop of silver nitrate
solution is stirred in, followed by a few mg. ammoniiun persulfate; the
mixture is then gently heated, A violet coloration indicates manganese.
Ldmit of Identification: 0.1 y manganese
Reagents: 1) Concentrated suKuric acid
S) Silver nitrate solution (0.1%)
3) Ammonium persulfate (solid)
2. Test by catalytic oxidation to permanganate in alkaline solution.^^^ In
the reaction between manganese salts and alkali hypobromites a precipitate
of manganese dioxide or higher manganese oxides is formed:
Mn++ + BrO- + 2 OH-' = MnOj + HjO + Br"
If the reaction is carried out by heating gently in the presence of small
amounts of copper, the oxidation proceeds further, and instead of the brown
precipitate, a violet solution .of permanganate is produced :^^'
2 Mn++ + 5 BrO- + 6 OH" = 2 MnOT + 5 Br" + 3 H2O
Cobalt and nickel salts, to a lesser degree, possess the same catalytic action.
The catalytic action of the copper is probably due to the intermediate
formation of higher copper oxides, which oxidize MnOa to MnOr, with
reformation of Cu(II) oxide. In support of this theory, is the fact that
periodic and telluric acids, which form stable Cu(III) salts, prevent this
catalytic action of copper.
The catalytic oxidation to permanganate can be used as a test for
manganese,^'' and it has the advantage that it is not affected by the
presence of colored metallic ions, as these are all precipitated as oxides
or peroxides. Only chromium should not be present; it is oxidized to
chromate, and renders difficult the detection of small amounts of per-
manganate. It is to be noted that in testing for manganese in the presence
" F . Feigl and E. Frankel, Ber., 66, 541 (1932),
" ' K. M. Filimanowitsch, Z. anal. Cherh., 86, 234 (1931), discovered this reac-
tion and applied it to detect copper; 0.2 7 Cu may be identified by its catalytic effect.
In this case precautions must be taken in the presence of Co and Ni salts (see
page 70).
" M. Duyk, Ann. chim. applieata, 12, 465 (1907), used KOCl and CuS04in an
analogous test for manganese.
134 II. TESTS FOK METALS
of much nickel or cobalt, an amount of copper exceeding the quantity of

nickel (or cobalt) should be added to the test solution, before heating with
hypobromite. i
UProcedureTwo ml. CUSO4 solution is placed in' a test tube, fol-
lowed by a drop of the test solution and 8 to 10 ml. sodium hypobromite.
After boiling for a short time, the supernatant liquid is colored red-violet
in the presence of manganese.
Limit of Identification: 2.5 y manganese
Reagents: 1) 1% copper sulfate solution
,8) 0.1 N sodium hypobromite (freshly prepared from
NaOH and bromine water)
3. Test with periodate and tetrabase.^'" Manganous salts are oxidized to
permanganate on warming with alkali periodates:
2 Mn++ + 5 107 + 3 H2O = 2 MnQr + 5 lOF + 6 H+

Larger amounts of manganese can be detected by the violet color
of the permanganate, while smaller amounts are revealed by adding a
solution of Arnold's base (tetramethyldiaminodiphenylmethane) in chloro-
form. An intense blue is formed, due to an oxidation product of the
tetrabase.^'"'
In this reaction the permanganate is reduced to manganous salt,
and this again oxidized by the periodate. Thus, the catalytic action of
manganese is the basis of this test.
Chromium salts should not be present, as they are oxidized by
periodate to chromate, which also give a blue color with the tetrabase.
^ProcedureA drop of the test solution is placed on the spot plate,
followed by a drop of a KIO4 solution, a drop of 2 iV acetic acid, and 2
drops of the solution of the tetrabase in chloroform. According to the
amount of manganese present, a more or less deep blue color is formed.
Limit of Identification: 0.001 7 manganese
Reagents: 1) Saturated solution of potassium periodate
2) 1% solution of tetrabase^*' in chloroform
4. Test with benzidine.-''^ The organic base benzidine (see page 55)
can be converted by. a number of oxidizing agents, as well as by autoxida-
tion, into a blue oxidation product^*' (see page 55). If precipitated
" ' H. H. Willard and L. H. Greathouse, / . Am. Chem-rSgc, 39, 2366 (1917).
" J. Tillmans and H. Milden, Chem. Abslracls,8, 3085 (1914).
" For preparation, see J. Biehringer, / . prakl. Chem., 64, 240 (1896).
" ' F. Feigl, Chem.-Zlg., 44, 689 (1920); Z. anal. Chem., 60, 24 (1921).
"5 W. Schlenk, Ann., 363, 313 (1908).
/ ^
MANOANISE 135
V
manganous hydroxide is brought into contact with air, hydrated man-
ganese dioxide forms quickly through autokidation:
2 Mn(OH), + 0, = 2Mn02-H20
This reacts with benzidine, giving benzidine blue. The reaction sequence:
precipitation - autoxidation - formation of "benzidine blue," can be
used in the form of a spot reaction on filter paper to detect quantities of
Mn02 that are too sUght to be seen. The test is not sensitive if carried
out on a spot plate or in a test tube. The paper functions here as an active
participant in the reaction, probably throu^ its capillary action and the
high dispersion of the MnO.
f ProcedureA drop of the test solution is treated on filter paper with
a drop of dilute alkali, and then with a drop of benzidine solution. A blue
color results where the manganese dioxide was formed. The intensity
depends on the manganese content. The color fades on drying, but
reappears with fresh addition of benzidine.
Limit of IderUification: 0.15 y manganese
Reagents: 1) 0.05 N potassium or sodium hydroxide
2) Benzidine solution: 0.05 g. benzidine base or hydro-
chloride dissolved in 10 ml. acetic acid, diluted to 100
ml. with water and filtered
Test for manganese in the presence of other metals'**
The manganese-ênzidine reaction, as just described, cannot be used
in the presence of other oxidizing agents or autoxidizable substances,
which also oxidize benzidine (chromates, ferricyanides, cobalt, thaUiiun,
silver, cerium salts). In such cases, special procedures must be used.
It must also be noted that large amounts of indifferent metalhc
hydroxides may coat the manganese hydroxide, and thereby reduce the
sensitivity of the test when testing for manganese in the presence of iron.
For instance, ferric hydroxide,"' although it has no effect on benzidine,
reduces the sensitivity of the manganese test so considerably that instead
of 0.15 -y (as in pure manganese salts) only 2.5 y can be detected in a drop
when 250 y iron are also present. If, however, the iron precipitation is
prevented by the addition of Rochelle salt, then manganese can be de-
tected in the presence of large amounts of iron. The entire procedure can
be accomplished on filter paper.
Limit of Identificaiion: 1 y manganese /in the presence of 1000
Concentration Idmit: 1:^,000 \times the amount of iron
In order to detect manganese in the presence of cobalt (which under
"* According to experiments carried out by S. Pickholz.
'" It should be noted that ferric salts likewise oxidize benzidine, if free acids
are absent.
the nonnal conditions of the test gives the autoxidizable cobalt hydroxide),
the cobalt should be converted into the very stable K3Co(CN)( by add-
ing potassium cyanide and wanning. The excess, potassium cyanide,
however, interferes with the manganese test by forming a complex man-
ganese compound. I t should be removed by the addition of a few drops
of cone, hydrochloric acid (in a hood). This also destroys any manganese
cyanide, whereas the cobalt complex ion remains unchanged^ This series
of reactions can be carried out in a microcentrifuge tube. I t must be
noted that the potassium cyanide solution of the complex cobalt salt will
gradually give a red-Adolet color with benzidine.
T- i f Tj , 1- n c fin the presence of 1200
Ltrrat of Idenhncahon: 0.0 yiaajxgajiese ].. f, . ,
n t 4- T -4 1.inn Ann itunes the amount of
Concentration Limit: 1:100,000 , ,,
[cobalt
In order to detect manganese in the presence of cerium, which forms the
autoxidizable Ce(0H)3, the test solution should first be warmed for 2 to 3
minutes with a little freshly prepared calcium fluoride. The cerium is
precipitated as insoluble fluoride, and is retained in the precipitate with the
unchanged calcium fluoride. The manganese test can be carried out on
the filtrate, as described.
T -t f Tj 4-r f c:' ^ fin the presence of 1000
Liimit of Identification: 5 y manganese J . fl A- t
Concentration Limit: 1:10,000 1
l^cenum
Copper salts form copper hydroxide and basic copper acetate, which
can mask the benzidine blue color. When small amounts of manganese
are to be detected in the presence of large amounts of copper, the test should
Limit out
be carried of Identification: 1.6 yofmanganese
as in the presence cobalt. The interference of the cupric
salt is prevented by the formation of KsCu(CN)4 or Cu2(CN)2.
times the amount of cop-
per
In order to detect manganese in the presence of silver and thallium, they
are best precipitated from the solution as chlorides, the precipitate filtered
or centrifuged off, and the test carried out on the clear filtrate. Thallic
salts can be reduced to thallous sulfate with sulfur dioxide, and then pre-
cipitated with sodium chloride. The sensitivity of the test remains the
same as for pure manganese salts. The silver and thalhum must be re-
moved before carrying out the test; otherwise the oxidizing agents AgjO
and T1(0II)3, and the autoxidizable Tl(OH) give the blue color with
benzidine..
It is best not to attempt to precipitate the silver Mid thallium directly
on the filter paper, as both AgCl and TlCl are able to react slowly with
benzidine. The blue color in this case depends on the photochemical
ZINC 137
dissociation of thallium and silver chloride: AgCl Ag + CI or TlCl *

Tl + CI. The minute amoimt of free chlorine liberated in this way is
suflBcient to oxidize the benzidine.
5. Test widi sUver anunine salts.'** The test fbr silver (see page 42)
utilizing the reaction between silver, manganese, aad hydroxyl ions**'
can also be carried out in ammoniacal solution:
Mn-H- + 2 Ag(NH,)2+ + 4 OH" = MnO, + 2 Ag + 4 NH, + 2 H,0
This formation of manganese dioxide and finely divided silver can be
used for a sensitive test for manganese. It can be applied in the presence
of Al-H-t-, Cr+++, Fe+++, Co++, m++, Zn++, Rg^, Pb-H-, and Bi+^+ ions.
It is especially useful in the detection of manganese in alloys and special
steels. The sensitivity is always decreased when colored metallic hy-
droxides are formed at the same time.
IfProcedureA drop of the ammoniacal silver nitrate solution is
placed on the spot paper and then a drop of the test solution. In the
presence of manganese, a black fleck appears, which, on warming, becomes
more distinct.
It must be noted that anunoniacal silver solutions are slightly reduced
by filter paper, so that a blank test is essential for small amoimts of man-
ganese.
Limit of Identification: 0.05 y manganese
Concentration Limit: 1 ,* 1,000,000
Reagent: Silver ammine salt solution. A saturated solution of silver
nitrate is treated with cone, ammonia until the initial
precipitate is dissolved; &en an equal volume of ammonia is
added
ZINC
1. Test mA ferricyanide aid diethylaniline.'** Alkali fenicyanides
oxidize diethylaniline'*' and other aromatic amines, as well as certain
monoazo dye stuffs, with a change of color. Ferrocyanide is formed.
This oxidation, by itself, proceeds very slowly and incompletely. How-
ever, if the ferrocyanide is removed by zinc ions afi sparingly soluble white
zinc ferrocyanide, then the oxidation proceeds rapidly. The white zinc
ferrocyanide is deeply colored by adsorption of the colored oxidation
products, and thus affords a sensitive test for zinc. The test is especially
useful in the presence of chromium and alumimmi. It can also be used
" N. A. TananaefE and I. TananaefE, Z. anorg. allgem. Chem., 170,118 (1928).
" ' Compare also D. Balarew, Z. anal. Chem., 60, 392 (1921).
" E. Eegriwe, Z. anal. Chem., 74, 228 (1928).
W. H. Cone and L. C. Cady, / . Am. Chem. Soc, 49, 2214 (1927).
138 n . TESTS FOB TUSftAXS
in oilier instances so long as no other cations'are present, which form col-

ored precipitates with potassium ferrocyanide (cobalt, nickel, iron (II),
manganese, copper). Traces of iron, which in practice are always to be
reckoned with, do not interfere with the zinc test. The reagents must be
mixed directly before the test. 1
IfProcedoreIn the depression of a spot plate, 15 drops potassium
ferricyanide. solution is mixed with 10 drops of a solution of diethylaniline
(in sulfuric or phosphoric acid). The sulfuric acid solution remains yellow
and clear during the time of observation of the reaction (5 min.). On
TABLE 3
ReactioD i&tsie after i i&inutes ludng:

1 diop test (ohitico con-
tafm (iasi(,}; Dietfa^laaiiine xddi&ed vith BtSOi IHetliyUiuUne sddiBed with BiFOk
1.0 Zn Dense brownish-red precipi- Dense dark brown-red precip-

tate . itate
0.1 Zn Pale brown-red precipitate Dense brown-red turbidity
and turbidity
0.1 Zn + 0.8 Al + -
+0.3 Cr +
+ 0.67 Na Pale brown-red precipitate Dense brown-red turbidity.
and turbidity
0.01 Zn Bed-yellow coloration and Yellowish to brown-red color
turbidity and turbidity
0.01 Zn + 0.8 Al +
+0.3Cr + 0.67Na Slight brownish-yellow color Definite turbidity
and turbidity
0.001 Zn Brownish yellow to red color Definite turbidity
and turbidity
0.001 Zn +0.8 A1 +
+0.3Cr+0.67Na Turbidity Defiiiite turbidity
O.OOOl Zn No reaction Marked turbidity
0.0001 Zn +0.8 A1 +
+ 0.3 Cr + 0.67
Na No reaction Marked turbidity
addition of a solution containing zinc, the yellow color changes to bright

brown to red-brown, and a precipitate or cloudiness appears. The phos-
phoric acid solution is dark yellow to red-yellow, and also remains CIMW
during the observation time (5 min.). Upon the addition of a drop of a
solution containing zinc, the color becomes more red or dark red-brown,
and a precipitate or cloudiness is observed. _ ~-
lite limits of identification and concoitration for'the zinc diethyl-
aniline test, for an observation time of 5 minutes, are ^ven in Table 3.
zmc 139
Reagents: 1) Potassium ferricyanide solution (2 g. in 100 ml. water)

2) Diethylaniline solution (free from monoethylaniline)
d) 0.25 g. diethylaniline (mono-free) in 200 ml. sul-
furic acid (1:1)
b) 0.5 g. diethylaniline in 200 ml. 50% phosphoric acid
2. Test with ditbizone.^" Diphenylthiocarbazone (dithizone) (see page
57) forms insoluble colored inner complex salts with a nimiber of salts of
the heavy metals. These products are easily extracted by organic sol-
vents. The purple-red zinc salt, formed in neutral, alkaline, and acetic
acid solutions, is soluble in carbon tetrachloride without change of color.
^ProcedureA drop of the test solution and a drop of a solution of
dithizone in carbon tetrachloride are shaken together in a small stoppered
test tube. In the presîce of snc, the green color of the reagent changes
to purple-red.
Limits of Ideniification.
0.025 7 zinc in neutral one sulfate solution
0.06 7 idnc in 2% amm(ua
0.06 7 zinc in the presoice of ammonia, ammonium salts, and
tartrates
0.9 7 zinc in 2% sddium hydroxide
0.9 7 ssinc in 10% acetic acid
0.05 7 zinc in 10% acetic acid and 5% ammonium acetate
Reagent: Solution containing 1 to 2 mg. dithizone in 100 ml. carbon
tetrachloride
When this test is carried out on paper or on a spot plate, 0.4 7 and
0.05 7 zinc, respectively, can be detected by a red fleck or coloration, if a
solution of 10 mg. dithizone in 100 ml. carbon tetrachloride is used.
This test for zinc is especially useful in the presence of nickel or
aliuninum salts. In a drop of neutral solution, 0.2 7 zinc can be detected
in the presence of 1600 times the amount of nickel, and 0.05 7 zinc in the
presence of 2200 times the amount of aluminum, when 1 mg. anunonium
acetate is added.
This dithizone test for zinc is very sensitive in neutral or acetic acid
fdiution, but is not specific, as many other heavy metals cause a color
change in the carbon tetrachloride layer. The use of doubly distilled
water is necessary to avoid the interference due to traces of heavy metals.
It is therefore more satisfactorj' to cany out the test in alkaline solution
although it is then less sensitive. The solution ttims red only in the
presence of zincates, and the color is quite evident even in the presence of
colored precipitates.*" When copper or mercury salts are present, these
H. Fischer, Z. angew. Chem., 42,1025 (1929); Mikrochemie, 8,319 (1930).
>" G. Rien&cker and W. Schiff, Z. anal. Chem., 94, 410 (1933).
140 U. TESTS FOR METALS
should be removed by precipitation with hydrogen sulfide^ This operation

is carried out amply in an Emich microcentrifuge tube.
^ProcedureA drop of the test solution is mixed on a watch glass
with a drop of alkali and a few drops of dithizone solution. The carbon
tetrachloride is evaporated by blowing, while stirring with a glass rod.
A raspberry-red solution shows the presence of zinc. The color of any
precipitate can be discounted.
Limit of Identification: 5 y zinc
8) Solution of 10 mg. dithizone in 100 ml. carbon tetra-
chloride
In this way 50 y zinc can be detected in the presence of 50 y Ag,
As, Fe(III), Mn, Pb, Sb, or Cd.
3. Test by coprecipitation ^tli cobalt mercury thiocyanate.^'^ Zinc salts
react with alkali mercury thiocyanates:
Zn-H- -I- [Hg(CNS)] = Zn[Hg(CNS)4]
giving a white crystalline precipitate. In the' presence of small amounts
of zinc, the precipitate appears quite slowly, owing to supersaturation
phenomena. Cobalt salts react similarly, producing blue crystalline
CoHg(CNS)4. If a veiy dilute cobalt solution, which only gives a blue
precipitate with the thiocyanate after long standiog, is treated with a
solution of a zinc salt, a blue precipitate is formed quickly, even though the
amount of zinc salt added is very small. Obviously the supersaturation
with respect to the two double thiocyanates is overcome, probably because
of the formation of mixed crystals.
ITProcedureÂ drop of the test solution, a drop of the cobalt solution,
and a drop of the mercury thiocyanalte solution are mixed on a spot plate
or in a microcrucible. The sides of the vessel are rubbed with a glass rod
for about 15 seconds. According to the amount of zinc present, a blue
precipitate is formed, either at once, or at the longest after 2 minutes.
In the absence of zinc, the precipitation begins only after 2 to 3 minutes.
Neatiml 0 N HCl
Limit of Identification: 0.2 y zinc 0.5 y zinc
Concentration Limit: 1:250,000 1:100,000
When very small amounts of zinc are present, a blank test should
be carried out on a drop of water in place of the test solution.
Table 4 shows the idefntification and proportion limits obtaindsle in
the presence of various foreign materials. ^
In the presence of iron (III) salts, red ferrictiuocysmateis formed and
affects the identification of the precipitate. In this case, the mixture
should be treated with a few milligrams of alkali fluoride, one or two
"' P. Erumholc and J. V. Sanche;:, Mikrochemie, 16,414 (1934).
ZINC 141
minutes after the addition of the reagents. The red due to the iron
disappears, because of the production of colorless FelV ions.
Reagents: 1) Cobalt sulfate solution: 0.02% Co in 0.5 A'' HCI
2) Alkali mercury thiocyanate solution. 8 g. mercuric
chloride and 9 g. ammonium thiocyanate in 100 ml.
water. Allow to stand several days
4. Other tests for zinc. 1. A blue color results if resorcinol is added to an
ammoniacal zinc solution.''' One drop of an alcohol solution of the re-
agent is mixed on a spot plate with 1 drop each of 6 iV ammonia and of the
zinc solution. The reaction may also be carried out in a micro test tube
with 1 ml. of the reagent. The blue color does not appear at once, but only
after several minutes (Id". Limit: 2 y Zn).
2. If a drop of a zinc salt solution is placed on paper impregnated
with K3Co(CN)6 and the paper then ashed, "Rinmann's green" (cobalt
TABLE 4
Identification limit, in y zinc Proportion limit

Accompanying Compound
In neutral
^SJS' In 0.5 W HCI solution In 0.5 N HCI
NH4CI... 2 250 1:520

KjSO*.... 1 1000 600
AlCl. 1 700 350
Cr(NO,). 0. 100 100
MnSO... 2 100 100
FeCl,...., 2 120 120
CdCl,.... 2 200 200
Pb(NO,). 2 SOO 250
rincate) is formed.'" In this way 0.6 7 Zn in 0.002 ml. (Concentration

Limit: 1:3300) may be detected.
S. The increase in oxidation potential of ferricyanide toward p-phenet-
idine (compare page 137) resulting from the precipitation of zinc ferro-
cyanide is applied as a test for zinc.'" A mixture is made of 6 drops of 2%
KFe(CN)(i, 2 drops of iV HjS04 and 12 drops of 1% p-phenetidine hy-
drochloride. 0.1 ml. of this freshly prepared, brown-yellow mixture is
placed on a spot plate, and 1 microdrop of the test solution added without
mixing. After 2 or 3 minutes, a blue precipitate or color is apparent on
the boimdary between the drops (Id". Limit: 1 y Zn). Using smaller
drops, even less may be detected, down to 0.05 y Zn. The proportion limit
*" G. Sensi and E. Testori, Ann. ehim. appKcata, 19, 383 (1929); see also J. H.
Yoe, A Laboratory Manual of Qualitative Analytit, Wiley, New York, 1938, p. 176.
" A. A. Benedetti-Pichler, Ind. Eng. Chem., Anal. Ed., 4, 336 (1932).
' L. SzebelUdy and I. Tanay, Z. anal. Chem., 108, 342 (1836).
142 II- TESTS FOR METALS
for the test in the presence of Pb, Bi, Sn, alkali and alkaline earth metaJs
may be 1:1000 (see the original paper). '
4. Zinc may be detected by placing a drop of jan acetic acid test
solution on paper impregnated with uranyl ferrocyanide."* A white
stain forms on the brown paper (/d". Ldmit: 0.1 7 Zn). The presence of
metal salts, which fonn insoluble ferrocyanides, interferes with this test;
so do large amounts of neutral salts.
ALUMINUM
1. Morin test."' The coloring matter of fustic is morin, a tetrahydroxy-
flavanol:
OH
HO O
\/\/V- -OH
Y
OH
OH O
reacting with aluminum salts in neutral or acetic acid solution to give an

intense green fluorescence. This is due to a neutral coUoidally dispersed
aluminum salt of morin A1(CUH90T)8."* This salt probably possesses
an inner complex structure analogous to that of the aluminum salts of the
hydroxyanthraquinones (see page 145). Be, Zn, Ga, and So salts also
form fluorescent compounds with morin.'"
f ProcedureTo test for aluminum in the presence of other metals
which give color or precipitation reactions with morin, the test solution is
precipitated with potassium hydroxide. A drop of the filtrate is acidified
on a black spot plate with 2 N acetic acid, and a drop of morin solution
is added. A green fluorescence appears in the presence of aluminum.
For small amounts, comparison with a blank test is advisable..
Ldmit of Identification: 0.2 7 aluminum
Concentration ldmit: 1:250,000
Reagents: 1) Saturated solution of morin in methyl alcohol
2) 2 N potassium hydroxide
3) 2 N acetic acid
The following procedure is more sensitive. Filter paper is impreg-
nated with freshly prepared morin solution, dried, and treated with a drop
of the neutral, or slightly acid test solution, and again dried. On spotting
' " F. Feigl, unpublished studies. - '"T -
"Fr. Goppelsroeder, Z anal. Chem., 7, 195 (1868). E. Eegriwe, ibid., 76,
440 (1929).
" E. Sohantl, Mikrochemie, 2, 174 (1924).
M' G. Beck, Mikrochim. Ada, 2, 9, 287 (1937).
ASiVmsxjH 143
with 2 N h}rdrochlonc add, a light greenflu(^8cingfleckcan be d)%rved

under the quartz analytical lamp.**"
Limit of Identification: 0.005 y aluminum
ConceTUration Limit: 1:10,000,000
If aluminum is to be detected in the presence of elements of the
ammonium sulfide group, it is necessary to wash away the morin otsn-
pounds of these elements by using several more drops of dilute hydro-
chloric acid.
2. Test with alizarin sulfonic add (alizarin S).'*^ Aluminum salts give
a red precipitate with alizarin S (I) in ammoniacal )luti(ai. TTie pre-
cipitate is a color lake, i.e., it is a mixture of AljO tod HjO with a colored
inner complex salt, whose structure is showii in (II).
OH
SOH 80,H
The color lake formed in ammoniacal solution is stable to dilute acetic

add, whereas the violet color due to the action of the base on the excess
alizarin sulfonic acid reverts to the origins^ yellow of the dyestuff on
addification.
^[ProcedureA drop of the caustic alpine test solution is treated
with a drop of alizarin S and then with acetic acid, until the violet color
disappears, and then with a further drop of Acetic acid. According to the
amoimt of aluminum present, a red precipitate or color appears. It intensi-
fies on long standing.
For the detection of small amoimts oSi aluminum, a blank test on
1 drop of 1 ^ alkali alone should be carried out, and the color ccunpared
with that of the test solution.
Limit of Identification: 0.65 y aluminuih
Reagents: 1) 0.1% solution of sodium alizarin sulfonate
S) I N sodiiun hydroxide: tliis should be kept in a bottle
made of resistant glass. A blank Ghould give no color
or only a faint pink
Studies with H. E. Ballaban.
F. W. Atack, / . Soc. Chem. Ind., 34, 936 (1916); see also K. Heller and P.
Krumhols, Mikroehemie, 7, 221 (1029).
144 n . TBSTS FOB METALS
Te^for aluminum in the presence of other ions !

Iron, cobalt, and copper salts give lakes with alizarin which are
partially stable towards acid. These elements must iherefore be removed
before the test. This is best done by precipitation, as hydroxides with
sodium hydroxide; the aluminimi remains in solution as aluminate.
Zinc salts do not interfere. Alkaline earth salts in concentrated
solutions also give red alizarin compounds, a fact that must be remembered
in carrying out this test.
In the precipitation of the hydroxides, alkaU of not more than 1 N
strength should be used, and not in too great an excess, as alkali almost
invariably contains traces of alimiinum. A blank should be carried out
using exactly the same amount of alkali as in the test to reduce the error
from this source.
Chromates interfere, owing to the high color of these salts. However
2 7 aluminum may be clearly detected in the presence of 120 times the
amount of chromium, if a comparative test is carried out on a 1% chromate
solution.
3. Test with alizarin.''*^ Aluminum salts give a deep violet lake with an
ammoniacal solution of alizarin in the same way as with alizarin sulfonic
acid (compare page 143). Probably an inner complex salt is the colored
constituent of this lake.
The red products formed by the action of alizarin on aluminum
hydroxide have no delSnite composition. They obviously are adsorption
compounds analogous to those produced in the test for magnesium (com-
pare page 172).
f ProcedureÂ drop of the test solution is placed on alizarin paper,
and held over a dish of ammonia until the fleck, due to the ammoniimi
salt of alizarin, turns violet.
If large amoimts of aluminum are present the red color is visible
mmediately. If the paper is dried in an oven, the violet color due to the
ammonium alizarinate disappears, as it is converted into ammonia and
alizarin; the red color of the aluminum lake then becomes clearly visible.
Limit of Identification: 0.16 y alimiinum "
Reagent: Alizarin paper. Quantitative filter paper is soaked in a
saturated alcohol solution of alizarin, dried, and kept in a
stoppered container
Test for ahiminum in the presence of other metols ofjhe ammonium sulfide
group ' -
Iron, chromium, uranium, and manganese also give colored alizarisi
lakes. In some cases (compare page 146) a separation of the components
' F. Feigl and R. Stern, Z. anal. Chem.. 60. OTlSSl).
ALXmiNTTM 145
of a solution occurs in the capillaries of the paper so that the various metal
lakes are formed in different zones of the paper. Unfortunately, this
procedure can only be used in the aluminum-uranium separation, as it is
only applicable within definite concentration differences for the other
metals. However, the fact may be utihzed that aliuninum, in contrast to
all the other ions of the anunoniiun sulfide group, gives no insoluble com-
pound with potassium ferrocyanide. Thus, when the reaction is carried
out as a spot test on filter paper impregnated with potassium ferrocyanide,
the aluminum diffuses through the capillaries to the zone or water ring
encircling the fleck of precipitate, and can be detected there by the alizarin
reaction.
IfProcedureA small drop of the neutral or weakly acid test solution
is placed on potassium ferrocyanide paper. The other ions are "fixed"
in the paper as insoluble ferrocyanides. The aluminmn remains dissolved
and diffuses with the water beyond the precipitate. Most of the aluminum
can be'washed into the outer zone by the addition of another drop of water
to the middle of the fleck.
A drop of alizarin is added; the paper is held over ammonia and
dried. A red ring of aUzarin-aluminiun lake is formed around the ferro-
cyanide precipitate. In order to make the product visible, it is advisable,
after the reaction is complete, to place the paper, for about 2 minutes, in
hot water. Some of the metal ferrocyanides are washed off and the alumi-
num lake is more visible.
The limits of identification for alvmiinum in the presence of varjring
amounts of the other metals, according to this method, are:
4.0 7 Al in the presence of 800 y Fe
3.0 T Al in the presence of 300 7 Fe + 750 -y Cr
1.4 Y Al in the presence of 3912 7 Mn
0.6 7 Al in the presence of 60 7 Fe + 372 7 Mn
0.6 7 Al in the presence of 30 7 Fe + 180 7 Zn
0.1 7 Al in the presence of 30 7 Zn + 20 7 Mn
0.5 7 Al in the presence of 100 7 U
0.6 7 Al in the presence of 30 7 Fe + 72 7 Oo
The following should be noted with reference, to the detection of

aluminum in the presence of other metals: When mtich iron is present, it
may happen that the potassium ferrocyanide in the paper in the area of the
drop is insuflBcient to bind all the iron. When the fleck is then moistened
with the wash water, unchanged ferric chloride diffuses outward and this
extends the Prussian blue fleck, thus rendering the detection of the alumi-
num difficult. It is best then to use very small drops, so that the fleck is
at most 6 mm. in diameter, and also to carry out a comparative test on
an iron solution under exactly the same conditions, on the same paper.
The difference then becomes quite easy to see.
In testiag for aluminum in the presence b/ uranium there is a danger

of spreading the uranium ferrocyanide fleck, owing to its slimy consistency
(especially when very little uranium is present). This can interfere with
the detection of very small amounts of the aluminuni lake. It is advisable
to soak the filter paper in an ammonium carbonate solution after the test is
completed. This reagent dissolves the uranium as (NH4)4[U02(COj)3]
and the aliuninum lake can be seen clearly.
In detecting a small amount of aluminum in the presence of much iron
and chromium, a control test should be carried out on an aluminum-free
iron chromium solution. Further, after the addition of the alizarin, the
paper should be placed in hot water for 1 minute and then dried. In this
way, the potassium ferrocyanide is removed, and the paper becomes white.
The lake color is thus rendered more visible. The controlflecksshow only
a very slight color change, if any, as the chromium ferrocyanide is also
washed away. The concentration of iron and especially the chromium in
the control solution should approximate that in the test solution. How-
ever, it has been found that the concentrations of iron and chromium may
vary within wide limits, and yet the solutions will give useful comparative
results.
Test for aluminum in the presence of uranium by capillary separation
Uranium salts give a blue lake with alizarin. When a drop of a
solution containing both aluminum and uranium is placed on filter paper
impregnated with alizarin, a fleck of the blue uranium lake forms in the
center of the drop. The aluminum diffuses outward and after being devel-
oped with ammonia, encircles the blue with a red ring. The width of the
ring depends on the aluminiun content. In this way, 0.1 y aluminum may
be detected in the presence of 200 times the amount of uranium.
Test far aluminum in the presence of cobalt and nickel
0.1 y aluminiun may be directly detected in the presence of 0.014 mg-
of cobalt or nickel by the lake method. Larger amounts of the two metals
interfere with the sensitivity, partly by lake formation, and partly by the
formation of colored anmiine salts. Under sucli conditions, the following
procedure should be used.
^ProcedureA drop of the test solution is placed on alizarin paper,
held over anunonia, dried, and then laid in hot 0.01 N hydrochloric acid.
The coloration due to cobalt or nickel lakes or ammines disappears, and
the aluminum lake can be redeveloped over ammonia. By this method
0.9 7 aluminum can be detected in the presence-of 0^12 mg. cobalt.
4. Test with quinalixariii.''" The compound quinalizarin (1,2,5,8-tetra-
hydroxyanthraquinone) (see page 148) which is especially useful for the
F. L. Hahn, Mikrochen{ie, 11, 33 (1932). ^
BERTLUUH 147
detection of beryllium, is also a sensitive reagent for the aluminum ion,

with which it fonns a lake stable to acetic acid. When used analytically
it is necessary to carry out the reaction in ammoniacal solution, as in the
formation of the alizarin lake, and then acidify with acetic acid.
1[ProcedureA drop of the test solution is placed on quinalizarin
paper; it is held for a short time over a bottle containing concentrated
ammonia, and then over glacial acetic acid, until the initial blue color
(ammonium salt of quinalizarin) disappears and the unmoistened paper
regains its brown color (free quinalizarin). According to the aluminum
content, a red-violet or faint red fleck remains.
Limit of Identification: 0.005 y aluminum (drop = 0.1 ml.)
Reagents: 1) Quinalizarin paper. 10 mg. quinalizarin"âre dissolved
in 2 ml. pyridine, diluted with 20 ml. acetone and
" quantitative filter paper soaked in this solution
2) Ammonia
3) Glacial acetic acid
This test with quinalizarin is especially useful for the detection of
aluminum in the presence of magnesium. The limiting ratio, as in many
other spot tests, depends on the concentration of the test solution. For
instioice:
Ratio,
Concentntios of Al:Mg Detection
1 7 per ml. Al 1:10^* Just barely good
2 7 per ml. Al l:10-< Good
6 7 per ml. Al 1:10~ Very good
5. Other tests for aluminum. 1. Pontachrome blue-black R (zinc salt of
4-sulfo-2,2'-dihydroxyazonaphthalene) gives an orange-red fluorescence
with aluminum salts in acetic acid solution*** {Id". Limit: 2 7 Al in 1 ml.).
This test appears to be specific for aluminum, as Be, Zn, and Ga, which
behave similarly to aluminum in thefluorescencereaction with morin, do
not react with this dyestuff. It is probable that this reaction can be
carried out as a spot test.
2. Ashless filter paper is impregnated with a solution containing
0.1% of the ammonium salt of aurintricarboxylic acid (aluminon)"* and
1% of ammonium acetate. One drop of an HGl-aluminum solution is
placed on the paper, developed over ammonia, and dried. A red lake is
formed266 (î^n Umit: 0.16 7 Al).
BERYLLIUM
1. Test with quinalizarin."' A slightly alkaline, very dilute solution of
beryllium is colored cornflower blue by the addition of a few drops of a
"* C. E. White and C. S. Lowe, Ind. Eng. Chem., Anal. Ed., 9, 430 (1937).
"> L. Hammett and C. Sottery, / . Am. Chem. Soe., 47, 142 (1925).
" W. E. Thrun, J. Chem. Education, 14, 281 (1937).
" ' H. Fischer, Z. anal. Chem., 73,64 (1928).
148 n . TESTS FOB HETALS
dilute solution of quinalizarin (1,2,5,8-tetrahydroxyanthraquinone) in

alcohol or alkali. The dyestuff solution alone with dilute alkali gives a
characteristic violet color that is quite distinct from the blue of the beryl-
lium solution. Nevertheless, for the detection of small amounts of beryl-
liiun, a blank test on pure alkali should be carried out. Considerable
quantities of berylhum give a precipitate.
Tie CGEnpomticm of the heryWium cGEopoand fomaed is stiJJ unknown ;
possibly it is an inner complex compound of quinahzarin and beryUium,
or a color lake (see page 145).
This test is afifected by the presence of ammonium salts, which
should therefore be removed beforehand.
Aluminiun, lead, zinc, and antimony salts do not interfere. The
colored solutions of copper and nickel salts can be decolorized by formation
of complex salts on the addition of potassimn cyanide. Cobalt salts with
potassium cyanide form the hght yellow colored soluble potassium co-
balticyanide KCo(CN)6, which does not interfere with the recognition
of the blue color of the quinaUzarin compound. Iron (III) salts may be
masked by the addition of tartrates. In the presence of aluminum, how-
ever, tartrates interfere, as then a red color is formed in the caustic alkaline
solution of quinalizarin. If beryllium is to be detected in the presence of
both iron and aluminum, the test solution should be treated with 5 ml. of
1 N NaOH, cooled, diluted to 15 ml., and then filtered, if necessaiy. The
filtrate contains Be as beryllate, and can be tested as described below.
Magnesium also gives a blue compound with quinalizarin, which'
is useful in testing for the metal (see page 172). Berylliimi call, however,
be detected in the presence of magnesium by utilizing the different sta-
bilities of their lakes toward oxidizing agents (see later). It must be noted
that Nd, Pi:, Ce, La, Zr, and Th salts also form lake colors with quin-
alizarin.**'
IfProcedureA drop of the test solution ig mixed on the spot plate
with a drop of freshly prepared solution of quinalizarin in sodium hydroxide
solution. For very small amounts of berylliunj, -a Saturated solution of
the dyestuff may be used. This solution wiU keep; it contains about
' A. S. Komarowsky and I. M. Korenman, Z. anal. Chem., 94, 247 (1933).
' BERYLUTTM 149
0.005% quinalizarin. After this, a drop of dilute ammonia or alkali is

added. A blue color (compared with a blank) indicates the presence of
beryllium.
Limit of Identification: 0.14 y berylliimi
Reagent: Saturated alcoholic solution of quinalizarin, or freshly
prepared solution of 0.05 g. quinalizarin in 100 ml. 0.1 N
sodiiun hydroxide
Test for beryUium in the presence of magnesium^^^

Magnesium salts give a blue precipitate or coloration on the addition,
of an alkaline solution of quinalizarin. Probably an adsorption compound
is formed between the dyestuff and magnesium hydroxide (see page 172).
In sodium hydroxide solution, bromine destroys the colored beryllium
compound, but the color of the magnesium lake persists longer. On the
other hand, in ammoniacal solution, the magnesium color is completely
destroyed or inhibited, but the beryllium lake retains its blue color. Beryl-
lium can therefore be detected in the presence of magnesium.
^ProcedureÂ drop of the neutral test solution is treated on the spot
plate with 2 diops of 0.05% solution of quinalizarin m2N ammonia, and 1 ml.
saturated bromine water is added. The originally deep blue solution is
made paler, but remains more or less permanently blue according to the
beryllium content, whereas a comparative test on a magnesium solution is
completely decolorized.
2. Test with jp-nitrobenzeneazoorcinol."" The yellow alkaline solution
of p-nitrobenzeneazoorcinol:
CH,
OZN/ SN=N<(^^ \OH
OH
forms an orange-red lake with beryllium salts. This azo dyestuff reacts
analogously to quinalizarin (see p. 147). It also reacts with Mg salts
(brown-yellow precipitate); on the other hand, it is without action on the
salts or hydroxides of the rare earths. Aluminum and the alkaline earths
do not affect the beryllixma test. Zinc hydroxide behaves similarly to
beryllium hydroxide, but the color disappears on the addition of potas-
siimi cyanide, owing to the formation of the soluble complex K2Zn(CN)4,
Similarly, the addition of potassium cyanide prevents the precipitation of
" H. Fischer, Z. anal. Chem., 73. 57 (1928).
"' A. S. Komarowsky and N. S. Poluektoff, Mikrochemie, 14, 316 (1933).
150 11. TKSTS FOB METALS
the hydroxides of nickel, cobalt, copper, cadmium, aiid silver, which would
interfere with the test.
IfProcedureA drop of the alkaline solution of jthe dyestuff is placed
on filter paper, and the tip of a capillary containiiig the test solution is
touched to the middle of the yellow area so that the liquid runs slowly
into the paper. The spot is then treated with a further drop of reagent.
In the presence of beryllium, either the whole fleck, or the middle only,
is stained more or less intensively orange-red. A
Limit of Identification: 0.2 y beryllium (in 0.04 ml.)
Reagent: 0.025% solution of p-nitrobenzeneazoorcinol"' in N NaOH
TITANIUM
1. Test with hydrogen peroxide.*" Hydrogen peroxide causes a yellow
color to develop in acid titanium solutions. In solutions containing sul-
furic acid the color is due to the formation of the complex peroxidic anion
Ti:02(SO)2~. It is furnished by the free peroxodisulfatotitanic acid*"
that is produced:
TiOSOi + HjOj + HsSOi = Hs[Ti02 (804)2] + HjO
Fluorides prevent the reaction; large amounts of acetates, nitrates,
chlorides, bromides, and colored ions, reduce the sensitivity. Chromates,
vanadates, molybdates, and cerium salts should not be present, as these
also give color reactions with hydrogen peroxide. Iron salts give a violet
color with the hydrogen peroxide, but this can be destroyed by the addition
of syrupy phosphoric acid.
^[ProcedureA drop of the hydrochloric or sulfuric acid test solution
is treated with a drop of hydrogen peroxide on the spot plate. According
to the titanium content, a more or less intense yellow color results.
Limit of Identifi,cation: 2 y titanium
Reagent: 3% hydrogen peroxide
2. Test with pyrocatechol."* Pyrocatechol (I) gives a yellowish-red.
color with weakly acidified aqueous solutions of titanium salts. This
color reaction is due to the formation of an inner complex pyrocatechate
(11) of tetravalent titanium:"'
n For preparation, see A. S. Komarowsky and N. S. Poluektoff, Mikroehemie,
U , 315 (1933). ,
" J. L. SchSnn, Z. anal. Chem., 9, 330 (1870).
"R. Schwarz and W. Sexauer, Ber., 60, 50a'(re27); R. Schwarz, Z. anorg.
allgem. Chem., 210, 303 (1933).
" J. Piccard, Ber., 42, 4343 (1909).
" A. Rosenheim, B. Raibmann, and G. Schendel, Z. anorg. allgem. Chem.,
19e, 160 (1931).
TITANIUM 151
H.[o.H.<^(<Ô.H.)J
Hi
(II) '
Large amounts of free mineral acids interfere with the reaction.

Colored ions, alkali hydroxides, and carbonates reduce the sensitivity.
Iron (III) salts should not be present, as they also give soluble colored
compounds with pyrocatechol. Since a number of other elements interfere
with the pyrocatchol reaction,"' the test is especially suited, for the
identification of titanium after it has been separated from other metals.
llProcedureA drop of the sulfuric acid test solution is placed on
filter paper impregnated with pyrocatechol. According to the titanium
present, a more less intense yellow-red fleck appears.
lAmit of Identification: 2.7 r titanium
Reagent: 10% aqueous pyrocatechol solution (freshly prepared)
3. Test with chromotropic acid.'" The sodium salt of chromotropic
acid (l,8-dihydroxynaphthalene-3,6-disulfonic acid):
HO,S SO,H
gives a brown-red color with solution of titanium salts, titanium hydroxide,

and titanic acid in hydrochloric and sulfuric acid solutions, but not in
solutions containing large amounts of nitric acid. A violet coloration
develops in cone, sulfuric acid solution (see page 152). The composition
of the compound formed is not known. It is probable that, due to the OH
groups in the peri position in the reagent, compounds are formed analogous
to those produced in the test with pyrocatechol.
^[ProcedureA drop of the test solution and of chromotropic acid
are mixed on filter paper or a spot plate. A red-brown fleck or coloration
of the solution results.
Limit of Identification: 3 y titanium
Reagent: 5% solution ot chromotropic acid
"' Compare N. R. Pike and co-workers, Ber., 68,1023 (1936).
" K. A. Hofmann, Ber., 46, 2480 (1912).
Test far titanium in the 'presence 0/ other eZemente"*

A special procedure must be used when titanium is not present in
pure solution, as chromotropic acid also reacts with other metal salts.
Iron (III) salts give a deep green, uranyl salts a brown. These colors
can be easily destroyed by the addition of a hydrochloric acid solution of
stannous chloride, as the resulting ferrous and uranous salts do not react
with chromotropic acid. Those mercury salts which dissociate give a
yellow, and silver salts form a black stain on the spot paper with chro-
motropic acid. The presence, however, of these two salts does not ma-
terially interfere, as the titanium color is still perceptible. The same is
true of iron, as the titanium color usually forms as a brown-red fleck in
the center of the green iron stain. Where there is any uncertainty as to
other elements present, the following procedure should be used.
IJProcednreA large drop of the test solution is mixed on a watch
glass with stannous chloride (a large excess is to be avoided). On gently
heating, the precipitate balls together. A drop of chromotropic acid is
placed on filter paper and then a drop of the clear solution from the watch
glass. In the presence of titanimn, a red-brown fleck appears. The pre-
cipitate, as well as the clear solution, may be placed on the filter paper,
as the precipitate remains in situ and the solution diffuses away. If the
moist portion is then treated with chromotropic acid, a red-brown circle is
formed.
An improvement on the above procedure is the use of chromotropic
acid in concentrated sulfuric acid solution.*" A violet product appears
and only large amounts of colored metallic salts or nitrates and other
oxidizing agents interfere. The latter may be completely removed by
fuming with concentrated sulfuric acid.
^ProcedureÂ drop of the test solution containing sulfuric acid is
well mixed on a spot plate or in a microcrucible with 5 drftps of the reagent
solution. A violet color indicates the presence of titanium. For very
dilute solutions, comparison with a blank test is advisable.
Limit of Identification: 0.1 y titanium
Reagent: 0.02 g. chromotropic acid dissolved, with warming, in 20
ml. cone, sulfuric acid
Detection of titanimn in minerals, see page 440.
4. Otiier tests for titaniiiin. 1. The tannin-antipyrine reaction produces a
red precipitate when applied to titanium salts.'*?, -filter paper soaked with
" ' N. A. Tananaeff and G. A. Pantschenko, Z. anorg. allgem. Chem., 180, 163
(1926).
" F. Feigl and H. E. Ballaban, unpublished studies.
" M. V. Gaptschenko and O. G. Scheinaiss, Chem. Ahiract, 81, 8430 (1937).
zmcoNiuM 153
10% tannin solution is treated successively with 1 drop 20% antipyrine

and 1 drop test solution (/d". Limit: 0.2 y Ti). The positive reaction of
other metals (except molybdenum) is prevented by spotting at the close
with 1:4 sulfuric acid. In this way, titanium can be detected in a solution
whose dilution is 1:20,000, containing as much as a thirtyfold excess of
accompanying materials.
2. One drop of the test solution is treated with 3 or 4 drops of 0.025%
methylene blue solution and a tiny particle of metalhc zinc.*'' The dis-
charge of the methylene blue is catalytically accelerated by titanium:
Ti(IV) *^ Ti(III). Comparison with a blank makes this effect distinctly
evident (Id". lAmit: 0.05 y Ti). This test is suitable for the detection of
titanium in the presence of iron, chromiimi, uranium, and manganese.
ZIRCONIUM
1. Test with g-nitroso-a-naphthol.'^^ Colored precipitates of the empirical
formula ZrO(ZioH602N)2 are produced by treating acid solutions of zir-
conium salts with an alcoholic solution of either of the two isomeric com-
pounds a-nitroso-/3-naphthol or j8-nitroso-a-naphthol. The zirconiiun
salt of the a-nitroso compound is green-yellow, that of the /S-compound
is red; both are inner complex salts. The salt formation is not due to the
phenol groups of the 1,2-nitrosophenols, but to a NOH group, in that these
nitrosophenols react in their isomeric quinoidal oxime forms. The j8-ni-
troso-a-naphthol functions accordingly:
O O ZrO/2
II II I
|/\''^\=NOH /\j/\=N=0
\/V"
When an alcoholic solution of /3-nitroso-a-naphthol is added to a
hydrochloric acid solution of zirconium, a deep red color with no precipita-
tion results; the latter coagulates only on the addition of sodium acetate.
The reaction is hindered in the presence of large amounts of sulfates or
fluorides. These form zirconosulfuric acid, or complex fluorides. Inter-
ference of sulfates can be prevented by the addition of bariirai chloride.
^[ProcedureFilter paper is impregnated with an alcohoUc solution
of )3-nitroso-a-naphthol, dried, and a drop of the hydrochloric acid test
solution is added. According to the zirconium content a more or less
intense red fleck is formed on the yellow-brown paper. The fleck becomes
more vivid on adding a little dilute acid.
" O. K. Dobroljubski, Chem. Abstracts, 82,4465 (1938).
" J. Bellucci and G. Savoia, Chem. Abstracts, 18, 3333 (1924).
Limit of Identification: 0.2 y zirconivim i

Reagent: 2% solution of jS-nitrOso-a-naphthoP" (in alcohol)
2. Test with alizarin.*'* Zirconium salts, in acid solution, give a red
brown to dark violet precipitate on the addition of an alcoholic solution
of alizarin. Other polyhydroxyathraquinones behave similarly. The
formation of the compoimd is accelerated by wanning. The composition
of the precipitate is unknown. ^
The test is hindered or prevented by the presence offluorides,sulfates,
phosphates, and organic hydroxyacids, and also by'molybdates and tung-
states. These materials reduce the ionic concentration of zirconiiun,
owing either to precipitation or complex ion formation. The interference
due to sulfates can be prevented by the addition of barium chloride.
The following procedure**' is for the detection of zirconium in the
presence of berylliimi, almniniun, titaniiun, and thoriiun salts.***
IfProcedureA drop of the test solution, which should be as nearly
neutral as possible, is mixed in a microcrucible with a drop of an alco-
holic alizarin solution, and boiled once. Zirconium and also the other
metals give red to violet colorations. A drop of dilute hydrochloric acid
is then added. Only the zirconium compound remains unaffected. Much
rirconium gives a deep red-violet color and precipitate; a little gives red-
brown flakes.
Limit of Identification: 0.5 T zirconium
The following amounts can be detected by this procedure:
1.6 7 zirconium in the presence of 500 times the amount of
aluminum
1.0 > zirconium in the presence of 600 times the amount of
thorium
Reagents: 1) Alcoholic alizarin solution. An alcoholic- solution
of commercial aUzarin is treated drop by drop with
dilute hydrochloric acid until the pure yellow color
develops; then it is diluted with ajQ equal volume of
alcohol and filtered
2) I N hydrochloric acid
M For preparation, see R. Henriques and M. Ilinsky, Ber., 18, 704 (1886).
" J. H. de Boer, Chem. Weekhlad, 21, 404 (1924); Chem. Abstracts, 19, 793
(1925).
' " According to experiments carried out by E. Rajmann. /
" According to F. Pavelka, Mikrochemie, i, 199 (1926) on placing a drop of the
solution of the pure salt on paper impregnated with alizarin, and holding over ammo-
nia, the following limits of identification are attained;
0.18 -y titanium (1:166,000) violet-red fleck
0.29 y zirconium (1:103,000) raspberry fleck
0.24 y thorium (1:126,000) violet flecks
ZIRCONIUM 165
3. Test with p-dimethylaminoazophenylarsoiiic acid.'^' Zirconium salts

in acid solution give sparingly soluble white precipitates with arsenic
acid and its organic derivatives, such as phenylarsonic acid C6H6AsO(OH)2.
This latter compound can be used in the preparation of different derivatives
among which are some that give colored insoluble zirconium salts. For
this purpose, the best are the azoarsonic acids, of which the p-dimethyl-
aminoazophenylarsonic acid (I) is especially useful, because of its avail-
abiUty. The zirconium salt of this acid forms in acid solution as a brown
precipitate (II) that stays in the pores of the filter paper as a characteristic
lake color, whereas the excess of colored reagent can be washed out with
dilute acid.
(CH.).N<^ ^N=N<^^ yA
(I)
HC1-(CH,),N/^ \N=N/^ \ABO/ \Zr/2
(II)
In concentrations exceeding 1 N, sulfuric acid causes a marked
reduction in the sensitivity of the test, due obviously to the formation
of complex zirconium-sulfuric acids. Phosphates, fluorides, and organic
acids, that give either precipitates or stable soluble complex compoimds
with zirconium salts, hinder the reaction. Antimony (V) salts give a
brown coloration similar to that formed by zirconium salts, but it disap-
pears after 2 or 3 minutes treatment with hydrochloric acid. Thus,
0.25 y zirconium may be detected in the presence of 1000 times the amount
of antimony. Antimony (III) salts give a slight colored fleck that im-
mediately disappears in the HCl bath. Thorium salts give a similar
reaction to zirconium, but the color disappears at once in the acid bath,
so that 0.2 y zirconium may be detected ,in the presence of 2500 times
the amount of thorium. Gold salts in concentrated solution, give a
violet fleck that disappears at once on bathing in HCl.
^[ProcedureA drop of the acid test solution is placed on filter paper
(S & S, Black band No. 589) that has been impregnated with the reagent
and dried. Large amounts of zirconium give a brown stain at once. On
soaking the paper for a short time in a bath of 2 N hydrochloric acid at
50 to 60 C , the reagent is quickly washed out of the paper. The brown
zirconium fleck or ring (at higher acidities of the test solution) becomes
clearly visible.
" F. Feigl, P. Krumholz, and E. Eajmann, Mikrochemie, 9, 395 (1931). The
preparation of the reagent is described.
Limit of Identification: 0.1 y zirconium fin 1 N hydrochloric acid

Concentration Ldmit: 1:500,000 \soIution
Reagents: 1) Solution of 0.1 g. p-ditnethylaminoazophenylarsonic
acid in 100 ml. alcohol ijontaining 5 ml. cone, hydro-
chloric acid '
2) 2 N hydrochloric acid
Test for zirconium in the presence of molybdenum, tungsten, and titanium

Molybdates, tungstates, and also titaniiun salts give red-brown flecks
when they are spotted on paper impregnated with p-dimethylaminoazo-
phenylarsonic acid. The flecks are acid resistant. The addition of
hydrogen peroxide converts any molybdate and tungstate into the corre-
sponding per-acids; the titanium goes over into the peroxo-compound (see
page 160). These products exhibit little if any reaction toward the
arsonic acid.
fProcedure-^Three drops of the test solution, which should contain
not more than 1% molybdenum or titanium, or 0.5 per cent tungsten, are
mixed on a spot plate with a drop of cone, hydrochloric acid and 1 drop of
30% hydrogen peroxide. A drop of this mixture is placed on the reagent
paper. On bathing the paper in warm HCl, a red fleck appears in the mid-
dle of the moist spot; this soon disappears. When zirconium is present, a
brown ring of the zirconium salt shows around the fleck. At the same time,
some of the stain due to tungsten (and to a slight extent also molybdenum)
remains, even after the paper has been in the bath for some time. The
zirconium thus induces the coprecipitation of the tungstate and molybdate
compounds. The simultaneous formation of, an acid-stable brown ring
with a red center makes it possible to detect very small amounts of zir-
conium in the presence of much txmgsten and molybdenum. If the molyb-
denima or tungsten concentration is small, only the brown zirconium ring
is formed.
fin the presence of 1000
Limit of Identification: 0.6 y zirconium I times the amount of
Concentratum ldmit: 1:100,000 |molybdenum or 500 times
[the amount of tungsten
Limit of Identification: 1 7 zirconium fin the presence of 600 times
Concentration limit: 1:60,000 \ the iamount of titanium
Test for zirconium in the presence of tin (IV)

Tin (IV) salts give a brown precipitate with the azoarsenic acid.
The precipitate, however, is not formed in high "concentration of acid and
low concentration of tin.
^ProcedureThree drops of the test solution, which should contain
mtANiuu 157
at most 0.1% tin, are mixed with a drop of cone, hydrochloric acid on a spot
plate. A drop of the mixture is placed on the reagent paper. After
brief bathing in the warm hydrochloric acid, a slight red fleck remains, at
the most. In the presence of zirconium, a more or less intense brown ring
or fleck is formed.
Limit of Identification: 0.2 y zirconium f when 250 times the amount
Concentration Limit: 1:250,000 \of tin is present
4. Other tests for zirconium. 1. Acid zirconium solutions give color
reactions with the dyestuffs, carminic acid and gallocyanin.'"* The
formation of the zirconium salt causes a change from yellow to red, or from
pink to blue. The reaction with carminic acid may be carried out as a
spot test (/d". lAmit: 0.5 7 Zr in 0.001 ml.).
2. An acetone-water solution of the dye chlorobromoamine acid
produces a red precipitate or color with acidified solutions of zirconium
salts^*' {Id"^. Limit: 0.5 7 Zr). Considerable quantities of trivalent metals,
or of materials that form complexes with Zr++++ ions, interfere.
URANIUM
1. Test with potassium ferrocyanide."" Neutral or acetic acid solutions
of uranyl salts give a red-brown precipitate with potassiimi ferrocyanide,
K4Fe(CN)6. Very dilute solutions give a coloration only, due to the
formation of uranyl potassium ferrocyanide or uranyl ferrocyanide.
The test is specific in the absence of ferric and copper salts, which
also give colored ferrocyanides. However, under the correct conditions
(see p. 158), the test may also be applied in the presence of these metals.
UProcedureA drop of the slightly acid test solution is placed on
filter paper impregnated with potassium ferrocyanide, or else a drop of the
test solution and then the ferrocyanide are placed on the filter paper.
According to the concentration of uranium, a more or less intense brown
stain is formed.
lAmit of Idenlijicaiion: 0.92 7 uranium^"
Reagerd: 3% potassium ferrocyanide solution
Test for uranium in the 'presence of iron
When the iron concentration is not too great, the uranium can be
detected by treatment of the stain with a drop of water. The uranium
" F. Pavelka, Mikrochemie, 8, 345 (1930).
" J. H. Yoe and L. G. Overholster, Ind. Eng. Chem., Anal. Ed., 16,173 (1943).
P. Feigl and R. Stern, Z. anal. Chem., 60, 39 (1921),
" F. Hernegger, Am. Akad. Wiss. Wien, Math.- naturw. Klasse, 144, 217 (1935).
F. Hernegger and B. Karlik, Chem. Abslracts, 30, 408 (1936), states that as little as
0.05 7 uranium (1:100,000) can be detected if a microdrop (0.001 ml.) is used.
precipitate, owing to its slimy consistency, spreads' more than the iron
precipitate, and appears outside the central stain of Prussian blue. It
forms a jagged brown fringe. When the proportions! of the two elements
are such that this test cannot be used, then the factimay be applied that
uranates precipitated by alkali are soluble in ammonium carbonate with
the formation of complex carbonates, such as (NH4)4 [1102(003)3]. This
solution, after acidifying with hydrochloric acid, may be used for the
uranium test.
IfProcedureA drop of concentrated ammonia is placed on filter
paper, and, before this is completely taken up, a drop of the test solution
is added and rubbed with a glass rod. The filter paper is then dried,
spotted with ammonium carbonate, and the site of the fleck rubbed with a
glass rod to insure that all parts of the fleck come into contact with the
ammonium carbonate. After redrying, dilute hydrochloric acid is spotted
around the fleck, but without touching it (in order to avoid formation of
Prussian blue when the ferrocyanide is added). The brown color is
especially distinct at the edges of the hydrochloric acid ring adjoining the
original fleck and extends to where the twofleckshave been superimposed,
producing a starlike picture.
Test for uranium in the presence of iron and copper^^^
The test for uranium with potassium ferrocyanide can also be carried
out in the presence of ferric and cupric salts, when these metals are con-
verted, before the addition of the ferrocyanide, into the nonreacting cuprous
and ferrous forms. This may be achieved by reduction with alkali iodide:
2 Cu++ + 4 I- = CU2I2 + I2
2 Fe+++ + 2 I- = 2 Fe++ + h
If the liberated iodine is decolorized with thiosulfate
h + NajSjOs = NajSA + 2 Nal
the uranium may then be detet^ted with potassium ferrocyanide.
^ProcedureA drop of cone, potassium iodide solution is placed on
filter paper, and, after it is soaked into the paper, a drop of the acid test
solution is added; iodine is liberated. In order to complete the reduction,
a further drop of potassium iodide is added, and then a drop of sodium
thiosulfate to remove the iodine. A drop of potassium ferrocyanide is
added to the decolorized fleck.- A more or less deeply colored circle is
formed, according to the amount of uranium present.
" ' N. A. Tananaeff and G. A. Pantschenko, Z. anorg. allgem: Chem., 160, 164
(1926).
URANIUM 159
It is more expedient to carry out the reduction to ferrous and cuprous

ions with sodiuii thiosulfate alone and to use a spot plate:
2 Fe+++ + 2 SiOT' = 2 Fe++ + S4O7"
2 Cu++ + 2 SjOr" = 2 Cu+ + 8407"
When copper is present it acts as a catalyst for the reduction of the iron
by thiosulfate (see page 63).
2. Other tests for uranium. 1. A rust-brown fleck is produced by uranium
when spotted on paper with 0.2% solution of quercetin or quercitrin"'"
(Id". Limit: 3 y U). See also page 128.
Detection of uranium in minerals, see page 439.
3. Fluorescence test.^'* Uranyl saltsfluorescebest when in the crystalline
form, and only slightly in solution. When a dilute solution of uranium
salts is allowed to evaporate slowly on a microscope slide, and then ex-
amined, single fluorescent crystals are observed. Traces of impurities, or
too rapid evaporation of the solution, interefere with the test, as they prevent
the formation of good crystals.
Borax beads which contain uranium exhibit an appreciable green
fluorescence. Fluoride beads of the alkalis and alkaline earth metals'"*
.fluoresce especially well. Sodium fluoride beads which light up to a deep
yellow color are most striking. They can be used to detect uranium.
In testing for uranium by means of activated beads, the shape of the
bead is very important. Thin flat beads are better than the round type,
as the ultraviolet light penetrates better. Neither SiOj, TiOj, nor sulfates,
etc., should be present, nor any other material that either hberates hydro-
fluoric acid or forms complex compounds with fluorides. Iron is also to be
avoided, as it makes the bead yellow and so absorbs the ultraviolet light
on the surface. Manganese salts, which color the beads blue, do not
interfere so much as iron. Thorium salts also greatly reduce the luminosity,
but it may still be perceptible provided sodium fluoride is present in excess.
Only niobium^'^ gives a similarfluorescence,but it is relatively so weak as
to be of no importance.
^ProcedureSodium fluoride is fused to form a bead in a loop of
platinum wire (diam., 1 mm.). On cooling, this appears only slightly vio-
let in ultraviolet light (reflected Ught). By means of a calibrated loop of
platinum, 0.001 ml. of the neutral test solution is placed on the bead and
> E. A. Kocsis, Mikrochemie, 26,13 (1938).
"* F. Hernegger, Am. Akad. Wiss. Wien, Maih.-naturw. Klasse, 144,217 (1935);
F. Hernegger and B. Karlik, Sitzber. Akad. Wiss. Wien, Math.-naturw. Klasse, Abt.
Ila, 144, 217 (1935); Chem. Abstracts, 30, 408 (1936).
" E. L. Nichols and M. K. Slattery, J. Optical Soe. Am., 12,449 (1926).
J. Papisch and L. E. Hoag, Proc. Natl. Acad. Set. U. S., 13, 726 (1927).
160 H- TESTS FOR METALS
evaporated. After fusing for a short time, the bea,d is cooled and examined
in ultraviolet light. '
Ldmit of Identification: 0.001 y uraniimi in 0.001 ml.
CERIUM
1. Test with hydrogen peroxide and ammonia.^^' Cerium (III) and (IV)
salts are precipitated by ammonia and hydrogen peroxide as yellow or red-
brown cerium perhydroxide,' Ce(0H)2(00H) and Ce(0H)3(00H). This
test is characteristic for cerium in a mixture of the rare earths, but may not
be used directly in the presence of iron, as the color of the cerium perhy-
droxide is similar to that of ferric hydroxide. In this case, the precipitation
of iron must be prevented by the addition of tartrate, but it should be noted
that this also reduces the sensitivity of the cerium test. The presence of
large amounts of colored ions renders the identification of small amounts
of cerium difficult., ,
^ProcedureÂ drop of the test solution, one of hydrogen peroxide,
and one of ammonia are mixed in a porcelain microcrucible and gently
warmed. In the presence of cerium a yellow precipitate or coloration
appears.
ldmit of Identification: 0.35 y cerium
Reagents: 1) 3% hydrogen peroxide
Z) Dilute ammonia
2. Test with anunoniacal silver nitrate.^'' Ammoniacal silver nitrate
reacts with solutions of cerous salts to form eerie hydroxide and elementary
silver:'
Ce+^^+ + Ag(NH,)2+ + 4 OH" = Ce(0H)4 + Ag + 2 NH,
The yellow cerium hydroxide precipitate is colored black by the finely
divided elementary silver. Probably an adsorption compound is formed
because the product is incomparably blacker than a mere mixture of the
components produced separately and then mixed.
The test is characteristic for cerium in a mixture with other rare
earths. Among the other elements, manganese (II), iron (III), and cobalt
(II) salts react in the same way as ceriimi (III) salts to give the higher
metal oxides and elementary silver.
fProcednreA drop of the neutral test solution and a drop of an
"Lecoq de Botsbaudran, Compt. rend,, 100, 605 (1885).
" ' L. Pissarjewsky, Z. an.org. allgem. Chem., 31, 360 (1902); see also A. Lawson
and E. W. Balson, / . Chem. Soc, 138, 362 (1935).
" W. Biltz and F . Zimmermann, Ber., 40,4979 (1907).
CERIUM 161
ammoniacal silver nitrate solution are mixed on a watch glass and gently
wanned. According to the amount of cerium present, a black precipitate
or brown colorationiis formed.
Ldmit of Iderdificalion: 1 y cerium
Concentrations: 1:60,000
Reagent: Ammoniacal silver nitrate solution: 0.4 N silver nitrate
solution is mixed with sufficient dilute ammonia to
redissolve the initial precipitate
3. Test with benzidine.^"" Benzidine (see page 55) is converted by a
number of oxidizing agents and autoxidizable substances into a blue semi-
quinoid compound. Both cerimn (III) hydroxide and the autoxidizable
cerous hydroxide may be used. The reaction, applied as a spot test, is
characteristic for cerium among the rare earths.
The reaction is not directly applicable in the presence of manganese,
cobalt, copper, silver, or thallium salts, as well as chromates. They con-
vert benzidine to the blue compound. In these instances it is advisable to
precipitate cerous fluoride (CeFj) from the neutral or slightly acid test
solution with hydrofluoric acid, then to spot with alkaU, and then with
benzidine.
fProcedureA drop of the test solution is placed on filter paper,
followed by a drop of sodimn hydroxide, and a drop of benzidine solution.
According to the cerium content, a more or less deep blue coloration results.
ldmit of Identification: 0.18 7 cerium
Coricentraiion Ldmil: 1:275,000
Reagents: 1) Dilute sodium hydroxide solution
2) Benzidine solution (see page 135)
The following tests were carried out with regard to the detection of
cerium in the presence of iron.
Sixty ml. of a solution containing Ce(III) and Fe(ni) sulfates was
treated with alkaU until a permanent precipitate was formed. Then a few
drops of hydrofluoric acid were added and the mixture boiled and filtered.
The precipitate was washed once with water, covered with dilute alkali
and tested with an acetic acid solution of benzidine. In this way the blue
color caused by 70 y cerium can be identified in the presence of 227 mg.
iron. This corresponds to a ratio Ce:Fe = 1:3230.
4. Test with phosphomolybdic add.^" The enhanced oxidizing action of
molybdic acid in certain heteropolyacids, for instance phosphomolybdic
acid H7P(Mo207) (silicomolybdic acid behaves similarly), is apphed to
" F. Feigl, Oesterr. Chem.-Ztg., 22, 124 (1919).
' " A. S. Komarowsky and S. M. Korenmann, Mikrochemie, 12,211 (1932).
cerium (III) salts. In the presence of alkali, these salts form the lower
blue molybdenum oxide and'CeOj-aq. As all the other rare earths, as
well as zirconium and thorium salts, are indifferenlJ toward phosphomolyb-
dic acid, cerium may be identified in a mixture of these elements as obtained
in the course of the systematic scheme of analysis. '
^[ProcedureÂ drop of the test solution and of phosphomolybdic
acid solution are mixed on a spot plate, and a drop of sodium hydroxide
is added. According to the cerium content, a more or less intense blue
color or blue precipitate appears.
Limit of Identification: 0.52 y cerium
Reagents: 1) Saturated solution of phosphomolybdic acid (for prep-
aration see page 85)
This method of detecting cerium in the presence of other rare earths
(especially zirconium and thorium salts) gives better limiting proportions
than the benzidine test (3). The comparative figures for 10 y cerium are:
Btnzidi&c leaction Phosphomolybdic &cid leaction
Ce:Pr = 1:13 ' Ce:Pr = 1:1100
Ce:Nd = 1:13 Ce:Nd = 1:90
Ce:La = 1:10 Ce:La = 1:2130
Ce:Th = 1:17 Ce:Th = 1:521
Ce:Zr = 1:1 Ce:Zr = 1:230 ;
5. Other tests for cerium. 1. Leuco malachite green is oxidized to mala-
chite green by Ce(0H)4, which is formed from Ce(PH)3 by autoxidation.
This reaction may be applied as a test for cerium.'"'' Interference due to
Mn(0H)2, Co(0H)2, T1(0H)3, and AgjO, which react in the same way,
may be prevented by hydroxidic precipitation of the cerium with KCN
(Id". Limit: 0.03 y Ce in 0.1 ml.).
2. Solutions of Ce(IV) salts containing much hydrpchloric acid form
precipitates with ammonium naphthoate (black-blue), with' ammonium
anthranilate (dark red-brown), with ammonium sahcylate (dark brown).""
As spot reactions, the precipitates are formed from 10~' to 10~* N Ce(IV)
solutions. Th, Pr, Nd, and Zr salts do not form precipitates.
INDIUM AND GALLIUM
1. Test for indium with alizarin or quinalizarin.^"^ Salts of indium form
lake colors with polyhydroxyanthraquinones. The products are probably
L. Kul'berg, Mikrochemie, 21, 35 (1936). ^
" F . A. Shemyakin and A. N. Belokon, Chem.'Abstracts, 32,.4470 (1938).
" A. S. Komarowsky and N. S. PoluektofE, Jlfifcrocfcemie, 16, 227 (1935).
INDIUM AND GALLIUM 163
similar in constitution to the aluminum, beryllium, and magnesium lakes.

The indium lake with alizarin is dark red, that with quinalizarin violet.
They may be formed on paper impregnated with aUzarin or quinalizarin,
respectively.
This lake formation with the hydroxyanthraquinones is not specific,
as numerous other metals form similar lakes. However, under carefully
controlled conditions, indium may be detected in the presence of Al, Zn,
Ni, Co, Mn, Cs, and Fe, provided the proportion of foreign metal is not
too high (see page 164).
IfProcedureFilter paper is impregnated with a saturated alcoholic
solution of aUzarin, or with a solution of quinalizarin in a mixture of
pyridine and acetone. When dry, a drop of the test solution is placed on
it. The test solution should be neutral or slightly acid with acetic acid.
The moip*^^ fleck is held over ammonia and then immersed in a saturated
aqu6ous solution of boric acid. , The violet ammonium alizarinate, or
quinalizarinate is decomposed, and the red, or violet, indium lake is
easy to see against the yellow or red paper.
Limit of Identification: 0.05 y indium (in 0.025 ml.">
Reagents: 1) Saturated alcoholic solution of alizarin or solution of
0.01 g. quinalizarin in 2 ml. pyridine and 20 ml. acetone
2) Ammonia
S) Saturated aqueous solution of boric acid
Test for indium in the presence of elements of the ammonium sulfide group
Almost all the elements of the (NH4)2S group form colored lakes with
polyhydroxyanthraquinones and interfere with the direct test for indium.
In a few cases the test may still be carried out. In the presence of alumi-
num, the interfering ion may be masked by the formation of the complex
MFJ' ion. The drop of the test solution is mixed with 3 or 4 drops of a
saturated solution of NaF in a microcrucible. The test, as described, is
then carried out using a drop of this mixture.
Limit of Identification: 1 y indium fin the presence of 375 times the
Concentration Limit: 1:25,000 \amount of aluminum
Probably Be, Zr and Th ions, which also interfere with the test, could
be similarly masked; they also form complex or insoluble fluorides.
In order to detect indiima in the presence of zinc, nickel, cobalt, and
manganese, which also give colored lakes resistant to boric acid, these
metals are converted to the complex cyanide ions, which do not react. The
paper impregnated with the dye is treated with a drop of 5% potassium
cyanide solution, followed by a drop of the test solution, and then another
drop of the cyanide solution. After immersion of the paper in boric acid,
the characteristic stain due to indium remains on the paper. The following
sensitivities were obtained, using this procedure on a drop of 0.025 ml.:
Limit of Identification: 0.13 y indium /in the presence of 2200 times
Concentration Limit: 1:192,000 \the, amount of zinc
Limit of IdentificMion: 0.06 y indium fin the presence of 5900 times
Concentration Limit: 1:400,000 |the amount of nickel
Limit of Identification: 0.1 y indium fin the presence of 2400 times
Concentration Limit: 1:250,000 Ithe amount of cobalt
Limit of Identification: 0.6 7 indium fin the presence of 550 times
Concentration Limit: 1:40,000 \the amount of manganese
In order to detect indium in the presence of chromium, 0.5 N sodium
hydroxide is substituted for potassium cyanide in the procedure. The
chromium is thus converted to chromite, which does not react.
Limit of Identification: 0.6 y indium fin the presence of 800 times
Concentration Limit: 1:40,000 \the amount of chromium
To detect indium in the presence of, iron, a drop of the test solution,
in a microcrucible, is treated drop by drop with a concentrated solution of
sodium thiosuUate until no more violet color forms. A crystal of Na2S0i
and 6 to 8 drops of 5% KCN solution are then added and the mixture is
warmed until the precipitate dissolves. The solution now contains the
iron in the form of potassium ferrocyanide. It may be used for the indium
test by spotting the impregnated paper with subsequent boric acid
treatment.
Limit of Identification: 1 7 indium fin the presence of 450 times
Concentration Limit: 1:25,000 \the amount of iron
2. Test for gallium with ferrocyanide and manganese (II) 88118.'"= Man-
ganese (II) salts form a brown insoluble salt with potassium ferricyanide.
The same insoluble salt is formed when an acid manganese (II) salt solution
is mixed with an oxidizing agent (KNO2, KBrOa) followed by potassium
ferrocyanide. The concentrations of the oxidizing agent and the manga-
nese (II) salt may be so selected that no brown precipitate of the manganese
salt is formed. When a gallium salt is added to such a solution, a red-brown
coloration or precipitate forms. The chemistry of this reaction has not
yet been elucidated. Probably the oxidation potential of the ferricyanide
is raised by taking up the insoluble gallium ferrocyanide (see page 137).
^ProcedureA drop of the test solution is mixed with 4 drops of a
dilute solution of a manganous salt in hydrochloric acid. One drop of a
mixture of potassium ferrocyanide and potassium bromate (10 drops KBrOs
to 20 ml. K4 [Fe(CN)(]) is added. In the presence-of gallium, a red-brown
precipitate or turbidity forms.
" N. S. Poluektoff, Mikrochemie, 19, 248 (193i5).
BARIUM 165
r Limit of Identification: 5 y gallium (in 0.04 ml.)

Reagenfs: 1) Acid solution of a Mn salt (0.5% MnCU va.&N HCl)
2) 2.5% potassium ferrocyanide solution
S) 0.1 N potassium bromate
The test is only specific in the absence of metals which react with
ferrocyanide. If such are present, the galUum must be separated before-
hand. For instance, extraction of GaCU with ether from strongly acid
solutions can be used*. For details, the original paper should be consulted.
C. AMMONIUM CARBONATE GROUP

BARIUM
1. Test with sodium rhodizonate.'"' An aqueous solution of sodium
rhodizonate (I) produces colored precipitates (II) with solutions of the
salts of divalent heavy metals (see page 57).
COCOCONa COCOC~^
I II. -* I II M e
COCOCONa COCOC-^
(I) (II)
Neutral solutions containing barium give a red-brown precipitate of barium

rhodizonate. Strontium salts react in the same way with rhodizonates,
but not caiciiun salts. Under suitable conditions, however, barium may
be identified in the presence of strontiiun. The rhodizonic acid test is
thus recommended only for the identification of barium within the am-
monium carbonate (alkaline earth) group, or for the detection of barium
when divalent heavy metals are known to be absent.
f ProcedureA drop of the neutral or slightly acid test solution is
placed on filter paper and then a drop of an aqueous solution of sodium
rhodizonate. According to the amount of bariiun present, a more or less
intense red-brown stain is formed.
Limit of Identification: 0.25 y barium
Reagent: 0.2% aqueous solution of sodium rhodizonate'"^
Paper may be impregnated with sodimn rhodizonate solution. The
paper must be dried in vacuo (over cone. H2SO4) and in the dark. Other-
wise, the rhodizonate is oxidatively decomposed.""
" F. Feigl, Mikrochemie, 2,188 (1924).
" ' For preparation, see G. Gutzeit, Helv. Chim. Acta, 12, 713 (1929).
" Compare A; L. Godbert and R. Belcher, Analyst, 64, 346 (1939).
Test for barium in the presence of strontium I

Strontium salts react similarly to barium salts jvvith the sodium rhodi-
zonate. However, strontium rhodizonate is easily soluble in dilute hydro-
chloric acid in the cold, whereas the barium compound is converted into an
insoluble bright red acid salt (similar in color to nickel dimethylglyoxime).
It must be noted that small amounts of barium rhodizonate, prepared in a
test tube in neutral solution, when treated with hydrochloric acid, seem to
dissolve, because the red barium salt is then formed in a fine state of division
and is hard to see. If, however, the reaction is carried out on paper, the
brown-red stain of barium rhodizonate is turned by dilute hydrochloric
acid (1:20) to a vivid red. Probably the red barium salt is adsorbed on the
paper so that even small amounts of the adsorbed compound become
plainly visible.
If no brown fleck is formed on treating a drop of the test solution with
a drop of sodium rhodizonate on filter paper, this indicates the absence of
both barium and strontium; a brownfleckmay mean either metal is present,
or both. If thefleckdisappears on treatment with dilute hydrochloric acid,
only strontium is present; if it turns red, barium (or barium and strontiiun)
is present.
Limit of Identification: 0.5 y barium fin the presence of 50 times
Concentration Limit: 1:90,000 \the amount of strontium
The following is of interest with respect to the detection of barium
in the presence of strontium.""
Barium carbonate is more soluble than calcium or strontium carbonate
and if it is thoroughly washed and then spot-tested, directly with sodium
rhodizonate a brown-red precipitate appears. Calcium and strontium
carbonate do not react under these conditions. However, this differential
behavior is only useful to distinguish pure BaCOj and SrCOj one from the
other. It cannot be used indiscriminately to detect barium in a mixed
carbonate precipitate, because barium rhodizonate is formed only if a very
large excess of barium carbonate is present. When a mixture of the
carbonates is thrown down, the barium carbonate may be enveloped by
calcium or strontium carbonate, and thus shielded from the action of the
sodium rhodizonate.
In this case the following procedure can be used: The alkaline earth
metals are precipitated together as carbonates by the addition of ammonium
carbonate to the solution obtained in the course of the usual qualitative
scheme of analysis. To detect barium, or strontium, or^ both, in this
precipitate, it suffices to place about 1 mg. of^the thoroughly washed
precipitate in the depression of a spot plate, add Idrop of 0.2% solution
of sodium rhodizonate, and stir. If a positive reaction is obtained, barium
" See F. Feigl and H. A. Suter, Ind. Bng. Chem., Anal. Ed., 14,840 (1942).
BARIUM 167
is present. If no reaction is observed, it is acidified with 1 drop ot 1 N

acetic acid. A red precipitate or coloration will indicate the presence of
barium, strontium, or both.
2. Test by induced precipitation of lead snlfate."" Lead sulfate is readily
soluble in an acetic acid solution of ammonium acetate; complex lead
acetates are formed. If such a solution, which contains free sulfate ions,
is mixed with a barium salt, then not only is barium sulfate precipitated,
but also a considerable amount of lead sulfate. Probably an addition or
adsorption compound of lead sulfate and barium sulfate is formed. Thfa
induced precipitation may be utilized to increase the sensitivity of the
barium sulfate reaction. Even solutions that are so dilute with respect
to barium as to give no visible precipitation with sulfuric acid, give a definite
cloudiness on the addition of the acetic acid solution of lead sulfate.
It must be noted that strontium and calcium sulfates behave similarly.
Consequently a positive reaction indicates merely the presence of alkaline
earth cations.
fProcedoreA drop of the neutral or slightly acid test solution is
treated on a watch glass or in a micro test tube with a drop of the reagent
solution. In the presence of bariiun, a more or less dense cloudiness or
white precipitate is formed. Observation against a black background is
advisable.
Limit of Identification: 0.4 y barium
Reagents: 2 ml. of a 10% lead acetate solution are mixed with 2 ml.
2 N sulfuric acid; the lead sulfate formed is dissolved by
addition of solid ammonium acetate. The reagent keeps.
3. Test by precipitation, of bariiim sulfate in the presence of per-
manganate.'^^ Bariiun sulfate is not affected by exposure to a solution of
potassium permanganate. If, however, it is precipitated in the presence
of this salt, the precipitate contains potassium permanganate, because of
inclusion in the lattice, and so receives a distinct violet color.''* The
permanganate retained by barimn sulfate is quite resistant to reducing
agents that normally attack it at once [HjOs, Fe(II) salts, SOj, oxahc
acid, etc.]. The retardation obviously is due to the absence of free, mobile,
hydrated MnOr ions. This resistance of permanganate-bearing bariiun
sulfate can be used under the conditions given here for the detection of
barium (or sulfate, see page 238).
" According to experiments carried out with J. V. Tamchyna and L. Weiden-
feld. Compare F. Feigl, Z. angew. Chem., 43, 550 (1930).
F. Feigl and W. Aufrecht, Rec. trav. chim., B8,1127 (1939).
" H. E. Wohlers, Z.'anorg. allgem. Chem., 69, 203 (1908); compare H. Yagoda,
J. Ind. Hyg. Tox., 28, 224 (1944).
Lead sulfate behaves like barium sulfate in thi^ respect. Strontium

sulfate is only slightly colored. Accordingly, it is possible to detect as
little as 5 7 barium in the presence of 2500 y strontiuin, if comparison tests
with pure strontium salts are made. Calcium sulfate does not take up
permanganate.
1[ProcedureÂ supply of sulfate paper can be prepared by soaking
strips of filter paper in sodium sulfate solution^ and drying. Three drops
of the solution to be tested for barium are mixed with 1 drop saturated
permanganate solution on a spot plate or in a microcrucible. Alternately,
1 drop of the test solution may be treated with about one third its volume
of permanganate solution. A drop of this violet mixturfe is placed on dry
sodium sulfate paper and kept for 7 to 10 minutes at 70 to 80C. in a
drying oven. The original violet color disappears. The cellulose reduces
the free KMnOi and the paper becomes uniformly brown by deposition ^
of the resulting MnOj. The dried paper is then soaked in a solution of
sulfurous acid until all of the MnOa has disappeared and the parts of the
paper which were not spotted become white. The complete reduction and
solution of the brown oxide and of the excess permanganate require about
1 or 2 minutes. The areas of the paper in which bariiun sulfate was formed
with simultaneous adsorption of KMn04 then show up on the perfectly
white paper as violet flecks or rings, according to the quantity of barium
present.
Limit of Identification: 5 y barium
The test may also be made in a small centrifuge tube. A drop of the
test solution is treated with 3 drops of cold, saturated permanganate solu-
tion, several drops of dilute sulfuric acid are added, and the color then
discharged by dropwise addition of sulfurous acid. The violet barium
sulfate precipitate is brought into the tip of the tube by centrifuging. Its
color can be distinctly seen there if examined against a white background,
using a magnifying glass if necessary.
Limit of Identification: 2.5 7 barium
Reagents: 1) Sodiiun sulfate paper. Prepared from 0.5 N T^&SO*
or dilute HjS04
S) Saturated solution of KMnOi
3) Water solution of SO2
4. Other tests for barium. 1. Tetrahydroxyquinone can bemused in place
of rhodizonic acid, whose action it resembles.'" A small quantity (tip of
knife blade) of the solid reagent, together with KCl,-is placed in a depres-
' " J. H. Yoe, A Laboratory Manual of Qualitative Analysis, Wiley, New York,
1938, p. 177.
CALCIUM 169
sion of a spot plate. One drop of the test solution is added, followed by 1
drop of water. If barium is present a brown color appears, at first in the
vicinity of the undissolved reagent. This changes to red on the addition
of 0.1 N HCl (Id". Ltmit: 5 y barium).
STRONTIUM
1. Test with sodinin rhodizonate.'" Of the metals of the alkaline earths,
only barium and strontiiun salts react in neutral solution with sodium
rhodizonate (see page 165), and form brown-red precipitates. In order to
detect strontiimi in the presence of barium, the bariimi must therefore be
converted into some compound which does not react with sodium rhodi-
zonate. Insoluble barium chromate is suitable, since strontium chromate
is sufficiently soluble in water to react normally with the sodium
rhodizonate.
UProcednreA drop of the test solution is placed on filter paper
impregnated with potassium chromate; the chromates are formed. After
a minute, a drop of an aqueous solution of sodium rhodizonate is placed
on the spot. A brown-redfleckor circle indicates the presence of strontium.
Limit of Identification: 3.9 7 strontium fin the presence of 80 times
Concentration Limit: 1:12,800 \the amount of barium
If an aqueous solution of strontium is used (instead of the chromate),
as little as 0.45 y of strontium can be detected by this spot test, in the
absence of other metals reacting with sodium rhodizonate.
Reagerds: 1) Potassium chromate paper. Filter paper impregnated
with a saturated solution of potassium chromate, and
dried
) 0.2% solution of sodium rhodizonate
CALCIUM
1. Test with anunoniiim f^rocyanide. Calcium salts precipitate crystal-
line, white calcium ammonium fenocyanide from ammoniacal, neutral, or
acetic acid solutions, in the presence of ammonium salts, when treated with
ammonium or potassium ferrocyanide :*"
Ca++ + 2 NH^ + Fe(CN)J Ca(NH)jFe(CN),
It is to be noted that, unlike this mixed ferrocyanide, the pure alkali or
alkaline earth ferrocyanides are soluble.
" F. Feigl, Mikrochemie, 2,187 (1924).
'" When using potassium ferrocyanide and ammonium salts, calcium potassium
ammonium ferrocyanide of varying composition is formed. Compare F. Flanders,
/ . Am. Chem. Soc, 28, 1509 (1906).
Magnesium behaves analogously to calcium, but strontium salts are

not precipitated by ferrocyanide; and the corresponding barium salts are
only precipitated from concentrated solutions. Thus the ferrocyanide
reaction can be used to test for calcium in the alkaline earth group.
KProcednreA drop of the test solution is stirred on a watch glass
with a few drops of a concentrated solution of ammonium ferrocyanide,
then a drop of alcohol is added. On stirring, a crystalline precipitate or
cloudiness indicates the presence of calcium. The watch glass is best
placed on glazed black paper.
Limit of Identification: 25 y calcium"*
Concentralicm Limit: 1:2000
2. Test with the osiUEone of dihydroxjrtartaric stdd.*" Aqueous solutions
of the sodium salt of the osazone of dihydroxytartaric acid (I) give bright
yellow flocculent precipitates with the alkaline earth salts (II):
C,H,NHN=CCOOH C,H,NHN=CCOOv
C,H.NHN=CCOOH C,H,NHN=CCOO^
(I) ' (II)
(Me = Ca, Ba, Sr)
Of these, the calcium salt is notable for its extremely low solubility in water.
This property is utilized to test for calcium in solutions of very low concen-
trations. As the reagent is not specific in action, other metals, with the
exception of alkali and ammoniimi salts, should not be present. Mag-
nesium does not interfere so long as its quantity is not more than 10 times
the amount of calcium present. In higher concentrations, the magnesium
salt is precipitated in the cold, though, on heating, it is relatively soluble.
At the same time, for reasons that are not yet known, the precipitation
of the normally insoluble calcium compound is completely prevented.
The reagent is very useful for the rapid differentiation-between tap
and distilled water; the latter remains clear, while in tap water the reagent
dissolves with precipitation of the calcium compound, which comes out in
large flocks. One part tap water can be detected in 30 parts distilled
water. If ammonia and ammoniimi salts are present, the mixture must
not be warmed; otherwise a condensation product of the dihydroxytartaric
acid osazone separates.
' " It should be noted that when the ferrooyanide-calcium test is carried out
in a micro test tube, the reaction succeeds down to dilutions of 1:1,000,000; see F .
Feigl and F. Pavelka, Mikrochemie, 2, 85 (1924). Small traces of cloudiness are
always difficult to see in single drops, as the layer observfeiTis too thin.
"'Unpublished studies with S. Pickholz; see also F. Feigl, Rec. trav. chim.,
58,472(1939).
BIA.GNESITJM 171
1fProcedure^-Â drop of the neutral test solution is treated with

several grains of the reagent in the depression of a black spot plate or on a
black watch glass. In the absence of calcium, the reagent dissolves com-
pletely. When calcium is present, first a fine skin covers the drop of the
test solution and, after a little while, a more or less dense precipitate is
formed, according to the quantity of calcium. A blank test with distilled
water should be carried out as a comparison when testing for very small
amounts of calcium.
Limit of Identification: 0.01 -y calcium
Reagent: Sodium salt of dihydroxytartaric acid osazone"* (solid)
D. ALKALI METALS, AMMONIA,

AND DERIVATIVES OF AMMONIA
MAGNESIUM
1. Test with alkali hypoiodite."" Freshly precipitated and washed
magnesimn hydroxide is colored an intense brown-red by a solution of
iodine in potassium iodide. The color fades on digestion with potassium
iodide, alcohol, potassium hydroxide, or other solvents for iodine. It is
also discharged by treatment with sulfite or thiosulfate. Likewise, on
precipitation of magnesiimi hydroxide in the presence of free iodine, a
brown-red compound appears at once. It is obviously an adsorption
compound of magnesium hydroxide and iodine. The most suitable condi-
tions for the formation of this colored compoimd (even in dilute solution)
are attained when an iodine solution is decolorized with sodium or potassium
hydroxide immediately before the addition of the magnesium. In the
hypoiodite solution, the following equilibrium prevails :
2 1 + 2 OH" ?=i r -I- I0~ -h H2O
The precipitation of magnesium as magnesium hydroxide removes the
hydroxyl ions from the solution, and thus the amount of iodine necessary
for the adsorption is produced. The use of a freshly prepared hypoiodite
solution is further necessary, because, on long standing, the reaction:
3 10" = l o i -f 2 r
occurs, and the concentration of the iodine-producing hypoiodite ions is
thus decreased. By taking this into account, as well as the fact that an
excess of hydroxyl ions is necessary for complete precipitation of mag-
" For preparation, see J. H. Ziegler and M. Locher, J5er., 20,836 (1887).
"F. Schlagdenhauffen, Z. oesterr. Apotk.-Ver., 16, 348 (1878); A. Hamy,
Compt. rend., 183,129 (1926); W. J. Petraschenj, Z. anal. Chem., 71, 291 (1927).
nesium hydroxide, the following procedure can be fecommended for the

detection of magnesium.
The hypoiodite reaction is quite selective fo^ magnesium. It is
interfered with by the presence of considerable quantities of reducing
agents, by ammonium and aluminum salts, and by such ions as form colored
hydroxides or higher oxides under the test conditions.
^[ProcedureA drop of the neutral or acid test solution is placed on a
spot plate along with a microdrop of potassium hydroxide, followed by a
microdrop of iodine solution; the mixture is stirred with a glass rod. The
solution should be definitely brown with free iodine; if necessary more iodine
should be added. After 1 minute, the alkali content is increased until the
solution becomes lemon yellow. In the presence of magnesiiun, the brown
flecks of the adsorption compound of magnesium hydroxide and iodine
are clearly visible in the yellow solution. A blank is necessary only when
very small amounts of magnesium are suspected.
Limit of Identification: 0.3 y magnesium
Reagents: 1) N iodine solution in 20% potassium iodide solution
S) N potassium hydroxide
2. Test with quinalizarin.^^" Magnesium salts give either a blue precipitate
or cornflower blue coloration, accerdiug to the concentration, with alkaline
solutions of quinaUzarin (1,2,6,8-tetrahydroxyanthraquinone) (see page:
148). The color is easy to distinguish from the blue-violet of the reagent
solution. The composition of the colored compound has not yet been
determined; probably it is an adsorption compound between magnîum
hydroxide and dyestuff, analogous to that formed in the color test for
magnesium to be described later. >
The test for magnesium with quinalizarin is not interfered with by the
presence of alkaline earth metals, nor (in suflicient concentration of alkali)
by aluminiun. If large amounts of other metals which are precipitated by
alkalis are present, it is best to carry out the magnesium test after the usual
ammonium carbonate separation.
Large amounts of ammonium salts, and also the presence of phosphoric
acid, decrease the sensitivity of the test.
Lanthanum and berj'llium salts react with quinalizarin in a similar
manner, although the berylliiun quinaUzarin compound is differentiated
from the magnesium compound by its stability towards oxidisang agents
(see page 149). It must be noted that Nd, Pr, Ce, La, Zr, apd Th salts
react with quinalizarin in the same way as magnesium.salts.*'*
f ProcedureA drop of the test solution and a drop of distilled water
are placed in adjoining depressions of a spot plate and mixed with 2 drops
of an alcoholic solution of quinalizarin. If the solution* is acid, it will be
" P. L. Hahn, H. Wolf, and G. Jaeger, Ber., 67ri3ft4 (1924).
> See A. S. Komarowaky and I. M. Korenman. Z. anal. Chem., U. 247 (1933).
MAGNESrOM 173
colored yellow-red by the reagent. Sodium hydroxide is then added drop

by drop until the change to violet, and then an excess of about i to | of the
volume then present. According to the amount of magnesium present,
a blue precipitate or coloration appears, while the blank test remains
blue-violet. The difference in shade is intensified on long standing, because
the dyestuff is gradually decomposed in magnesiimi-free solutions (oxida-
tion), whereas the colored magnesium compound is stable.
lArfiit of Identification: 0.25 y magnesiimi'^*
Concentration lAmit: 1:200,000
Reagents: 1) Alcoholic quinalizarin solution (10 to 20%)
8) 2 N sodium hydroxide
3. Test with l>-iiitrobeiizeneazo-a-naphtfaoI.^'' Magnesium hydroxide ex-
hibits a remarkable adsorptive property for certain organic dyestufiFs,
This adsorption is to a certain degree the organic coimterpart of the
adsorption of elementary iodine on magnesium hydroxide, which is also
applied in analysis (see page 171), when a great deepening of color occurs
(the magnedum hydroxide is colored chocolate brown). For certain
dyestuffs of the asBO and anthraquinone series, there is a difference in color
between the adsorption product and the nonadsorbed dyestuff. Since the
dyestuff adsorption is instantaneous, the reaction affords an excellent test
for magnesimn.
Two compoimds especially useful for this test are the azo dyes,
p-nitrobenzeneazoresorcinol (I)*** and p-nitrobenzeneazo-a-naphthol (II):
OJN/ \N=N<(^ \OH O,N<^^^ \N=N<(^^ \ OH
OH
(I) (II)
These compounds are red to red-violet in alkaline solution; when they
are taken up by magnesium hydroxide deep blue complexes result. Doubt-
less this coloration of magnesium hydroxide by the dyestuffs (I) and (II)
is due to the adsorption of their alkaU salts. The pure dyestuffs, dissolved
in chloroform or alcohol, are adsorbed by magnesium hydroxide without
color change, whereas the color changes immediately when alkali is added.
The sensitivity of the test obviously depends on the hydroxyl ion concen-
tration, for if the dyestuff solution is made up with ammonia or some other
weak base instead of sodium hydroxide, it gives a much smaller effect."'
a By means of.even more refined technique, P. L. Hahn, Mikrochemie (Pregl
Festschrift), 1929, p. 133, has been able to identify as little as 0.001 7 in a miorodrop.
" According to hitherto unpublished experiments by K. Weisselberg, Diiserta-
tion, Vienna, 1930.
* The reagent is also used by K. Suitsu and K. Okuma, J. Soc. chemi Ind.
Japan.SS, 132 (1926), by W. L.RuJgh,/..4OT. Chern.Soc.,Bl, 1547(1929),and by E.W.
Engel, J. Am. Chem. Soc, 62,1812 (1930). Other &zo dyestuffs of similar behavior
are described by E. Eegriwe, Z. anal. Chem., 76, 354 (1929).
< L. Kul'berg, Chem. Abslracts, 38.3781 (1939), has advanced a different view
as to the mechanism of the color cluuige.
It is remarkable that the violet alkaline solution of p-nitrobehzeneazo-

a-naphthol is taken up with a blue coloration not only by magnesium hy-
droxide, but also by pure filter paper quite free fromlmagnesium.'^* This
is additional evidence that the color change is due to adsorption and not
to the formation of a compQim.d. Consequently, this spot test for mag-
nesiiun should be carried out only on a spot plate.
The magnesium test is best carried out so that the precipitation
and coloration of the hydroxide are simultaneous, which is achieved by
adding an alkaline solution of the dyestufi to the test solution. In this
way a blue precipitate is immediately formed with as little as 0.025 mg.
magnesium. With smaller amounts a blue coloration only is seen, owing
to the colloidal dispersion of the colored magnesium hydroxide particles.
The intensity of the blue color is dependent on the magnesium content.
The hydroxides of nickel, cobalt, and cadmium are also colored by
p-nitrobenzeneazoresorcinol; the hydroxide and carbonate of calcium are
colored by p-nitrobenzeneazo-a-naphthol. Special conditions are necessary
to detect magnesium in the presence of these metals (see page 175).
IfProcedureA drop of the test solution is treated, on a spot plate
with 1 or 2 drops of the alkaline dyestu^. According to the magnesium
content, a blue precipitate is formed, or there is a color change from red-
violet to blue. It is always necessary to see that sufficient alkali is present;
if the solution is too acid, the yellow of the free dyestuff appears, and a
few drops of strong alkali must be added. If only traces of magnesium ar^
to be detected, a comparative test on distilled water should be carried
ovit.
This reaction will reveal the magnesium in oiie drop of tap water.
The magnesium in the ash of qualitativefilterpaper, after treatment with
dilute acid, also responds positively.
Sensitivities
p-Nitrobenzene- p-Nitrobenzene-
azoresorcinol azo-a-naphthol
Limit of Identifi-cation: 0.5 y magnesium"" 0.19 7 magnesium
Cmcentration Limit: 1:100,000 1:260,000
Reagents: The reagent solutions of both dyes'are made up by dissolving
0.001 g. dye'2 m 100 mL 2N alkali /
' " Kolthoff (see p. 176) has observed the same effect with Titan yellow, and
states that filter paper (S & S 589) impregnated with 0.01% solution of the dyestuff
containing 0.05% MgCIs, on treating with 0.005 JV NaOH still gives a red ring.
' " J. Stone, Science, 72, 322 (1930), detects 5 -y Mg as follows* filter paper is
soaked in an 0.01% alcoholic solution of the azo dyestuff, drie,d, and a drop of the acid
test solution is placed on the paper. After drying, the pa'per is dipped in 1% sodium
hydroxide solution. A blue stain of magnesium shows up against a red background.
The reagent paper will keep for months in dark bottles.
*" For prepa.ration of p-nitrobenzeneazo-oi-naphthol, see E. Bamberger and
F. Meimberg, Ber., 28,848 (1895).
MAGNESIUM 175
Test for magnesium in the presence of other metals

In carrying out the test for magnesium in the presence of other metals,
it must be noted that interference can arise from the formation of hydrox-
ides, which either consume the dyestuff with color formation, or else are
themselves colored. Further, the presence of aluminates, zincates, stan-
nates, etc. can inhibit the adsorption of the dyestuff on the magnesia, more
or Fess, in favor of adsorption on the aluminate, zincate, etc. Finally, as
is to be expected, the sensitivity of the test is decreased when large amounts
of hydroxides are formed at the same time, even though they are colorless
and take up no dyestuff. Their coprecipitation in the alkaline solution
renders it difficult to see the color change. Alkaline earth hydroxides,
bismuth hydroxide, etc. are cases in point.
The interference of the metals forming complex cyanide ions may be
greatly decreased by the addition of a large excess of potassium cyanide
to the test drop on the spot plate. Thus 1.3 7 magnesium may be de-
tected in the presence of:
1000 times the amount of nickel
1000 times the amount of cadmium
1000 times the amount of copper
200 times the amount of cobalt
600 times the amount of zinc
Lead, which is brought into solution as plumbite with sodiiun hydrox-

ide, affects the test very Httle.
Iron (in), chromium (III), aluminum, and tin interfere considerably
with the test. The following procedure must be used if they are present:
f ProcedureTwo drops of the test solution are treated with a few
small crystals of sodium nitrite in a small test tube and heated by plac-
ing the tube in boiling water. Iron, aluminum, chromium, and tin are
thus precipitated as hydroxides. The mixture is then centrjfuged and the
supernatant Uquid transferred to a spot plate. The rest of the test is car-
ried out as described.
In this way 13 y magnesium may be detected in the preserux of 1000
times the amount of iron (III), chromium (III), tin (II), and aluminum.
In spite of their deep color, chromates affect the magnesiuin test only
slightly.
In order to detect magnesium in the presence of manganese, 2 drops
of the test solution are treated with colorless ammonium sulfide and,
without heating, the precipitate of manganese is centrifuged down. The
supernatant Uquid is transferred to the spot plate, by means of a capillary
siphon, and is treated with the dyestuff solution. The dyestuff is reduced
in a few minutes by the excess ammonium sulfide to form a red aminoazo
dye. It is therefore essential to carry out a blank test.
Proportion Limit: 13 y magnesium in the preseiice of 500 times the

amount of manganese ,
In testing for magnesium along the alkaline earth metals, it must be
remembered that calcium hydroxide is colored blue by p-nitrobenzene-a-
naphthol in the same way as magnesium. Because of the larger solubiUty
and lesser coloration of the calcium hydroxide, 0.13 7 magnesium may still
be identified in the presence of 5000 tim^s the amount of calcium if the
following procedure is used:
UProcedureA drop of the test solution, on a spot plate, is slightly
acidified and then treated with 1 or 2 drops of a slightly alkaline solution
of the dyestuff. Dilute alkaU is added drop by drop until a slight precipi-
tate of calcium hydroxide appears. If the solution appears blue compared
with a blank test conducted under exactly similar conditions on a, calcium
solution, magnesium is present. The calcium hydroxide precipitate is
colored blue only if a large excess of alkali is present.
Strontiimi and barium hydroxides are not colored by the dye. Con-
seguently magnesium can be detected in the presence of strontium and barium.
A large excess of alkali should be avoided, lest too much precipitate be
formed, which might tend to mask the magnesium.
Test for magnesium in silicate rocks, see page 440.
4. Other tests for magnesium, i . Alkaline solutions of the dye Titan
yellow are turned from yellow-brown to a bright flame red'" by Mg(OH)i
(Id". Limit: 1.5 7 Mg).
^. Volatile acids and ammonium salts are removed by evaporation
of the test solution with H2SO4 and heating. A drop (0.005 ml.) of the
aqueous solution of the residue and a drop of ammonia are placed on
phenolphthalein paper and dried. The paper turns pink in the presence
of magnesium"" on moistening with water {Id". Limit: 0.6 y Mg).
SODIUM
1. Test with zinc uranyl acetate.''' Sodiimi is precipitated from neutral
or acetic acid solution by an acetic acid solution of zinc uranyl acetate,
giving yellow, crystalline sodiimi zinc uranyl acetate, NaZn(U0j)3-
(CH|C00)-91120. The reaction is specific for sodium. Salts of Cu,
Hg, Cd, Co, Ni, Al, Mn, Zn, Ca, Sr, Ba, Mg, and NH* only affect the
sensitivity in concentrations greater than 5 g. per 1. Lithium salts are
precipitated from solutions containing 1 g. per 1., and potassium salts
from solutions exceeding 5 g. per 1. ^
I. M. Kolthoff, Chem. Weekblad, 24, 254 (1927).' Mikrochemie (Emich
Festschrift), 1930, p. 180.
" N. A. Tananaeff, Z. anal. Chem., 88,93 (1932).
M I. M. Kolthoff, Z. anal. Chem., 70,398 (1927).
POTASSIUM 177
The sensitivity of the test is increased when it is carried out in dilute

alcoholic solution; sodium may thus be detected in potassium salts.
f ProcedureA drop of the test solution, which should be as neutral
as possible (if necessary by preliminary treatment with anmionia or zinc
oxide), is placed on a dark spot plate or black watch glass. It is treated
with 8 drops of the reagent solution and stirred with a glass rod; the forma-
tion of a yellow turbidity or precipitate indicates the presence of sodium.
Limit of Identification: 12.5 y sodium
Considerably smaller amounts may be detected by utilizing the fact
that sohd sodium zinc uranyl acetate gives a bright greenish-yellow fluores-
cence in ultraviolet light, whereas the reagent solution gives no
fluorescence."^
If ProcedureA drop of the test solution is placed, by means of a capil-
lary pipet, on a strip of filter paper (S <fe S 601). (The paper should
previously have been washed twice with dilute hydrochloric acid and 4 to 6
times with distilled water and dried, in order to wash out any sodium salts.)
After the adsorption of the drop of test solution, the paper is carefully
dried over a microbumer. A drop of reagent solution is added to the
center and another from the side of the treated portion. The fleck is
examined under the quartz lamp while still moist. In the presence of
larger amounts of sodium, a green-yellow fluorescent fleck is seen at once;
amounts smaller than 10 y require 1 to 4 minutes to develop a similar
fluorescing border.
Limit of Identification: 2.5 7 sodium
Reagent: Solution of zinc uranyl acetate. 10 g. uranyl acetate is
dissolved by warming in 6 g. 30% acetic acid, and diluted
with water to 50 ml. (solution a). Thirty g. zinc acetate is
stirred up with 3 g. 30% acetic acid, and diluted with water
to 50 ml. (solution b). Warm suspensions o and b are
mixed and give a clear solution. A trace of sodiima chloride
is added, and after 24 hours the solution is filtered from the
precipitated sodium zinc uranyl acetate
POTASSIUM
1. Test with sodium cobaltinitrite and silver nitrate.'" Neutral or slightly
acid solutions of potassium salts give a yellow crystalline precipitate with
sodiiun cobaltinitrite Na3Co(NOj)s:
3 Na+ -I- Co(NO,)r"" 4- 2 K+ -^ KâCo(NO,), -|- 2 Na^
" F. Feigl, Rec. trav. chim,, 68, 473 (1939).
" L. L. Burgess and O. Kamm, J. Am. Chem. Soc., 34, 651 (1912). ^
178 n . TESTS FOB METALS /
The dipotassivun salt is the chief product, though, according to the pre*
cipitation conditions, varying amounts of the mono- and tripotassium
salts are formed.*'* I
The precipitation of potassium salts with sodium, 'cobaltinitrite is
appreciably more sensitive if silver salts are present, but this requires that
the solution be halide-free. The compound KiAgCo(NOj)8 is formed in
this case. The increase in molecular weight due to the substitution of
silver for sodiiun makes the precipitate less soluble than the corresponding
sodium compound.
Lithium, thallium, and ammonium salts must not be present, as
they also give-crystalline precipitates with sodium cobaltinitrite. Am-
monium salts may be removed by evaporation and ignition.
procedureA drop of the neutral or acetic acid test solution is
placed on a black spot plate and treated with a drop of silver nitrate and a
little solid sodium cobaltinitrite. A precipitate or turbidity indicates the
presence of potassiuDu.
a) Without addition of silver nitrate
Limit of Identification: 4 y potassium
6) With addition of silver nitrate
Ldmil of Identification: 1 y potassium
Reagents: 1) Solid sodium cobaltuiitrite
) 0.05% silver nitrate solution
2. Test with dipicrylamine.'" Bright yellow dipicrylamine (hexanitro-
diphenylamine) (I) is a moderately strong acid because of its acid NOj
groups. This is in contrast to its parent substance, the weakly basic,
colorless diphenylamine. The acid character is exhibited in rts ability to
form stable salts with strong bases. Accordingly, the bright "yellow
dipicrylamine dissolves in sodium hydroxide and carbonate, producing
orange-red solutions. This deepening of color is due to a change in struc-
ture. Hydroxyl ions convert the basoform of dipicrylamine (I) into the
aci-form (II), in which a continuous chain of conjugated double bonds
effects the deepening of color. The orange-red aci-form is reconverted to
the bright yellow baso-form by H+ ions:
" L. de Koninck, Z. anal. Ghent., 49, 53 (1910). ^
> N. S. Poluektoff, Mikrochemie, 14, 265 (1933/34); eee-alfo J . Feigl and P. E.
Barbosa, Rev. soc. braail. quim., 10, 137 (1941).
POTASSIUM 179
NOJ
OH-
0,N-^__%N/^__\-N0,
H+
\ 1
NOj N0
(I) baso-form
NO, HON=0
0.N^
^ " = ^ > '
NO, NO,
(II) aci-form
A solution of the sodium salt of dipicrylamine which contains, there-
fore, the aci-form, reacts with salts of rubidium, cesium, and thallium, all
of which produce strong bases. Red crystalline precipitates of the corre-
sponding dipicrylaminates are formed. After they have once been pre-
cipitated, all salts of dipicrylamine, that are difficultly soluble in water,
will not dissolve in dilute acids. However, they cannot be precipitated
from acid solutions. This apparent anomaly is due likewise to the differ-
ence in structure of dipicrylamine in its two forms.
Ammonium dipicrylaminate is precipitated by the action of consider-
able quantities of ammonium salts; but these, as well as thallium salts,
can be removed by igniting the material to be tested. Other metal ions
show no reaction with solutions of sodium dipicrylamine, or they are pre-
cipitated as hydroxides or basic salts by the sodium dipicrylamine solution,
which acts as an alkali because it is hydrolyzed. Under such conditions,
the dipicrylamine itself precipitates in its water-insoluble baso-form, which
is inactive toward potassium ions. Consequently, considerable quantities
of metal salts, which of themselves form no colored dipicrylaminates, can
impair the test for potassium. They lower the concentrations of the aci-
form that is necessaryior the precipitation of the potassium salt. There-
fore, if potassium is to be detected in the presence of considerable amounts
of metal ions, which can be precipitated as hydroxides, it is better to warm
the test solution beforehand with mercuric oxide. This precipitates the
metal ions as hydroxides. The filtrate from this preliminary step, or parts
of it, are evaporated, ignited, and the ignition residue then tested for
potassium.
The identification limit of this test is only 3 r potassium. Conse-
quently, it can be detected directly in the presence of sodium, only if not
more than 10 times the quantity of the latter is present. Otherwise,
180 II. TESTS FOR UBTALS
sodium dipicrylaminate is salted out. If potassium isi to be tested for in

tiie presence of greater amounts of sodiimi, the latter should be removed
beforehand as sodium zinc uranyl acetate (see page 176). The filtrate is
evaporated to dryness, ignited, and the residue subjected to the test for
potassium.
^ProcedureFilter paper impregnated with sodium dipicrylaminate
is spotted with 1 drop of the neutral test solution, or several grains of the
ignition residue are placed on the paper. In the latter case, the material
is then moistened with a drop of water. The paper is dried in a current of
heated air, and placed in 0.1 AT nitric acid. If potassium is absent, or
present in quantities less than the identification limit, the original orange-
red paper turns bright yellow (color of free dipicrylamine). If sufficient
potassium is present to form its dipicrylaminate, a red fleck or ring remains
at the site of the spot.
Limit of Identification: 3 y potassium
Reagent: 0.2 g. dipicrylamine"' is dissolved in 2 ml. 2 N sodium
carbonate and 15 ml. water. The solution is filtered if
necessary. Strips of filter paper (3 X 6 cm.) are soaked in
the solution, the excess liquid drained off, and the paper
dried in a blast of heated air. If the paper, moistened with
the reagent solution, is dried in the air, it is not as effective,
though uniformly impregnated, as paper that has been
spread' on glass and then dried in a blast of heated air.
The latter treatment results in an acciunulation of the
reagent on that side of the paper struck by the warm air.
The reagent paper should always be freshly prepared
Test for potassium in ash, silicates, etc., see page 441.
LITHIUM
1. Test with complex iron (HI) periodate.*" Periodates give precipitates
with solutions of ferric salts and also with solutions of most of the tri-
and tetravalent metals. These precipitates are soluble in excess potassium
hydroxide and periodate. The alkaline solution of the iron (III) periodate
complex is a selective reagent for lithium, which alone of the alkali metals
forms a precipitate with the reagent, even from dilute solutions and in the
cold. The composition of the yellow-white precipitate, which is difficultly
V soluble, depends on the experimental conditions; with excess of alkali
periodate, the ratio of the components is 1 lithium :2iron: 2 periodic acid,
'" For preparation, see K. H. Mertens, Ber., 11, 845 (1878).
" O. Procke and R. Uzel, Mikrochim. Acta, 3,105 (1938).
LITHIUM 181
The test for lithium with the complex iron (III) periodate is specific
for Uthium in the presence of even large amounts of sodium, potassium,
rubidium, and cesium.
Saturated solutions of sodium chloride do not react at room tempera-
tures. At 90 to 100 C. high concentrations of sodium chloride (more
than 20 T in a drop) are precipitated. If, however, small amounts of
lithium are also present, a precipitate is formed in a few seconds even at
45 to 50 C. .The precipitation of Uthium induces that of sodium with
iron (III) periodate, and in this way the sensitivity of the lithium test
may be increased,
Ammonimn salts interfere by reducing the alkalinity of the solution,
and must be removed before the test by boiUng with potassium hydroxide,
or by igniting the solid sample. Bivalent metals also form precipitates
with the complex iron (III) periodate; they may, however, be removed by
precipitation with 8-hydroxyquinoline in potassium hydroxide solution.
The lithium test is then carried out on the filtrate.
^ProcedureA drop of the neutral or alkaline test solution is mixed
in a micro test tube with a drop of a saturated solution of sodium chloride,
followed by 2 drops of the reagent. A blank test mth water is started
at the same time. Both tubes are dipped in water at 45 to 50 C. for 15 to
20 seconds. In the presence of lithium, a yellow-white turbidity forms in
the test tube containing the test solution, while the blank remains clear.
Limit of Identification: 0.1 y lithium
Reagents: 1) 2 g. KIO4 are dissolved in 10 ml. 2 N KOH (freshly
prepared); diluted to 50 ml. with water and mixed with
3 ml. 10% FeCls solution and made up to 100 ml. with
2 A'KOH. The reagent is stable
2) Saturated solution of sodium chloride
With reference to the detection of lithium in the presence of other
alkali chlorides, the following data are available:
0.06 7 Li may be detected in 1 drop of a saturated solution of NaCl.
Proportion Limit: 1:100,000.
0.2 y Li may be detected in 1 drop of a saturated solution of KCl
(after addition of NaCl).
Proportion Limit: 1:30,000.
In a drop of solution containing 0.35 7 Li in the presence of either
0.025 g. RbCl or CsCl, an appreciable turbidity forms, compared with a
pure Rb or Cs solution. This corresponds to ratios of:
Li:Ilb = 1:50,000
Li:Cs = 1:60,000
182 11. TESTS FOR METALS
CESIUM ,
1. Test with gold platinibromide."' Cesium salts jgive a deep black
precipitate of CsjAujPtBru, with a mixture of gold andj platinuin bromides
(AuBra plus H2PtBr6). The other alkaU metals (as chlorides), with the
exception of rubidiiun salts, which react similarly to cesium in concentra-
tions exceeding 2%, do riot react with the reagent.
llProcedureA drop of the reagent, followed by a drop of the neutral
test solution are placed on filter paper. In the presence of cesivim, a gray
to black stain is formed.
Limit of Identification: 0.25 y cesium (in 0.001 ml.)
Reagent: Solution of 0.36 g. platinum bromide and 0.60 g. gold bro-
mide in 10 ml. water
2. Test with potassium bismuth iodide.^^^ Cesiiun salts form a bright
red precipitate of the double iodide CsjBils with the pale yellow Solution of
KBil4 or the free acid. Among the other alkalis, or monovalent metals
similar to the alkalis, only thallium reacts with this reagent; it gives a cinna-
mon colored precipitate. When thallium is present, or any metal that is
precipitated by iodide, it is advisable to precipitate with potassium iodide
beforehand and carry out, the cesium test on the filtrate.
^ProcedureA drop of potassium bismuth iodide is mixed with a drop
of the test solution on filter paper. An orange or yellow- stain, compared
with a blank test, indicates the presence of cesium.
Limit of Identification: 0.7 y cesium (in 0.001 ml.)
Reagent: Potassium bismuth iodide. 1 g. BijOs is dissolved, by
boiling, in a saturated aqueous solution of 6 g. KI, and
treated with 25 ml. acetic acid, added in small amoimts at a
time
3. Other tests for cesium.
On mixing a drop of a solution of a cesium salt with a drop of a 10%
equivalent solution of AuCIa and PdClj, a black-brown fleck of CsjAuPdClr
is formed"' (Id". Limit: 1 7 Cs in 0.001 ml.). Rb and Tl salts behave in
the same way.
AMMONIA (AMMONIUM SALTS)
1. Test with j>-nitrobenzenediazonium chloride.**" A good^ sensitive test
for ammonia depends on the red coloration with p-nitrobenzenediazonimn
" ' E. S. Burkser and M. v. Kutschment, Mikrochemie, 18,18 (1935).
' " N. A. Tananaeff, Z. anal. Chem., 88, 343 (1932).
' " E. Riegler, Chem.-Ztg., 21, Repertorium 307 (1897).
AMMONIA (AMMONIXTM S A L T S ) X83
chloride (I) when it is shaken with a solution containing an ammonium

salt and 10% sodium hydrowde, added drop by drop. A colored am-
monium salt of p-nitrophenylnitrosamine (II) is formed:***
0,N<^^ ^N=NC1 OjN<(^^ \N==N0NH4
(I) (II)
This test cartoot be carried out on paper, as the slight excess of alkali
cannot be added conveniently, and a deep red may be formed even in the
absence of ammonium salts. However, the test can be carried out on a
spot plate,'** if lime is used as aUcalizer.
ITProcedureA drop of the slightly acid or neutral test solution is
placed on the spot plate followed by a drop of RiegUr's reagent. Then a
particle of calcium oxide is added. In the presence of ammonium salts, a
red zone forms at once around the calcium oxide. In the absence of am-
monium salts, any reaction is very slow. For very small amounts, a blank
test should be carried out on a drop of water.
Limit of Identification: 0.67 y ammonia
Reagents: 1) Calcium oxide (solid)
S) Riegler's solution. 1 g. p-nitraniline is dissolved by
warming in 20 ml. distilled water and 2 ml. dilute
hydrochloric acid; the solution is diluted with 160
ml. water while it is vigorously shaken. On cooling,
it is mixed with 20 ml. of 2 to 5% sodium nitrite solution;
afteralittleshaking,everythingdissolve8. This becomes
cloudy on keeping, but may be used after filtering
2. Test after liberation of ammonia. As free ammonia is liberated by
means of alkali from solid or dissolved ammonium salts, this serves as a
characteristic test for ammonium ions even in the presence of other
cations.**' The presence of cyanides should be avoided as these also give
ammonia with warm alkalis (KCN -f 2 H2O = HCOOK + NH3) and can
thus be confused with ammonium Salts.'** The interference can, however,
be greatly reduced if mercury salts are added before the alkali. Undis-
'* C. R. Fresenius, op. cit. (this text, page 101), page 130.
F. Feigi, Mihroehemie, 7, ,12 (1929).
* Mercury-amido compounds behave in the same way as NH salts.
HgjONHil is an exception and it is only slowly decomposed. This latter material
(oxydimercuriamido iodide) is formed in the familiar Nessler reaction.
"< Compare W. Bottger, "Qualitative Analyse anorganischer Verbindungen,"
in Berl-Lunge, Chemiich-techniache Unlersiiehungsmethoden. 8th ed., Springer, Vol.
I, Berlin, 1932.
sociated Hg(CN)2, which is stable to alkali, is produced. Two very sensi-

tive tests will be given. They are based on the liberation of ammonia and
can be carried out in the gas-generating apparatus despribed on pages 30
and 31. The familiar Nessler reaction can also be made in this apparatus
(see page 185).
(a) Test with red litmtcs paper
For a spot test, red litmus paper is preferable to the neutral paper,
as the color change is more definite.
IfProcedure'"The apparatus used is that shown in Figure 29. A
drop of the test solution or a httle of the solid is mixed with a drop of sodium
hydroxide in the apparatus. A small strip of moist red Utmus paper is
hung on the hook, the apparatus is closed and warmed to about 40 C
for 5 minutes. For small amounts of ammonia, the color of the paper
should be compared with some moist red htmus paper.
Ldmit of Identification: 0.01 7 ammonia
Reagents: 1) 2 N sodium hydroxide^
2) Red litmus paper
(6) Test with manganese sulfate and silver nitrate^**
A black precipitate is formed on treating solutions of manganese and
silver salts with alkalis:
Mn++ + 2 Ag+ + 4 OH- = MnOj + 2 Ag + 2 HjO
This reaction can be used as a sensitive test for ammonia, since a neutral
solution of manganese and silver salts (sulfate or nitrate) on being treated
with a drop of ammonia or exposure to ammonia gas, gives a black precipi-
tate or dark color, according to the amount of ammonia present. The
sensitivity can be increased if the precipitate is treated with a drop of an
acetic acid solution of benzidine, as in the manganese test described on
page 135. The resulting blue color will plainly reveal a precipitate that
was hardly visible.
TlProcedureThe apparatus shown on page 31 (Figure 27 or 28) is
used. A drop of the test solution is mixed with a drop of alkali, a drop of
the reagent solution placed on the knob of the stopper, or on the thickened
'end of the glass rod. The apparatus is closed and heated on a warm
asbestos plate to about 40 C. for 5 minutes. The drop of the reagent
solution is then wiped on to a strip of quantitative filter paper. A black
F. Feigl, Mikrochemie, 13, 132 (1933).
"F. Feigl, Mikrochemie, 13, 134 (1933).
AMMONIA (AMMONIUM SALTS) 185
or grayfleckis left. Several drops of water are added and then a drop of an
acetic acid solution of benzidine. The fleck turns more or less blue.
Limit of Identification: 0.005 y NH3
Concentration Limit': 1:10,000,000
3) Manganese nitrate-silver nitrate solution. 2.87 g.
Mn(N03)2 are dissolved in 40 ml. water and filtered.
To this is added a solution of 3.35 g. AgNOa in 40 ml.
water, and the mixture diluted to 100 ml. In order
to neutralize the acid formed by hydrolysis, dilute alkali
is added, drop by drop, until a black precipitate is
formed; this is filtered off. The reagent solution thus
prepared will keep if stored in a dark bottle
3) Benzidine solution (see page 135)
3. Other tests for ammonia. 1. A mixture of silver nitrate and formalde-

hyde is instantaneously reduced by NHs.'^' A silver nitrate-tannin mix-
ture is similarly reduced'^' (Id". Limits: 0.05 7 NH3 and 0.1 y NHj).
Both tests may be carried out in the apparatus described on page 31.
2. The well known Nessler reaction may be carried out as a spot
test.'^' A drop of the test solution is mixed with a drop of concentrated
alkaline hydroxide on a watch glass; a drop of the resulting suspension is
placed on filter paper with a capillary tube and treated with a drop of
Nessler solution: A yellow or orange-red stain or ring is formed {Id".
Limit: 0.3 7 NH3 in a drop of 0.002 ml.). In the presence of Ag, Hg,
and Pb salts, the paper is treated with a drop of 2 iV alkali, a drop of the
test solution, a further drop of alkali, and finally the Nessler solution
added crosswise (Id". Limit: 2 y NH3 in a drop of 0.002 ml.). It has
been suggested"" that it is advisable to liberate the ammonia in the ap-
paratus (Fig. 27) described on page 30, and to place a drop of the Nessler
solution on the knob of the apparatus. Very small amounts of the yellow
oxydimercuriaminoiodide can readily be identified, after wiping on to
a strip of filter paper {Id". Limit: 0.025 y NH3 in 0.05 ml.).
3. Instead of Nessler's solution, a drop of a neutral MnS04-Hj02
solution can be used. MnOs is formed, which can be smeared on filter
paper and spotted with benzidine solution. A blue color develops (see
page 135) {Id". Limit: 0.03 y NH3).
*'C. Zenghelis, Compt. rend., 173, 153 (1921).

" G. K. Makris, Z. anal. Chem., 81, 212 (1932).
" N . A. Tananaeff and A. A. Budkewitsch, Chem. Abstracts, 30, 5905 (1936).
" M. Ishidate, Tokyo, private communication.
HYDRAZINE I
1. Test with salicylaldehyde.'" Benzaldehyde aiid other aromatic
aldehydes combine with hydrazine or its salts, with separation of a mole-
cule of water, to form aldazines, which are white, -wâter-insoluble sub-
stances. Owing to its greater solubility in water,, salicylaldehyde (o-hy-
droxybenzaldehyde) is especially useful as a reagent. It reacts:
/ \ - , OH... ..HOr/ \
N,H4 + 2 C,H4(0H)CH0 =
J^^K + 2 HiO
\y
(I)
The slight solubility of salicylaldaziae is connected possibly with the

fact that it may be formulated (I) as an inner complex salt."^ . The test
for hydrazine by the aldazine reaction is not affected by the presence of
hydroxylamine, as this reacts with sahcylaldehyde to give a soluble oxime.
However, in the presence of much hydroxylamine, it must be remembered
that the reagent may be consumed in the formation of the oxime.
P*rocedureA. drop of the reagent is mixed with a drop of the test
solution in a micro test tube. According to the amount of hydrazine
present, a white precipitate or cloudiness appears on standing for a short,
time.
Limit of Identification: 0.1 y hydrazine
Reagent: 5 g. salicylaldehyde are boiled with 600 ml. water and
20 ml. 50% acetic acid, until the oil disappears. After
cooling, the mixture is filtered from any undissolved
salicylaldehyde. The solution will keep, but after any
considerable tune should be refiltered, as traces of salicyl-
aldehyde frequently separate
HYDROXYLAMINE
1. Test with diacetyhnonoxime and nickel salt.".' Diacetylmonoxime
reacts with hydroxylamine; water is split out and diacetyldioxime results.
The product is widely used as a reagent for nickel. Consequently, if the
reaction occurs in the presence of an ammoniacal nickel solution, red,
slightly soluble nickel dimethylglyoxime is formed direcfly from the
coisponents: -- T
" F. Peigl, Rec. trav. chim., 68, 474 (1938).
' " Compare F. Feigl, op. dt. (this text, page 2), page 35.
W. N. Hirschel and J. A. Verhoeff, Chem. Weekblad, 20, 319 (1923); see also
F. Feigl, Rec. trav. chim., 68, 474 (1939). ^
HYDROXYLAUINE 187
H,CC=0
2 1 + 2 NHjOH + [Ni(CH,),l++ =
H.CC=N
1
OH
0 0
H.CC=Nv /N==CCH,
I >NK I + 2 NHi" 4- 2 H,0
H.CC=N-' --N^CCH.
1 I
OH HO
I t is advisable to saturate the reagent (a mixture of the ketone with
ammoniacal nickel solution) with nickel dimethylglyoxime, and to carry
out the test as a spot reaction on filter paper.
This test cannot be used in the presence of large amounts of hydrazine,
as it reacts with the reagent solution to give a red-brown precipitate. How-
ever, less than 6 y hydroxylamine can be detected in the presence of 300 y
hydrazine.
f ProcedureFilter paper is impregnated with the reagent solution
and dried. A drop of the test solution is placed on it. According to the
amount of hydroxylamine present, a more or less intense red fleck or ring of
nickel dimethylglyoxime is formed on the yellow paper.
Limit of Identification: 1 y hydroxylamine
Reagent Solution: 1.2 g. diacetylmonoxime"* are dissolved in 35 ml.
hot water, 0.95 g. NiCls-6 HjO is added and, on
cooling, 2 ml. cone, ammonia. This solution is
poured into a solution of 0.12 g. hydroxylamine
hydrochloride in 200 ml. water. After standing 24
hours, the precipitate of nickel dimethylglyoxime is
filtered off. The red-brown filtrate is used as
spotting reagent
2. Test with salicylaldehyde and copper salts.'" On mixing sahcylalde-
hyde with hydroxylamine arid copper acetate, the following reaction occurs:
OH
+ NH,OH + i(CH,COO),Cu =
^ ^
S
H
/N/0\Cu/2
-t- CH.COOH + H,0
NOH
H
< For preparation, see O. Diels and H. Jost, Ber., 86,3292 (1902).
" F. Feigl, Rec. trav. chim., 58, 474 (1939).
188 11. TESTS FOB METALS
Pale yellow, complex copper salicylaldoxime is precipitated. This is

used as a test for copper. This test like 1 consists in the formation of an
inner complex salt from its components. A stock mixture of salicylalde-
hyde and copper acetate cannot be used as a reagent, because, depending
upon the concentration, on short or long standing, a green copper salt of
salicylaldehyde is precipitated. The reagents must therefore be added
separately to the test solution in a definite order, and in definite concen-
trations.
^ProcedureA drop of the reagent solution {1) is mixed in a micro
test tube with a drop of the test solution and 2 drops of the reagent solution
{2). A bright yellow precipitate or cloudiness is formed according to the
amount of hydroxylamine present.
Limit oj Identification: 1 y hydroxylamine
Reagents: 1) Salicylaldehyde solution. 5 grams salicylaldehyde are
boiled in 600 ml. water and 20 ml. 60% acetic acid
until the oil globules disappear. After 24 hours the
solution is filtered, and is ready for'use
^) Copper acetate solution. 5 g. copper acetate are
warmed mth 150 ml. water and 1 or 2 ml. 60% acetic
acid, and filtered after cooling
Detection of hydrazine and hydroxylamine when together.
The formation of salicylaldazine (page 186) and copper salicylal-
doxime (page 187) may be used as tests for hydrazine and hydroxylamine
when together. However, the ratios of the compounds to be detected
must be taken into account, as the reagent (salicylaldehyde) has a limited
solubility in water.
The relative insolubility of hydrazine sulfate may be applied for the
detection of a little hydroxylamine in the presence of much hydrazine. A
saturated solution of hydrazine sulfate (at 32 C.) contains 2.95 g. hy-
drazine sulfate in 100 ml. water, that is, about 360 r in a drop. This
amount can be precipitated by salicylaldehyde as aldazine, without appre-
ciably increasing the volume. Thus the main portion of the hydrazine
can be precipitated as sulfate, and the test carried out on the filtrate.
^Procedure1.5 ml. of the test solution is treated with sulfuric acid
(4:10) until a drop (tested separately) gives no further precipitate with
sulfuric acid. The mixture is centrifuged after 10 minutes, and 0.5 ml. of
the centrifugate is rendered alkaline with strong ammonia /and then
acidified with 1 or 2 drops 2 N sulfuric acid. 2.5 mj.-of salicylaldehyde
solution are then added, the salicylaldazine is centrifuged after 30 minutes
Standing, and 3 drops of the supernatant liquid is tested in a micro test
tube with a drop of copper acetate solution. In the presence of hydroxyl-
amine, a yellow-green precipitate of, copper salicylaldoxime is formed.
HYDROXYLAMINF 189
Limit of Identification: 10 7 hydroxylamine in the presence of 5000 y

hydrazine
If a little hydrazine is. to be detected in the presence of much hydroxyl-
amine, then the reagent is also consiuned in the formation of saUcylal-
doxime. A drop of the test solution should therefore be placed in 4 ml, of
reagent. The turbidity due to saUcylaldazine is filtered off, and copper
acetate is added to the filtrate. The solution is examined for the deposition
of copper saUcylaldoxime.
Blank tests should be carried out when testing for very small amounts
of hydrazine or hydroxylamine.
Limit of Identification: 1 y hydrazine in the presence of 4000 7
hydroxylamine
For the preparation of reagents, see pages 186 and 188.
3. Test by conversion into nitrous acid. Hydroxylamine may be oxidized
rapidly and quantitatively to nitrous acid by means of iodine in acetic
acid solution.'" When this oxidation is carried out in the presence of
sulfanilic acid, the latter is diazotized. After removal of the excess iodine
with thiosulfate, the diazonium salt may be coupled with a-naphthylamine
to give a red azo dye. This is the basis of the well-known and sensitive
Griess reaction of nitrites'^' (see page 248). The following reactions occur
in this test for hydroxylamine:
NHjOH + 2 I, + H , 0 - * 2 HNO2 + 4 HI
HNO, + HCl + HO,S<(^ NNH2 -> HO,S<(^ \ N , C 1 + 2 H,0
I2 + 2 NajSjO, - ^ 2 Nal + NajS.O.
J10,S<(' V-N2CI +
-NH,
This test for hydroxylamine by conversion to nitrous acid and syn-

thesis of an azo dye, is decisive even in the presence of much hydrazine,
if a sufficient excess of iodine has been used in the oxidation. The test is,
of course, inapplicable in the presence of nitrites.
f Procedure'^'A drop of the test solution is mixed with a few mg.
sodium acetate, 1 to 2 drops sulfanilic acid, and a drop of an acetic acid
" F. Raschig, Schwefel-und Stickstoffstudien. Verlag Chemie, Leipzig, 1924,
page 183.
" J. Blom, Ber., 69,121 (1926); compare G. Endres, Ann., 618,109 (1935).
" F. Feigl and V. Demant, Mikrochim. Acta, 1,132 (1937).
190 n. TESTS roR METAI^S
solution of iodine, either on a spot plate or in a microcrucible. The mix-

ture is allowed to stand for 2 or 3 minutes. The excess iodine is then
removed with thiosulfate, and a drop of a-naphthylamine solution is
added. A pink to deep red indicates hydroxylamine.
lAmit of Identification: 0.01 y hydroxylamine
Reagents: 1) 0.1 N iodine in acetic acid (1.3 g. iodine in 100 ml.
glacial acetic acid)
2) Sulfanilic acid solution. 10 g. acid in 750 ml. water
and 250 ml. glacial acetic acid
3) 0.1 N NajSsO,
4) a-Naphthylamine solution. 3 g. of the base in 700
ml. water and 300 ml. glacial acetic acid
4. Other tests for hydroxylamine.
The test for ammonia involving the reaction:
2 Fe(OH)j + NH2OH + HjO = 2 Fe(OH), + NH
can be applied to the detection of hydroxylamine in the presence of hy-
drazine"* (Id". Limit: 0.1 y NH2OH). Ammonium salts and nitrites
must not be present. The precipitation of ferric hydroxide can be com-
bined with the test for ammonia described on page 184. It is sufficient
to add 1 drop of ferrous sulfate solution to the specimen before making the
solution alkaline.
" f. Feigl and R. Uzel, Mikrockemie, 19,136 (1936).
III. TESTS FOR ACID RADICALS
Anions
In general, tests for volatile acids can be made directly, if necessary
after decomposing the sample. The number of anions and their possible
combinations in mixturesis far less than those of cations. The systematic
search, for acid radicals is usually made in solutions that contain no cations
except the alkali metals and univalent thallium. Such solutions (sodium
carbonate extracts) are obtained by treating the test solution with sodium
carbonate and filtering off the resulting precipitate, or by fusing the solid
sample with sodium carbonate (or NaKCOs); the melt is extracted with
water and filtered. In both procedures, the metals forming cations are
transformed to their slightly soluble carbonates or hydroxides, and thus
separated from the water-soluble alkali salts of the acid radicals. Thal-
lium, whose carbonate is soluble, presents an exception; likewise the
complex anions formed by certain heavy metals with organic acids. Spot
reactions to detect the various acid radicals can be successfully made on
drops of the soda extract.
It is advisable to make preliminary tests before proceeding to the
systematic search for acid radicals. Such tests should especially include a
study of the behavior of the sample toward water and chemically active
solvents, keeping in mind the cations whose presence has been established
by a prelimin.ary, separate test. Furthermore, it must always be remem-
bered that the proved presence of oxidizing anions excludes the presence of
reducing anions, and trice versa.
The discussion (page 41) should be referred to relative to the choice
of spot tests for acid radicals, giving due consideration to the objectives
of the macro- or microchemical analysis, the necessity of adhering closely
to the procedures as given, and the making of model tests when using
unfamiliar methods of detection. What has been said there relative to
tests for metals applies equally to acid radicals.
Since no really satisfactory scheme is known for the separation of
acid radicals into definite groups, the acid-forming nonmetal is used as the
basis of arranging the acid radicals in this section. The sensitivity data
given for the various tests are valid, unless otherwise stated, for solutions
of pure alkali salts tested by the respective procedures.
HYDROCHLORIC ACID
1. Test by formation of chromyl chloride. Chlorides which are decom-
posed by sulfuric acid to give hydrochloric acid, on "belssg mixed with
191
192 III. TESTS FOR ACID RADICALS
potassium dichromate and treated with cone, sulfuric acid, give chromyl
chloride:
6 H2SO4 + KjCrjO, + 4 HCl -> 2 CrOjClj + 3 H0 + 6 KHSO4
This compound boils at 116C. and so can be distilled out of the reaction
mixture. The sample must be in the solid form because water hydrolyzes
chromyl chloride to dichromic acid and hydrochloric acid. Since chromyl
chloride can be saponified to give chromate, which even in great dilution
gives a deep violet color with diphenylcarbazide (see page 128), chlorides
may be detected in a few milligrams of solid or the evaporation residue from
a drop of liquid.^ This test does not apply to insoluble chlorides such as
AgClorHgjCh.
^[ProcedureA few grains of the solid sample, or a drop of the test
solution, is placed in the glass bulb of the apparatus shown in Figure 27,
(see page 31) and evaporated there to dryness. A little powdered K2Cr20T
and a drop of cone, sulfuric acid are introduced, and the apparatus is then
stoppered. The knob on the stopper carries a drop of dilute alkali.
The apparatus is heated for a few minutes. After cooling, the knob is
dipped iBto a drop of the reagent solution that has been treated with a
drop of dilute sulfuric acid (spot plate).. In the presence of chlorides the
chromyl chloride causes the reagent to change to violet.
Limit of Identification: 1.5 7 chlorine
Reagents: 1) Potassium dichromate (solid)
2) Cone, and dilute sulfuric acid '
3) 1% alcoholic solution of diphenylcartjazide
It must be noted that in this chromyl chloride reaction there is always
also a hberation of chlorine:
KjCrÔT + 6 KCl + 7 H2SO4 = 3 CI2 + 4 KjSO* + Cra(S04)8 + 7 HjO
This oxidation increases with increase of bichromate relative to chloride,
and obviously explains why the chromyl chloride reaction is not very
sensitive.
I t has now been found' that if iodide is present and the molecular
ratio iodide:chloride exceeds 1:15, the CrOjCla formation is prevented
completely in favor of the liberation of chlorine.'
Small amounts of bromides do not interfere with the test, although,
under the conditions of the experiment, they are oxidized to elementary
' Studies with H. J. Kapulitzaa and M. Ishidate. _.
W. Krings, Z. angew. Chem., 60, 414 (1937).
The failure to form CrOaCU in the presence of iodine is due to the production
of HIOj from iodide and chromic acid. The iodate, in the presence of cone. H1SO4
and especially on warming, liberates chlorine from chlorides, regenerating iodide.
HYDROCHLORIC ACID 193
bromine. Larger amounts of bromine interfere because they cause oxida-

tion of the diphenylcarbazide. Under such conditions the bromine may
be removed without materially affecting the sensitivity of the chromyl
chloride reaction by adding phenol to the reagent solution. This removes
the bromine as tribromophenol.
The presence of nitrates' interferes, as then, instead of chromyl
chloride, nitrosyl chloride may be formed. Other oxidizing materials,
such as nitrites, chlorates, etc., liberate chlorine. Fluorides should be
removed before carrying out the chromyl chloride test, as fluorine forms a
volatile compound resembling chromyl chloride.
2. Test by volatilization of hydrochloric acid/ On heating solid, decom-
posable chlorides with cone, nitric acid, hydrochloric acid is liberated which
turns silver nitrate cloudy by formation of silver chloride. Other halides
behave similarly to chlorides. The reaction is therefore especially suitable
for a rapid and sensitive preliminary test for halogen hydracids.*
UProcedureÂ few particles of the soUd sample are placed in the glass
bulb of the apparatus described on page 31, Figure 27, or a drop of the test
solution is allowed to evaporate there. Two drops of cone, nitric acid are
then added. A drop of dilute silver nitrate solution is placed on the glass
knob of the stopper which is fitted into position. The apparatus is then
wanned over an asbestos plate until the first bubbles rise. For very small
amounts of hydrochloric acid, the turbidity due to AgCl is rendered more
visible by transferring the drop to a black porcelain plate.
lAmit of Identification: 1 y hydrochloric acid
Reagents: 1) Cone, nitric acid
2) Dilute silver nitrate solution
3. Identification of silver chloride.* Silver chloride reacts with potassium
ferrocyanide:
4 AgCl -f K4[Fe(CN),] ^ Ag4[Fe(CN),] + 4 KCl
This reaction cannot be detected by mere observation because both silver
salts are white. If, however, a precipitate of AgCl that has been treated
with K4Fe(CN) is moistened with a drop of cone. HNO3, silver ferro-
< F. Halla and F. Ritter, Mikrochim. Ada, 1, 365 (1937).
' A preliminary test for halides, that may be carried out on a neulral solution
of alkali halide in the absence of other anions precipitated by Ag+, is to mix a little
well-washed AgjCO. with a drop of the test solution and of phenolphthalein solution
on a spot plate. In the presence of halides, alkali carbonate is formed: AgjCOj +
2 Hal- = 2 AgHal -1- CO.. This turns the phenolphthalein red [Id". Limit: 0.5
7 KCl (KBr) and 1 7 KI]. F. Feigl and R. Seboth, unpublished work.
N. A. Tananaeff and A. M. Schapowalenko, Z. anal. Chem., 100, 344 (1935).
cyanide is converted to silver fen-icyanide, which results in a color change

from white to red-brown:
3 Ag4Fe(CN), + 4 HNO, = 3 AgNOa + NO + 2 HJO + 3 AgjFeCCN),
i
For this test to be specific, it is necessary that the silver chloride
be free from silver nitrate, as other silver halides react similarly with
ferrocyanide and nitric acid.
The AgCl may be isolated from a mixture of silver halides by warming
with a mixture of 4 parts saturated ammonium carbonate solution and
1 part ammonia. The silver chloride is completely soluble in this mixture,
and can-be reprecipitated, after filtration, by acidifying with nitric acid.
Only a trace of silver bromide dissolves in the NH3-(NH4)sCOs mixture,
while silver iodide is insoluble.
HYDROBROMIC ACID
Test by oxidation to bromine.
1. Fluorescein test.^ Free bromine can convert the yellow dyestuff
fluorescein (I) '
HO- OH OH
into red tetrabromofluorescein (II) (eosin). Filter paper impregnated

with an aqueous solution of fluorescein consequently turns red~6n coming
into contact with bromine vapor.
In order to carry out this test for bromides, they must be oxidized to
/ree bromine. This is best carried out by heating with chromicacid, or
lead peroxide and acetic acid:'
2 KBr + Pb02 + 4 CH,COOH -> (CH3C00)jPb + 2 CH3COOK +
' 2 H2O + Br2
' D. Ganassini, Cfcem. Zentr., 1904,1, 1172. -^ '
F. L. Hahn, Mikrochemie, 17, 228 (1935), recommended chloramine-T. This
oxidizing agent has the great advantage that the reaction takes place in a homogene-
ous medium, without going through the gaseous phase, and is applicable even in the
presence of large amoiuts of chloride.
HTDBOBROHIC ACID 195
Chlorides do not affect the fluorescein test for bromides, as they remain
practically unchanged after treatment with lead peroxide and acetic
acid. Thus bromides may be detected in the presence of large amounts
(up to 1:10,000) of chlorides.' Iodides, however, are oxidized to free
iodine under the conditions of the experiment, and can change the color of
the fluorescein owing to the formation of iodoeosin." In this case, the
bromide can be identified by Procedure (a).
tProcednre(a) The gas apparatus shown on page 31 (Figure 30)
is used. A drop of the test solution is placed in it together with a few
particles of lead peroxide and acetic acid, or with a few drops of chromic
acid. The apparatus is closed with the funnel stopper and a piece of filter
paper impregnated with fluorescein is placed on the top of the funnel.
The apparatus is gently warmed, and, according to the amount of bromine
present, a circular red fleck is formed more or less rapidly on the yellow
test paper. The apparatus. Figure 31, page 31, may alternatively be used
for this test.
Limit of Identification: 2 y bromine
Reagents: 1) Lead peroxide (solid)
2) Acetic acid
S) Chromic acid
4) Fluorescein paper or solution. Saturated solution of
the dyestuff in aqiieous alcohol (1:1). For the detec-
tion of traces, it is advisable to recrystallize the dyestuff
twice from 80% alcohol
The liberation of bromine from bromides and formation of eosin also
takes place on prolonged heating with an acetic acid-hydrogen peroxide
mixture, in the presence of fluorescein. The following procedure" is
strongly recommended for the detection of bromine.
^Procedure(b) A drop of the test solutionis mixed with a microdrop
offluoresceinsolution and a microdrop of a mixture of glacial acetic acid and
hydrogen peroxide, either in a microcrucible or on the spot plate, and
evaporated to dryness over the water bath. A pink to red color appears,
depending upon the size of the sample. A blank test, for comparison,
on a drop of water, is advisable when testing small amounts. -
Limit of Identification: 0.3 y bromine
Reagents: 1) 0.1% fluorescein solution
2) Glacial acetic acid-30% hydrogen peroxide (10:1)
R. G. Aiokin, Ghem. Abstracts, 31, 7358 (1937).
" According to 0 . Frehden and C.-H. Huang, Mikrochemie ver. Mikrochim.
Acta, 26, 47 (1939), as little as 6 7 iodine effect a color change.
" Communication from O. Heim, East Hempstead, England.
196 HI. TESTS FOR ACID RADICALS
2. Fuchsin test.'* The triphenylmethane dyestuff, fuchsin
'H,N< 1
\
C = ./~-
< >==NH, CI
CH,
is converted by bisulfite into a colorless addition product (see page 234).

A fuchsin solution thus decolorized is turned blue by free bromine, due to the
formation of a brominated dyestuff.^' As neither free chlorine nor iodine
color this colorless fuchsin bisulfite compound, the reaction is suitable
for the detection of even small amounts of bromides in chlorides and
iodides.
The liberation of bromine from bromides is best efiected by a cone,
chromic acid solution; the bromine is allowed to act on filter paper impreg-
nated with the reagent. In the absence of bromine, the paper becomes
pink on warming; small amounts of bromine, however, give a distinct
violet.
Bromine that is present along with other halogens in organic com-
pounds, can also be detected by this means.
f ProcedureA drop of the test solution, or a small amount of the
solid substance, is placed in the glass bulb of the apparatus described
on page 31 and shown in Figure 31. It is mixed with 2 to 4 drops of chromic
acid solution and the apparatus is closed with the capillary fitting, which
contains a drop of the reagent solution. The apparatus is then carefully
warmed over a wire gauze (the liquid should not be allowed to boil).
After a period that varies according to the bromide content, the liquid in
the capillary turns violet.
lAmit of Identification: 3.2 y bromine
ConcentrcUion Limit: 1:15,000
Reagents: 1) Fuchsin-bisulfite solution. 0.1% fuchsin solution, de-
colorized with sodium bisulfite
2) 25% chromic acid solution
3. Test with, permolybdate and a-naphthofiavone.'^ a-Naphthofiavone
forms an insoluble blue-violet adsorption compound \vith iodine, and an
I. Guareschi, Z. anal. Ckem., 62, 451, 538, 607 (1913); 63, 490 (1914).
" For more details about the mechanism of this color reaction see H. Wieland
and G. Scheuing, Ber., 54, 2527 (1921).
" F . Schulek, Z. anal. Chem., 102, 111 (1935); E-.tJzel,- Chem. Abstracts, 29,
6623 (1935); 30, 1683(1936).
HYDRIODIC ACID 197
orange-red compound with bromine. Therefore, if bromine is liberated

from bromides by the use of a suitable oxidizing agent {e.g., permolybdic
acid),^^ the colored bromonaphthoflaVone compound is formed. In the
presence of iodides, the iodine compound is precipitated first. However,
it is decomposed by further action of the oxidizing agent, and iodic acid
results. Free chlorine does not react with naphthoflavone.
IfProcedureA small amount of soHd molybdic acid (H2M0O4) is
added to a drop of test solution followed by a drop of a solution of a-naph-
thoflavone in glacial acetic acid, and finally 1 or 2 drops of a mixture of
dilute sulfuric acid and hydrogen peroxide. An orange color develops; its
intensity depends on the amount of bromide present.
Limit of Identification: 1 7 bromine
Concentration Limit: \:bO,(Mi
Reagents: 1) Molybdic acid (solid)
a) 0.1% solution of a-naphthoflavone in glacial acetic acid
3) Mixture of 3 parts 60% sulfuric acid and 1 part 30%
hydrogen peroxide
This procedure, including decomposition of any iodine compound
by the addition of excess permolybdic acid, will reveal as little as 0.5 7
iodine and 0.5 7 bromine (as halide) in 1 drop of saturated solution of
NaCl.
4. Other tests for bromides. 1. A drop of the acid test solution is mixed
with a few drops of a warm, saturated solution of KMn04 and one drop of
CUSO4 solution.^* Bromine is liberated, which will turn potassium iodide-
starch paper blue, if placed over the crucible containing the mixture (/d".
Limit: 5 7 Br). This reaction is not applicable in the presence of iodides.
2. A blue-violet ring is produced on filter paper if 1 drop of KBr-
CuBra solution is dried and then spotted with H2SO4 (1:1)^' {Id". Limit:
0.02 7 Br).
HYDRIODIC ACID
1. Test with palladous chloride. Palladous chloride reacts with solutions
of iodides to form a brown-black precipitate of palladous iodide, Pdl2,
insoluble in mineral acids. In concentrated salt solutions (sodium chloride,
magnesium chloride, etc.) the palladous iodide is, however, markedly
soluble. Palladous nitrate must not be used, as this gives a red-brown
precipitate of palladous bromide with bromides (especially from concen-
" F. Feigl, op. cit., (this text, page 2), page 128.
" N. A. Tananaeff and A. M. Schapowalenko, Z. anal. Chem., 100, 345 (1935).
" F. Kirchhof, Chem. Abstracts, 33, 942 (1939).
trated solutions). Even insoluble iodides such as Cuilj, Agl (see page 303)
produce Pdlj on treatment with PdClj.
IfProcedureA drop of the test solution is spotted on filter paper
with a drop of palladous chloride solution. A more or less intense black-
brown precipitate forms, according to the quantity of iodide present.
Ldmit of Identification: 1 y iodine
Reagent: 1% aqueous solution of palladous chloride
2. Test by oxidation to free iodine. In acid solution, iodides can be con-
verted to free iodine by means of a number of oxidizing agents, and this
gives the well known iodine-starch reaction. The deep blue compound or
colloidal solution is easily recognized.'*
An acid solution of potassium nitrite, that is, nitrous acid, is best for
liberating the iodine from iodides:
2 HI -h 2 HNO2 = I2 + 2 NO + 2 H,0
It should be noted that the starch-iodine reaction is more sensitive
the lower the temperature. Blue starch-iodine solution loses its color
when heated; the color reappears on cooling. The sensitivity is decreased
by the presence of large amounts of alum, magnesium sulfate, alkaU sulfate,
and the like. Certain organic materials (proteins, resorcinol) when present
in large amounts can completely prevent the starch-iodine reaction."
Cyanides, which impair the test by formation of cyanogen iodide,
HON + 1, ;^ CNI + HI
can, however, be removed before the test by acidifying and heating.
The test for iodide by oxidation with nitrite can be carried out (a)
on a spot plate or (b) on filter paper containing starch. The spot reac-
tion*" described under (b) ia the more sensitive and is particularly recom-
mended for neutral or alkaline test solutions. -^ -^
^Procedure(a) A drop of the acid test solution is mixed on.a spot
plate with a drop of starch solution and a drop of potassium nitrite solution.
A blue coloration indicates the presence of iodide.
Limit of Identification: 2.5 7 iodine /
Concentration Limit: 1:20,000 '
" A discussion of the extensive literature on the starch-iodine reaction, to-
gether with more information on its sensitivity, is to be found in Gmelin's Handbuch
der anorg. Chem., 8,197 (1931). '
" Fr. Goppelsroeder, (abstract) Z. anal. Chem., 2,398 (18S3); J.Lowe,/.profc.
Chem., [11,74,348 (1858).
" C. L. Wilson, Chemistry & Induttry, 59, 378 (1940).
HTDKIODIC ACID 199
Reagents: 1) 10% potassium nitrite

S) Starch solution." 1 g. soluble starch and 5 mg. mercuric
iodide (as preservative) are mixed with a little water
and the paste poured into about 500 ml. boiling water
Various varieties of filter paper suitable for spot reactions contain
slight quantities of starch, which suffice to give the test when the iodine is
set free. The test for iodine on paper is about 100 times as sensitive as on
a spot plate. This heightened sensitivity is due to the fixation of the
iodine on the surface of the paper and to the contrast with the white
background.
fProcedore(b) Filter paper, tested beforehand for starch, is treated
successively with single drops oi2 N acetic acid, test solution, and 0.1 N
potassium nitrite. A bluefleckor ring shows the presence of iodine.
lAmit of Identification: 0X)25 y iodine
3. Test by conversion to iodate.** When very small amounts of iodide
are to be detected, that is, less than the limit of identification of test 2, the
iodide may be oxidized to iodate. From this the iodine can be liberated by
the addition of potassium iodide and acid:
lOs- + 5 I- + 6H+ = 3 Ij + 3 HjO
As one molecule of iodide gives one molecule of iodate, and this liberates 6
atoms of iodine, the sensitivity of the test is thus markedly increased.
The oxidation of iodide to iodate may be carried out by means of bromine
water in neutral, solution:
I- + 3 Brj + 3 H2O = lOr + 6 H+ + 6 Br- (1)
or by means of alkah and permanganate:
2 I- + 4 MnOr + 2 HjO = 4 MnOj + 4 OH- + 2 lOi" (2)
Acid solutions can be buffered by adding Na2HP04.
Before the iodate, formed according to equation (1), can be detected,
the excess of oxidizing agent must be completely removed. If bromine
water is used, the excess is destroyed by adding phenol or 80% formic acid.**
Potassium permanganate (together with the manganese dioxide formed)
is removed by adding sodium azide and acid.
* Preparation according to M. Mutnianski, Z. anal. Chem., 36, 220 (1897).
' Studieawith E. Rajmann.
"Compare F. Viebock, Pharm. Monaish., 10, 59 (1929); Chem. AbstTacis, 23,
3418 (1929).
200 III. TKSTS FOB ACID RA.MCALS
The respective equations for the decompositions are:

3 Brj + CeEUOH = CH^BrsCOH) + 3 HBr
Brs + HCOOH = 2 HBr + CO2
2 MnOr + 10 HN3 + 6 H+ = 2 Mn++ + 8 H2O + ' l 5 Nj or
MnOa + 2 HN3 + 2 H+ = Mn-H- + 2 HjO + 3 N2
TfProcedure(a) A drop of the neutral test solution is mixed in a
porcelain microcrucible with a few drops of bromine water and heated.
The excess bromine is removed by stirring with a few crystals of phenol or
a drop of 80% formic acid. After cooling, the mixture is acidified (any
precipitation or cloudiness due to tribomophenol may be neglected) and a
drop of 5% potassium iodide solution and one of starch solution are added.
A blue color indicates the presence of iodide.
Limit of Identification: 0.1 7 iodine
Reagents: 1) Bromine water
2) Phenol (solid) or 80% formic acid
3) Dilute sulphuric acid
4) 5% potassium iodide solution
5) Starch solution
llProcedure^(b) A drop of the test solution is mixed in a porcelain
microcrucible with a drop of an alkaline 0.1 A^ potassium permanganate
solution and heated. Manganese dioxide separates. The solution is
acidified with 4 N sulfuric acid while still warm, and 1 N sodium azide
solution added drop by drop until the precipitate disappears and the
the solution is clear. The excess of hydrazoic acid ;is removed by heating
(fume cupboard). After cooling, the iodate formed is detected by means
of potassium iodide as described in (a).
Limit of Identification: 0.1 7 iodine
Reagents: l) 0.1 N potassium permanganate solution containinjg a few
drops of sodium hydroxide
B) 4L N sulfuric acid
3) 1 N sodium azide solution
4) 0% potassium iodide solution
5) Starch solution
4. Tests by means of catalytic acceleration of the reduction of cerium (IV)
salts.''^ The reduction of cerium (IV) salts by the arsenite ion in
acid solution: , - ~'^
2 Ce++++ + AsOr~~ + H2O = 2 Ce+++ + AsOr~" + 2 H+ (1)
"" I. M. Kolthoff and E. B. Sandell, J. Am. Chem. Soc. 56, 1426 (1934).
HYDBIODIC ACID 201
takes place extremely slowly. The completion of this reduction is easily

determined by the disappearance of the yellow color of the eerie solution.
Iodides accelerate the change,^^ and so small amounts may be detected by
this catalytic action. This catalytic effect of iodides is obviously due
to the iodine liberated in the instantaneous reaction (2) acting on the arsen-
ite according to (3), to reform iodide, which is able to react again with the
ceriimi (IV).salts according to (2):
2 Ce++++ + 2 I- = 2 Ce+++ + I, (2)
AsOr~~ + I2 + HjO ;: As07~"" + 2 H+ + 2 I- (3)
This iodide ion catalysis is thus similar in principle to an analogous inter-
mediate reaction catalysis of the decomposition of permanganates and
arsenites by means of iodide ions.
Alkali bromides, chlorides, sulfates, and nitrates interfere only when
very small amounts of iodide are to be detected. Bromides have the great-
est effect; however, if the amount of bromide present is approximately
known, small amounts of iodine may still be detected if a comparative test
is carried out. The metal salts which give colored aqueous solutions
interfere [Fe(III), 1102, Ni, Cu, Co salts]. Cyanides, mercuric, silver,
and' manganese salts impair the reaction, as do also compounds which
reduce Ce(IV) salts. In such cases the difficulty may occasionally be
averted by using more concentrated solutions of Ce(IV) salts. Under the
experimental conditions, barium and strontium salts are precipitated as
sulfates, which are colored yellow by coprecipitation of Ce{IV) salt.
Osmium salts behave similarly to iodides.
^ProcedureA drop of the test solution, a drop of sodiimi arsenite,
and a drop of Ce(IV) solution are mixed on a spot plate. The yellow color
disappears at a rate varying with the iodide content. For small amounts,
a blank test should be carried out; in this the yellow color usually disappears
in about 30 minutes.
Limit of Identification: 0.05 y potassium iodide
Reagents: 1) 0.05 N cerium (IV)-ammonium sulfate in 2 iV sulfuric
acid
2) 0.1 N sodimn arsenite (neutral or slightly acid)
5. Other tests for iodides. 1. Filter paper is impregnated with a 0.1 N
AgNOs solution and dried out of contact with air. A solution containing
iodide dropped on this paper forms a bright yellow fleck or ring of Agl^
(/d". Limit: 5 7 iodine). In mixtures which also contain chlorides and
" Compare H. H. Willard and Ph. Young, / . Am. Chem. Soc, 60, 1372 (1928).
A. J. Velculescu and J. Cornea, Z. anal. Chem., 94, 255 (1933).
202 lU. TESTS FOR ACID RADICAIS
bromides, the silver balides are fractionated, and form in jconcentric zones,
so that 5 7 iodide may be identified in the presence of 5 mg. CI or Br.
2. A drop of the test solution is placed on filter paper and exposed
briefly to an open bottle of cone, hydrochloric acid. The fleck is then
spotted with dilute TINO3 solution. Yellow Til is formed," A more
sensitive test is the formation of brown-black Pdlj, produced by bringing
together, on filter paper, 1 drop each of the test solution and 1% PdClj
solution.
HYDROFLUORIC ACID
1. Test with zirconiiun-alizarin solution.^' Hydrochloric acid solutions
of zirconium chloride are colored deep red-violet by sodium alizarin sulfo-
nate (see page 154); such solutions turn yellow at once on the addition of
excess fluoride. The zirconium forms colorless coniplex anions (ZrFa) ,
and is thus removed from the alizarin compound. Only the color of the
liberated alizarin remains.
Other anions, which give either complex ions or a precipitate with
zirconium, behave similarly to fluorides. Large amounts of sulfates,
thiosulfates, phosphates, arsenates, and oxalates, have this effect. Conse-
quently, they must be taken into account when carrying out the spot test."
Fluorine in complex combination (silicofluoride, boron fluoride) behaves
similarly to fluoride ion.''
f ProcednreA strip of quantitative filter paper is impregnated with
jsirconium-alizarin solution. The dried paper is moistened with a drop
of 50% acetic acid and a drop of the neutral test solution \B placed on the
moist fleck. A yellow spot appears in the presence of fluorides. When
only small amounts of fluorine are present it is advisable to hasten the
reaction by warming the paper in steam.
Limit of Identification: 1 y fluorine
Reagents: Zirconium-alizarin paper. Commercial zirconium oxide
(ZrOj) is warmed with dilute hydrochloric acid and
filtered from any insoluble matter. The solution should
contain about 0.5 mg. zirconiimi in 1 ml. Several ml.
of the zirconium solution a,re treated with; a slight excess
of an alcoholic solution of alizarin. The'excess alizarin
may be recognized by extracting a portion of the solution
with ether, which becomes yellow. The zirconium-
G. Gutzeit, Helv. Chim. Acta, 12,,713 (1929).
" J. H. de Boer, Chem. Weekhlad, 21, 404 (1924).
'F. Pavelka, Mikrochemie, 6, 149 (1928); compare also J. P. Alimarin, Z.
mal. Chem.,81,8 (1930).
" J. Stone, / . Chem. Education, 8, 347 (1931).
HTDROFLTTOBIC ACID 203
alizarin solution thus prepared is wanned for ten minutes

in the water bath. Filter paper is impregnated with
the warm solution and dried.
When testing for larger amounts offluorine,the folIo\ring
preparation is advised.^ Dry filter paper is soaked in a
5% solution of zirconium nitrate in 5% hydrochloric acid
and, after draining, is placed in a 2% aqueous solution
of sodium alizarin sulfonate. The paper is colored red-
violet by the zirconium lake. It is washed tmtil the wash
water is nearly colorless, and then dried.
Oxalates can be removed by igniting before beginning the test. In
the presence of sulfates, some benzidine hydrochloride should be added to
the test solution, and then a drop of the benzidine sulfate suspension placed
on the reagent paper. Any yellow coloration of the red reagent paper
caused by fluorine can easily be seen on the under side of the paper.
Detection offluorinein solid substances^^

Direct detection of even insolublefluoridesis also possible by means of
the zirconium-alizarin test. Use is made of the fact that precipitated or
naturally occurring calcium fluoride, in the presence of small amounts of
acid, is readily soluble in warm aqueous solutions of salts that form complex
fluorides. Pure calcium fluoride dissolves to give a clear solution; impure
products leave behind only the "gangue."
Among the salts which may be thus used for openyig up calcium
fluoride by the wet method, is borax, (when, no doubt, fluoboric acids are
formed), and also beryllium, aluminum, iron, and chromium salts, which as
expected, have a solvent action, since the respective fluometallic acids are
known, at least in the form of their alkali salts. The solvent action, of the
compounds named depends on their effect on the equilibrium:
? Ca++ + 2 F-
The equilibrium is not appreciably shifted by hydrogen ions, owing to the

great dissociabiUty of hydrofluoric acid. However, the removalof fluoride
ions and their incorporation in complex anions (fi.g., in A1F7 or BeFT")
disturbs the equilibrium until all the calcium fluoride is brought into
solution.
A hydrochloric acid solution of the zirconium-alizarin compound also
dissolves insoluble calcium fluoride with formation of ZrFT" ions, Ca''"'"
" W. BiltJt, Ausfahrung qualiiativer Analysen. Akadem. Verlagsgesellschaft,
Leipzig, 1930, p. 44.
" F. Feigl, MikrochemU, 7, 13 (1929).
204 m . TESTS FOR ACID RADICALS
ions, and free alizarin.'^ The test can accordingly bfe carried out on a
microscope slide by stirring a very small amount of thes powdered fluoride
with a drop of the violet reagent solution. A yellow color is formed
instantaneously.
The test may be successfully carried out on a crystal face on naturally
occurring fluorspar by contact with the reagent solution for about ^ to 1
minute. Small amounts of powdered fluorapatite, 3 Ca3(P04)2-CaF2 {ca.
3% fluorine) also give a yellow color immediately. However, precipitated
tertiary calcium phosphate, under the same conditions, only reacts after a
few minutes. The color change is due to the production of acid-insoluble
zirconium phosphate.
In a mixture of calcium fluoride and barium sulfate in the ratio 1:200,
calcium fluoride was easily detected in a sample of about 2 mg. which
represents an absolute amount of about 10 y CaFj.
The fact that even solid calcium fluoride reacts with zirconiiun ali-
zarinate renders it possible to carry out the fluoride test in the presence of
phosphates and oxalates. These interfere with the detection of fluorine
in aqueous solution, because of the formation of either insoluble or complex
zirconium phosphates or oxalates. They thus destroy the red zirconium
alizarin compound and also produce the yellow color. The calcium
fluoride may be isolated by precipitating the alkaline or neutral
test solution with calcium chloride; the precipitate is ignited and digested
with dilute acid. The residue then may easily be tested for fluoride by
the zirconiumralizarin solution.^'
Reagent: 0.05 g. zirconium nitrate is dissolved in 50 ml. water and
10 ml. cone, hydrochloric acid. The solution is mixed
with a solution of 0.05 g. sodium alizarin sulfonate in 50
ml. water.
2. Test with zirconium azoarsonate.'^ The brown insoluble zirconium
azoarsonate, formed by the action of p-dimethylaminoazophenylarsonic
acid on zirconium salts (see zirconium test page 155), reacts with Juorides
and produces colorless ZrFr~ ion and free azophenylarsonic acid,
which is red. Thus, if a drop of an acid fluoride solution is placed on filter
paper impregnated with zirconium azoarsonate, the. color change from
brown to red indicates fluorine (in the absence of interfering compounds).
IJProcedureThree drops of the neutral or alkaline test solution are
acidified with a drop of 2 iV hydrochloric acid either on a spot plate or in a
" J. H. de Boer and J. Basart, Z. anorg. allgem. Chem., 152, 213 (1926), were the
first to observe that insoluble fluorides dissolve in zirconium chloride solutions, and
the fluorine can then be titrated, using alizarin as indicator.
" Communication from W. Bottger.
*F. Feigl and E. Rajmann, Mikrochemie, 12, 133 (1932).
HYDROFLTJORIC ACID 205
small porcelain crucible. A drop of this mixture is transferred to the light

brown reagent paper. When fluorine is present, the middle of the
moistfleckis colorless, and is surrounded by a red circle of the liberated azo
dyestuff.
Limit of Identification: 0.25 y fluorine
Reagent: Zirconium azoarsonate paper. 0.025% solution of
p-dimethylaminoazophenylarsonic acid (preparation see
page 156) is made up in a mixture of 9 parts alcohol and
1 part cone, hydrochloric acid. Filter paper (S & S
589g) is laid in this solution for a few minutes. After
drying in the air, the bright red paper is placed in a
0.01% zirconium oxychloride (ZrOCl2) solution in 1 iV
hydrochloric acid. The paper turns brown at once.
After 10 minutes, the paper is washed 5 minutes each
with cold, and warm (50C.) 2 N hydrochloric acid,
then with water, finally rinsed with alcohol and ether,
and dried in vacuo.
With regard to interference with this fluorine test, the same holds
as with the zirconimn-alizarin test. Such anions interfere as give insoluble
orin the same way as thefluorideionstable soluble complex compounds.
These interfering ions include phosphates, arsenates, sulfates, and thio-
sulfates. The interference due to sulfates is, however, appreciably less
than in the zirconium-alizarin test. The test may be made completely
specific, and also applicable to insoluble compounds, minerals, etc., by
releasing the fluorine as hydrofluoric acid or HjSiFe, before the spot test
is finally carried out. The apparatus described on page 31 (Fig. 27) is
suitable. A few particles of the sample (or 1 or 2 drops of liquid which are
evaporated there to dryness) are placed in the bulb of the dry apparatus.
Then a drop of cone, sulfuric acid is added, and the stopper is replaced,
after placing a drop of dilute hydrochloric acid on the knob. The liberation
of hydrofluoric acid is hastened by warming the apparatus over an asbestos
plate. As too lengthy heating causes the volatilization of appreciable
amounts of sulfuric acid, it is advisable to add a crystal of tartaric acid to
the mixture and to stop the heating when the contents of the- apparatus
begin to char. After 1 or 2 minutes' heating, the drop on the knob of the
apparatus is touched to the filter paper impregnated with zirconium azo-
arsenate. A red color appears if the test is positive.
In this way, in a mixture of pure ignited aluminum oxide and calcium
fluoride, 0.4 y CaF2 was detected in the presence of 16,000 y AI2O3, which
represents a limiting proportion of 0.2 7 F in the presence of 80,000 times
the amount of foreign substance.
206 III. TESTS FOB ACID KADICAL8
3. Test by couTersion into sUicomolybdic add."' Both soluble and in-

soluble fluorides, on warming with quartz sand and cone, sulfuric acid are
converted into volatile siUcon tetrafluoride: .I
MeFj + HsSO* = MeSOi + 2 HF !
SiOj + 4 HF = SiF* + 2 HjO
The gas may be absorbed in a drop of water; it reacts and produces silicic
and fluosilicic acids:
3 SiF4 + 4 H2O = H4Si04 + 2 HjSiF,
Ammonium molybdate converts these compoimds into silicomolybdic acid,
H8[Si(Mo207)s]. The latter can be identified, since unhke free molybdic
acid, it oxidizes benzidine in acetic acid solution to a blue dyestuff, with
concurrent production of molybdenum blue.
The apparatus described on page 31 and shown in Figure 27 is most
useful for the hydrofluoric acid test. In this Japparatus, SiF*, developed
from the sample by sulfuric acid, is collected without loss in a drop of water
hanging on the knob under the stopper, and is there hydrolyzed.
IfProcedureThe sample, mixed with very pure quartz sand, is
placed in the bulb of the apparatus and moistened thoroughly with 1 or 2
drops of cone, sulfuric acid. The stopper with its suspended water drop
is put in place and the apparatus gently heated for about 1 minute. After
removing the flame, the apparatus is allowed to stand 3 to 6 minutes. The
water drop is then washed into a microcrucible, 1 or 2 drops of ammonium
molybdate added, and the mixture warmed until bubbles begin to rise.
When completely cool, a drop of benzidine and a few drops of sodium
acetate solution are added. A blue color shows the presence of silicic acid
and hence fluorine, in the original sample.
Limit of Identification: 1 y fluorine
Reagents: 1) Quartz sand: commercial quartz sand is heated with
cone, sulfuric acid, washed with water, and dried
8) Cone, sulfuric acid
S) Atnmonium molybdate solution: 15 g. ammonium
molybdate is dissolved in 300 ml. water and poured into
100 ml. nitric acid (sp. gr. = 1.2)
4) 1% solution of benzidine in 10% acetic acid
Samples containing carbonates, thiosulfate, sulfides, and sulfites, must be
ignited before the fluoride test, in order to prevent any^^ considerable evolu-
tion of carbon dioxide, and interference with silicomolybdate reaction by
" F. Feigl and P. Krumholz, Mikrochemie {Pregl Fettachrift), 1929, p. 83.
HYDBOFLUOBIC ACID 207
hydrogen sulfide and sulfur dioxide, which produce molybdenum blue.

Iodides and bromides interfere, in so far as they liberate the halogen under
the experimental conditions. The halogen is taken up in the drop of water
and can oxidize the benzidine to form a blue coloration. It is advisable
therefore, in the presence of these haUdes, to remove them by precipitation
with silver nitrate, after opening up the solid sample. Large amounts of
chlorides should also be removed in order to prevent frothing due to hydro-
gen chloride. Large amounts of nitrates also interfere, as the nitric acid
liberated by the cone, sulfuric acid accumulates in the drop of water and
decomposes benzidine with the formation of a yellow color. In the presence
of nitrates, therefore, the soUd sample or the residue from evaporation must
be ignited; the fluorides remain unchanged. When solutions are to be
tested for fluoride, a small amount (if necessary after precipitation with
silver sulfate) is evaporated on, quartz sand and the dry residue treated
further as described.
Detection of fluorine in rocks and mineral waters, see page 463.
4. Test by etching glass.'* The "etching test" was formerly much \ised-
Hydrofluoric acid attacks glass, producing gaseous SiF4, and the surface is
etched or roughened. Very small amounts of hydrofluoric acid, which give
an invisible effect may, however, change the surface, or the surface tension
on the glass, so that cone, sulfuric acid no longer runs off it smoothly, but
collects in drops, like water on an oily surface. This phenomenon may be
applied, under proper conditions, to the detection of fluoride, and also of
silicofluorides, which behave in the same way. The presence of substances
which form complexes with fluorine, decreases the sensitivity. Silicic and
boric acids are outstanding instances.
f Procedure"A few particles of potassium dichromate are dissolved
in 1 to 1.5 ml. cone, sulfuric acid in a narrow test tube. The walls are
completely covered with the hot mixture, in order to remove completely
any traces of grease. When the walls are clean enough, the mixture runs
evenly over the surface. A few grains of the solid or a drop of the test
solution is added and the mixture warmed. On rotating the tube, an
uneven flow of the sulfuric acid, with formation of unmoistened areas,
indicates fluorine. Large amounts of fluorine cause this result even
without heating.
Limit of Identification: 0.5 7 fluorine
Reagents: 1) Potassi\mi dichromate (powdered)
S) Cone, sulfuric acid
B. Fetkenheuer, Chem. Ahstracla, 17, 1398 (1923).
" S. K. Hagen, Mikrochemie, 16, 313 (1934).
HYDROCYANIC ACID l
1. Test with copper acetate-benzidine acetate." Copper salts react with
benzidine to give "benzidine blue" in the presence of' cyanides (or other
halides) (see page 67). This reaction takes place because the oxidation
potential of copper (II) salts is increased when copper (I) salts are taken
up by cyanide. The reaction may be applied as a test either for copper or
for cyanide. Consequently, by passing hydrocyanic acid into a solution
of copper and benzidine acetates, or by allowing the gas to come into
contact with filter paper impregnated with a solution of these materials, a
blue color due to the oxidation product of benzidine appears instantly.
This very sensitive color reaction is characteristic for prussic acid,
provided oxidizing or reducing compounds are absent, and can be used both
for cyanides that are decomposed by acids,'' and those that are not attacked.
Either procedure (a) or (b) may be followed.
If Procedure(a) A drop of the test solution is mixed with a drop of
dilute sulfuric acid in a porcelain microcrucible, which is then covered by
a piece of filter paper moistened with a drop of the reagent. A small
watch glass placed on top provides a sufficifently tight seal. A more or less
intense blue circle is formed on the white paper, depending upon the
amount of prussic acid Uberated.
Limit of Identification: 0.25 y cyanogen
IfProcedure(b) A drop of the test solution or a few mg. of the soUd
is placed in the reaction bulb of the apparatus (page 31, Fig. 30). One or
two thin pieces of zinc and 2 or 3 drops of dilute sulfuric acid are added.
The apparatus is closed with the funnel attachinent. A small piece of
filter paper moistened with the reagent solution is laid across the funnel.
The apparatus is warmed gently. The paper turns blue if any hydro-
cyanic acid is carried along with the hydrogen.
Limit of Identification: 1 y cyanogen
Reagents: 1) Dilute sulfuric acid
2) Zinc metal, in thin strips
3) Copper acetate-benzidine acetate solution
The solutions of copper acetate and benzidine acetate
are best stored separately in well-stoppered, dark
bottles, and the reagent prepared freshly each time it is
" J. Moir, Chem. News, 102,17 (1910); C. Pertusi and E. Gastal&i, Chem.-Ztg.,
37, 609 (1913); A. Sieverts and A. Hermsdorf, Z. angew. CAem'Si, 3 (1921).
" A. M. Schapowalenko (Chem. Zentr., 1930, II, 588) recommends that the
prusaic acid that is to be identified with benzidine be liberated from the test solution
by heating with sodium bicarbonate, in order to prevent any interference with the
test due to oxidizing or reducing compounds.
HTDROCTANIC ACID 209
needed (the mixture of acetates will not keep longer

than 2 weeks). The reagent is prepared from:
Solution (I) 2.86 g. copper acetate in a liter of water.
Solution (II) 675 ml. of a solution of benzidine ace-
tate, saturated at room temperature, and 525 ml. water.
Solutions (I) and (II) are mixed in equal volumes to
form the prussic acid reagent.
2. Test with copper sulfide.^" Copper sulfide is readily soluble, in the
cold, in potassiimi cyanide, giving the complex potassium copper cyanide:
2 CuS + 4 KCN -> 2 Cu(CN)a + 2 KjS
2 Cu(CN)2 -^ Cu2(CN), + (CN),
Cuj(CN)2 + 2 KCN - K2Cu(CN),
Thus, a suspension of copper sulfide is completely clarified by cyanides.
This phenomenon may be used to detect cyanides even in the presence of
ferro- and ferricyanides, iodides, bromides, chlorides, and thiocyanates.
The test may also be made on paper impregnated with cupric sulfide. The
sensitivity is greater in this case.
, IfProcedure(a) A drop of a freshly prepared copper sulfide suspen-
sion is placed either on filter paper or on the spot plate, and a drop of the
test solution added. In the presence of cyanide, the brown fleck or color
disappears at once.
Limit of Identification: 2.5 y cyanide
Reoigent: Copper sulfide suspension. 0.12 g. crystallized copper
sulfate is dissolved in 100 ml. water. After adding a
few drops of ammonia, the solution is brought to tur-
bidity with a little hydrogen sulfide
^[Procedure(b) Filter paper is impregnated with an ammoniacal
solution of 1 g. copper sulfate per Uter and dried. Immediately before the
test, hydrogen sulfide is blown on to the paper, thus turning it a uniform
brown. A drop of the test solution placed on this paper forms a white
circle when cyanide is present.
Limit of Identification: 1.25 y cyanide
3. Test by formation of thiocyanate. A very simple test, applicable also
in the presence of sulfide or sulfite, is the conversion of cyanide into thio-
cyanate, which can be identified by the sensitive iron reaction. The
thiocyanate is formed by heating with yellow ammoniimi sulfide:
CN- -1- (NHOJSJ = CNS- + (NHOiS
" O. L. Barnebey, / . Am. Chem. Soc, 36,1092 (1914).
210 ni. TESTS FOR ACID RADICAIJS
Should thiocyanatea be present from the beginning, it is necesaiiry

to isolate the cyanide befordiand {e.g., by precipitation as zinc cyanide).
UProcedureA drop of the test solution is stirred with a drop of
yellow ammonium sulfide on a watch glass and wanned until a rim of sulfur
is formed aroimd the liquid. (Evaporation to dryness should be avoided.)
After the addition of 1 or 2 drops of dilute hydrochloric acid, the mixture
is allowed to cool, and 1 or 2 drops of a solution of ferric chloride are added.
A red color indicates the presence of cyanide in the test solution.
T .. J. TJ ^ < .? J 1 -J fill tlie presence of 500 times
Limit of Identtficatton: 17 cyanide J., ^ - j- icx
, ,. T -^ 1 r nAn 1 "16 affiount of sodium sulfite
ConcerUratton Ltmit: 1:50,00u , ,~ ,
Reagents: 1) Yellow ammonium sulfide
2) Dilute hydrochloric acid
S) 1% ferric chloride solution
MERCURIC CYANIDE
1. Test by precipitation with silver nitrate in alkaline solution. Mercuric
cyanide is so little dissociated in aqueous solution that the addition of
silver nitrate produces no silver cyanide precipitate, because the solubility
product of silver cyanide is not attained. For the same reason, mercuric
cyanide does not respond to the other cyanide reactions. For instance, on
acidifying mercuric cyanide (or a potassium cyanide solution mixed with
excess mercuric chloride) with mineral acids, no prussic acid is Uberated.
The cyanide is not oxidizable, etc.^' However, the addition of alkalis to
mercuric cyanide renders the cyanide reactive again. Insoluble silver
cyanide is then precipitated by silver nitrate, and all the other character-
istic cyanide reactions occur.*' The reason for this increase in the re-
activity of mercuric cyanide is the fact that caustic alkali effects the forma-
tion of the complex compounds, e.g. K[Hg(CN)2(H20)OH], whose complex
anion dissociates:
[Hg(CN),(H,0)OH]- = ON- -f HjO -I- Hg(CN)OH
The anion is also formed:
Hg(CN) -f OH- + H,0 = [Hg(CN)2(H,0)0H]-
on the addition of sodium acetate or all alkaU salts of weak acids whose
solutions are basic due to hydrolysis. Cyanogen may thus be identified
in mercuric cyanide.
" K. A. Hofmann and H. Wagner, Ber., 41, 317,1628 (1908).
" Compare K. A. Hofmann and H. Kirmreutter, Ber., 41, 314 (1908), and also
F. Feigl and J. V. Tamchyna, iUd., 62,1897 (1929).
MERCURIC CYANIDE 211
lyProcedureA drop of the acid test solution is mixed on a watch

glass with silver nitrate; the solution remains clear. On adding a drop of a
cone, solution of sodium acetate, silver cyanide is precipitated.
Limit of Identification: 5 7 mercuric cyanide
2. By conversion into HglT" and CN-.' Due to the slight dissociation
of mercuric cyanide in aqueous solution, the concentration of cyanide
ions is so small that the hberation of prussic acid, CN" + H+ HCN,
occurs only to a minute extent. The action of mineral acids on mercuric
cyanide may, however, be appreciably increased by the addition of excess
potassium iodide. The following reaction takes place:
Hg(CN)2 + 4 KI = KjHgli + 2 KCN
the equilibrium lying so decidedly on the potassium cyanide side, that
hydrocyanic acid is formed when acid is added. The prussic acid can be
identified by the test given on page 208. A blank, from which the KI is
omitted, should be run.
3. Test by formation of cyanogen iodide.^^ Mercuric cyanide, a non-
electrolyte, will not react in neutral water solution with either potassiuni
iodide or silver nitrate to give mercuric iodide and silver cyanide, respec-
tively.. However, it reacts immediately with a solution of iodine in
potassium iodide because cyanogen iodide is formed:
Hg(CN)2 -I- 2 K H - 212 = KiHgli -1- 2 CNI
An iodine solution is thus decolorized by mercuric cyanide, and in the
absence of other substances which react with iodine, this fact may be used
as a decisive and sensitive test for mercuric cyanide. The iodine solution
must contain considerable potassium iodide, to prevent decolorization by
other mercury salts (Hgl2 formation).
^ProcedureA drop of the test solution is mixed on a spot plate
with a drop of a dilute iodine solution. Decolorization will result if
mercuric cyanide is present. The test may also be carried out by placing
a drop of a dilute solution of iodine on potassium iodide-starch paper, and
then spotting a drop of the test solution on the moist fleck of starch-iodine.
A white patch is formed on the blue background, owing to the formation of
cyanogen iodide.
Limit of Identification: 0.25 7 mercuric cyanide
Reagents: 1) 0.005 N iodine solution
2) Potassium iodide-starch paper
" I. M. Kolthoff, Z. anal. Chem., 67,14 (1918).
" Studies with H. J. Kapulitzas.
212 n i . TESTS FOR ACID RADICALS
4. Other tests for cyanide. 1. Filter paper is bd,thed in saturated solution

of picric acid and then in sodium carbonate solution. One drop of the
test solution is placed on the dried paper. A red color indicates the
presence of cyanide.''^ Sulfides produce a similar color.
2. Prussic acid combines with iodine (HCN + I2 > HI + CNI),
forming colorless cyanogen iodide. Consequently, if the acid is liberated
from cyanides and allowed to act on blue starch-iodine, the color is dis-
charged. Wanning with dilute sulfuric acid suffices for cyanides that
decompose easily; insoluble or complex cyanides require the addition of
metallic zinc. The evolution of HCN can be made from 1 drop of solution
in the apparatus (Fig. 27, page 31, and Fig. 30, page 31). 0.1 N iodine
or a potassium iodide starch paper spotted with acidified 0.1% EJOs can
be used for the decolorization** (Id". Limit: 1 7 C2N2).
S. Cyanides discharge the color of brown, cupric ferricyanide, produc-
ing colorless K2Cu2(CN)4.^' This test can be carried out as a spot reaction
under the conditions described on page 209).
THIOCYANIC ACID
1. Test by catalysis of the iodine-azide reaction. ^^ Both soluble and insolu-
ble thiocyanates accelerate the decomposition: 2 NaNs + I2 2 Nal +
3 N2, which, by itself, proceeds very slowly if at all. Consequently thio-
sulfates can be detected by the evolution of nitrogen that ensues when they
are added to an iodine-azide solution. In the presence of sulfides and
thiosulfates, which behave similarly, special precautions must be taken
(see pages 213,227, and 240).
[[ProcedureA drop of the test solution and of the iodine-azide
solution are mixed either on the plate or in the capillary tube shown on
page 25, Figure 18. Gas bubbles (nitrogen) are formed in the presence
of thiocyanates.
Limit of IderitifiMition: 1.5 7 potassium thiocyanate
This'test is especially useful for the rapid detection of thiocyanate in
the presence of oxalic, tartaric, and other organic hydroxy acids, also
phosphoric acid, and ferrocyanic acid, and especially in the presence of
iodides. It is well known that the thiocyanate reaction for iron does not
occur in the presence of these organic acids or phosphoric acid, owing to
formation of complex iron salts, while with ferrocyanide, Prussian blue
is formed. In the presence of iodides, the test with ferric chloride cannot
be used because the iodine Uberated: 2 Fe"'~^+ -kTl- -^ 2 Fe++ 4- I
G. Gutzeit, Helv. Chim. Acta, 12,713 (1929).
*' F. Feigl, unpublished studies. .
*' L. Rossi and collaborators, Chem. Abstracts, 33, 84 (1939).
" Experiments by G. Hirsch; see also F. Feigl, Mikrochemie, 7, 12 (1929).
THIOCYANIC ACID 213
renders it impossible to detect the red iron thiocyanate. The acceleration

of the iodine-azide reaction by thiocyanates is unaffected by the presence
of these anions (with the exception of phosphate and ferrocyanide). The
sensitivity is somewhat decreased by the presence of much sodium phos-
phate or potassimn ferrocyanide.
Test for traces of potassium thiocyanaie in potassium iodide
As stated, the ferric thiocyanate test for thiocyanates is not applicable
in the presence of iodides, as the iodine Uberated makes it impossible to
recognize the red color of the ferric thiocyanate. In the presence of small
amounts of iodides, the iodine-azide reaction may be carried out without
modification. However, when large amounts of iodides are present, for
reasons that are not yet explained, the sensitivity of the test is considerably
reduced, and it may be completely prevented. As the interference can
only be due to the presence of iodide ions, it may be obviated by reducing
the iodide ion concentration. This may be done simply by tê addition of
mercuric chloride. The reaction: Hg++ + 4I~ = HglJ" produces com-
plex mercuri-iodide ions, which do not interfere with the catalysis of the
iodine-azide reaction.
IfProcedureA drop of the test.solution is placed on a watch glass,
and very small drops of a cold saturated solution of mercuric chloride are
added, with a capillary tube, until a trace of a permanent precipitate of
red mercuric iodide remains. A drop of the iodine-azide solution is added
and the mixture observed for the evolution of nitrogen. The mercuric
chloride may be added after the iodine-azide solution, if preferred.
Limit of Identification: 1.5 7 to 3 7 potassium -_^ cnnn +
,, . , I ooUU' or ouuu tunes
thiocyanate <,, . ,
Concentration Umit: 1:33,000 or 1:16,500 , amount ot po-
l^tassium iodide
Test for thiocyanates in the presence of sulfides and thiosulfqtes
Since sulfides and thiosulfates also catalyze the iodine-azide reaction
(see page 227) such compounds must be removed before thiocyanates can
be detected by the catalytic action. The removal is best carried out by
precipitation with mercuric chloride, which reacts with sulfides and
thiosulfates:
S ~ + Hg++ = HgS
S,Or~ + Hg++ + H,0 = HgS + 2 H+ + SOr"
The test for thiocyanate can be carried out on the clear filtrate obtained
after filtering or centrifu^g down the mercuric sulfide. (When excess
mercuric chloride has been used, the white compound 2 HgS-HgCU is
formed).
214 III. TESTS FOR ACID RADICALS ,
Limit of Identification: 10 y potassium thiocyanate in the presence of

360 y sodium thiosulfate
. I
2. Test by conversien into prussic acid.^^ Soluble thiocyanates may be
converted into cyanide and sulfate by numerous oxidizing agents. The
cyanide can then be identified by the benzidine reaction for prussic acid
(see page 208). The conversion into cyanide takes place in acid solution
by the addition of potassium permanganate. At room temperatures the
reaction is quantitative:
5 CNS- + 6 MnOr + 8 H+ = 6 Mn++ + 5 S O r " + 5 CN" + 4 H2O
In testing for thiocyanate by the formation of cyanide, it is of course
essential that no soluble cyanide should be present from the first. When
this is the case, the prussic acid must be volatiUzed off completely from the
sample by heating it with dilute acid (hood).
Chlorides, bromides, and iodides should not be present, as the cor-
responding free halogens are liberated by potassium permanganate. They
oxidize benzidine to benzidine blue. The production of any oxidizing or
reducing gases lowers the specificity of the test.
f ProcedureThe gas apparatus (page 31, Fig. 30) is used. A drop
of the test solution is mixed with 1 to 3 drops of an acid potassium per-
manganate solution. For small amounts of thiocyanates, the mixture is
gently warmed. The hydrocyanic acid formed, when thiocyanate is
present, is revealed by the blue color on copper acetate-benzidine paper
laid on the funnel of the apparatus, or by any other prussic acid reaction."
Limit of Identification: 1 y thiocyanogen
Reagents: 1) Sulfuric acid-potassium permanganate solution
) Copper sulfate-benzidine acetate paper. For prepara-
tion, see page 209
3. Test with cobalt salts." Cobalt salts give a blue solution of K2Cô(CNS)4
with thiocyanates in the presence of acetone. The reaction may be used
not only in the detection of cobalt (see page 112), but also as a iensitive
test for thiocyanate.
llProcedureA drop of the test solution is mixed in a microcrucible
with a small drop (about 0.02 ml.) of a 1% solution of cobalt sulfate,
and evaporated to dryness. The residue is red-violet. The color fades
on the addition of a few drops of acetone, if no thiocyanate is present,
" W. P. Malitzky and M. T. Koslowsky, Mikrochemie, 7, 98 (1929).
" If the apparatus described on page 31, Figure 31, isjised, as little as 0.12
y thiocyanate can be detected. ' " -
" I. M. Kolthoff, Mikrochemie, 8, 176 (1930).
FBHKOCTANIC ACID 215
whereas the acetone becomes blue-green to green in the presence of thio-

cyanatea.
Limit of Identification: 1 y thiocyanogen
Large amounts of halides, especially of iodides, give only a slight
greenish color under these conditions. However, 6 y thiocyanate may be
detected in the presence of 1000 times the amount of iodide, bromide,
chloride, thiosulfate, and acetate. The latter two ions, on evaporation
with cobalt salts, give a green color, which, unUke.that developed by thio-
cyanate, does not enter the acetone. Nitrites interfere because they react
with thiocyanates to give red nitrosyl thiocyanate.
HYDRAZOIC ACID
Test by formation of silver or iron azide.'' Hydrazoic acid reacts with
Ag+ ions and forms white, insoluble AgNs. Red, soluble FeN9 is produced
by reaction with ferric salts. As the acid is completely expelled at 37 C.
from its aqueous solutions, it can be easily arid decisively detected, even
in the presence of other halogen hydracids.
The test is interfered with by sulfites, thiosulfates, or sulfides, that
are decomposed by acids [formation of Fe(II) salts or AgjS]. This mter-
ference can be avoided by oxidizing the neutral or alkaline test solution
beforehand with several drops of hydrogen peroxide.
^ProcedureA drop of the test solution is placed in the bulb of the
apparatus described on page 31 (Fig. 27) and treated with 1 or 2 drops of
dilute hydrochloric acid. A drop of dilute silver nitrate solution or of
ferric chloride solution is placed on the knob of the stopper. The apparatus
is closed, and the bulb is heated gently. A tui-bidity or red color indicates
hydrazoic acid.
Limit of Identification: 5 y sodiiun azide
Concentration Limit: 1:10,000 ^
Reagents: 1) Dilute silver nitrate solution
2) Dilute ferric chloride solution
Insoluble azides can be decomposed by means of metallic zinc. It is
merely necessary to add a bit of the metal to the sample in the apparatus
and to use somewhat more acid.
FERROCYANIC ACID (HYDROFERROCYANIC ACID)
1. Test with uranyl acetate." Soluble ferrocyanides give a brown pre-
cipitate of uranyl ferrocyanide (U02)2Fe(CN), with uranyl salts. Ferri-
F. Feigl, Rec. trav. chim., 68, 476 (1939).
" F . Feigl, Bee. trav. chim., 58, 477 (1939).
cyanides react only in concentrated solutions and after either long standing
or heating, and then give dirty yellow uranyl ferricyanide. Thus, uranyl
salts may be used to detect ferrocyanides in the. presence of ferricyanides .
and halide ions. When much ferricyanide is present, the precipitation of
uranyl ferrocyanide induces that of the ferricyanide. Therefore, when the
test is carried out on a spot plate, the sensitivity is increased by the pres-
ence of ferricyanides. The test may also be carried out on paper impreg-
nated with uranyl acetate, but in this case, ferricyanide should not be
present, as it is partially reduced in the paper to ferrocyanide, which reacts
with the uranyl acetate and thus interferes with the test.
IfProcedureA drop of the test solution is either mixed on the spot
plate with a drop of uranyl acetate solution, or placed on paper impreg-
nated with uranyl acetate. According to the amount of ferrocyanide
present, a brown precipitate or ring is formed.
Limit of Identification: 1 y .K4Fe(CN)
Concentration Ldmit: 1:50,000 j P P
Limit of Identification: 0.5 y Kte{Cl>i)i \ , ^x
Concentration Limit: 1:100,000 /
Reagent: 1 N uranyl acetate solution
2. Test with iron (III) chloride.^* Potassium ferrocyanide reacts with
iron (III) chloride thus to give Prussian blue:
K4re(CN)8 + FeCU - 3 KCl -t- KFe[Fe(CN)6]
soluble Prussian blue
3 KFe[Fe(CN),] + FeCU - 3 KCl -f- Fe4[Fe(CN)6]3

insoluble Prussian blue
These equations only summarize the course of the reaction. It is Ukely

that the ferrocyanide acts as a reducer, so that the ferrous salt of ferricyanic
acid (TumbuU's blue) KFe[Fe(CN)6] is also formed."
By mixing a drop of potassium ferrocyanide and iron (Ill)-^chloride
on the spot plate, 1.3 7 potassium ferrocyanide may be detected, which
corresponds to a limiting concentration of 1:400,000. The test is appre-
ciably more sensitive when carried out on paper impregnated with iron
(III) chloride, as the capillary localization of the Prussian blue then comes
into play. As little as 0.07 y K4Fe(CN)6 may be detected, which corre-
spends to a limiting concentration of 1:700,000.
When carried out on the spot plate, the test is not affected by the
presence of ferricyanide, but this is not the case on filter 'paper. The
reducing effect of the paper is such that some iron (n)'Salt is always formed
" Studies with H. Molterer.
" Compare D. Davidson, J. Chem. Education, 14, 238 (1937); see also E. Mtil-
ler, J. prakt. Chem., [2] 90,117,123 (1914).
FKRROCYANIC ACID 217
from the iron (III) chloride, and the TumbuU's blue reaction takes place.
Further, when ferricyanide is placed on paper, some of it is reduced to
ferrocyanide, and thus gives a spurious positive reaction. It is only
permiîble to use the paper when ferricyanides are absent.
Test with iron (III) chloride in tlie presence of thiocyanates and iodides,
using capillary separation'^^
The sensitive Prussian blue test for ferrocyanides, using iron (III)
chloride, is interfered with by the presence of thiocyanates and iodides,
when carried out either in a micro test tube or on the spot plate. There is
simultaneous formation of red ferrithiocyanate and of free iodine, which
interfere with the decisive identification of small amounts of Prussian blue.
If, however, the test is carried out on a paper impregnated with iron (III)
chloride, no difficulty is experienced in the presence of thiocyanates and
iodides. A capillary separation may be carried out, utilizing the fact
that ferric thiocyanate is readily decomposed by mercury (II) chloride,
sodium fluoride, or sodium thiosulfate. Where there is danger of any
interference by ferricyanide, the second procedure should be followed.
1[Procediire(a) A drop of the acid test solution is placed on filter
paper impregnated with iron (III) chloride. The ferrocyanide reacts
immediately with the ferric chloride of the paper producing a blue circle ,
or ring. Some distance away from the Prussian blue, a concentric ring of
ferric thiocyanate appears.
T uofi-Identification:
Limii rJ J -^ J 1.5 1ey T ^ /~(TVT\ ],.
Fe{CN)s f"! tlie presence
,, of 2000
. e
n 4 ,- r -t 1.00 nrvf> Stimcs the amount of
Concentraiion Limit: I'.AifMi ,,.
[thiocyanate
A far lower concentration limit is attainable for the detection of
ferrocyanide in the presence of thiocyanate when use is made of the fact
that ferric thiocyanate is decomposed by mercuric chloride, sodiimi fluoride
or sodium thiosulfate.
^ftocedure(b) When a drop of a solution containing a consid-
erable amount of thiocyanate is placed, on paper impregnated with ferric
chloride, only a deep red fleck of thiocyanate is seen. If this is treated
with a solution of mercuric chloride, sodium fluoride, or sodiiun thiosulfate,
then the red color due to the ferric thiocyanate is bleached. The circle
or ring of Prussian blue, due to the presence of ferrocyanide, is readily
visible on the paper, which is now white.
T ; of^ Identification:
Limit Tj i-j: s- ns 0.5 y -cy //~ns.T\ I,.
Fe(CN)t i^^ ^^^., presence. of, ...
5000
n , I- T- -4 i.innknn
Concentration Limit: 1:100,000 Uunes the Hjnount of thio-
l^cyanate
" According to experimental work of R. NoyAoek. The capillary separation
Fe(CN) CNS" was first recommended by G. Gntzeit, Helv. Chim. Acta, 12,
828 (1929).
218 i n . TESTS FOB ACID RADICALS
In order to detect fenoeyanide in the presence of both thioeyanate and

iodide, a drop of the test solution is placed on ferric chloride paper. In
the presence of much iodide, only a deep brown fleck {of free iodine is
formed. On the addition of a drop of a cone, sodium thiosulfate solution,
the iodine, the ferric thioeyanate, and also the yellow paper are cwnpletely
decolorized, \nth formation of tetrathionate. The fleck of Prussisui blue,
which was previously hidden by iodine and thioeyanate, is now easily
seen against the white background.
{
times the amount of thio-
eyanate and 2000 times
the amount of iodide
FERRICYANIC ACID (HYDROFERRICYANIC ACID)
The usual test for ferricyanides, formation of Tumbull's blue with
iron (II) salts," is not very successful when carried out as a spot test.
On filter paper, reduction of the ferricyanide and also of any added iron
(III) salts, may be effected by the cellulose of the paper, thus giving rise
to a blue color. When the test is carried out on a spot plate it must be
remembered that ferricyanides often contain ferrocyanide that reacts with
the iron (III) salts which are almost always present in ,the iron (II) salts,
and thus form Prussian blue. In.addition, white ferrous ferrocyanide
turns blue on exposure to air. Furthermore, it is not feasible to precipi-
tate a mixture of ferro- and ferricyanides with ferric chloride, and to form
Prussian blue from the soluble ferricyanide by adding a, reducing agent to
the filtrate. For reasons that are not clear, the ferricyanide is coprecipi-
tated with the Prussian blue. Consequently, the only safe test for ferri-
cyanide (in the presence of ferrocyanide) is the benzidine reaction.
1. Test with benzidine.** Benzidine acetate is oxidized by soluble ferri-
cyanides, with formation of insoluble blue meri-quinoid compoimds (see
page 56). This reaction is specific for ferricyanides in the absence of other
oxidizing compounds (chromates, peroxo-compounds, etc.). The test
can also be used in the presence of ferrocyanides." However, it should be
noted that the benzidine salt of ferrocyanic acid separates as a white pre-
cipitate, similar to benzidine sulfate. Thus more reagent is consumed,
and the detection of very small amounts of ferricyanide is rendered more
difl&cult. To detect very small amounts of ferricyanide in the presence of
" For the detection and distinction between Prussian blue and Turnbull's
blue see M. Kohn, Monatsh., 66, 394 (1935). For the formulae of the iron cyanide
compounds see H. Reihlen, Ann., 461, 75, (1927); 469, 30 (1929) and 476,101 (1929).
" F . Feigl, iJec. <ro. cfttm., B , 478 (1939).
" It should be noted that ferrocyanide solutions on standing, and especially
ia direct light, are appreciably oxidized to ferricyanide.
FBRBICTANIC ACID 219
large amounts of ferrocyanide, the following procedure must be followed.

Before carrying out the benzidine reaction, add sufficient lead acetate to
precipitate insoluble lead ferrocyanide; ferricyanides remain in solution.
On addition of benzidine, the white PbjFe(CN) turns blue.
[fProcedureA drop of the test solution is mixed on a spot plate with
benzidine acetate solution, if necessary after the addition of a drop of 1%
lead nitrate solution. According to the ferricyanide content, a blue
precipitate or coloration appears.
Idmit of Identification: 1 y potassium ferricyanide
Concentration Idmit: 1:60,000
Linvit of Idrntifimtion: 5 7 K,Fe(CN). f^^ t^^^ f ^sence of 1000
n , f i- M i.innnn <tuncs the amount of
Concentration Limit: 1:10,000 , .,
(.ferrocyamde
Reagent: Acetic acid-benzidine solution: 2 N acetic acid saturated in
the cold with benzidine
2. Test with phenolphthaUn/o If a red alkaline solution of phenol-
phthalein (I) is heated with metallic zinc, the color is discharged because of
reduction to colorless phenolphthalin (II). Oxidation regenerates, the
phenolphthalein:
O O-
nd.
COO- oxid. V. J COO-
^C^s~<Z> H
(1) (II)
A colorl^s alkaline solution of phenolphthalin gradually turns pink on
standing in contact with air (oxidative formation of phenolphthalein).
An intense red color is produced immediately on addition of strong oxidiz-
ing agents. (In tius connection, see page 270.)
Alkali ferricyanides oxidize alkaline phenolphthalin solutions in-
stantly. This same behavior is exhibited also by insoluble metal ferri-
cyanides that are decomposed by the free alkali in the phenolphthalein
solution, producing alkali ferricyanide and insoluble hydrous metal oxide.
A test for ferricyanide in the presence of other oxidizing materials is based
on this. The neutral or weakly acidified test solution is treated with zinc
sulfate; insoluble zinc ferricyanide separates. The washed precipitate is
tested.
A. G. Kniga, Chem. AbstracU, 31. 7000 (1937); see also 0. Baudisch, Biochem.
Z., 282, 34 (193S).
^ProcedureA drop of the neutral or slightly acidified test solution

is placed on filter paper or a spot plate and treated with a drop of the re-
agent. A red or pink appears if ferricyanide is present;
Ldmit of Identification: 0.5 y potassium ferricyanide
Reagent: Phenolphthalin solution. 2 g. phenolphthalein, 10 g.
NaOH, 5 g. zinc dust, and 20 ml. water are warmed for
about 2 hours under a reflux condenser. After cooling,
the liquid is passed through a hardened filter apper and the
colorless filtrate is made up to 60 ml. with water. The
solution must be stored in the dark; if necessary, it is de-
colorized by adding several granules of zinc
3. Test by indaced oxidation of tetrabase.'^ Tetrabase, i.e., p-tetra-
methyldiaminodiphenylmethane (I) may be regarded as a stable leuco
form of a diphenylmethane dye (II). Its intense blue color is due to the
development of quinoidal linkings.
y \ Hi y V ox.
(CH.).N<^ /C<^ ^N(CH.); 5==^
(I)
{CH,),N^^ \C=/ \=N(CH,),HX

(II)
Strong oxidizing agents convert the tetrabase (I) into the blue dye (II).
Ferricyanides or'Fe(CN)7 ions by themselves have no action on
tetrabase; however, immediate oxidation occurs when Hg++ ions or Zn++
ions are added. The reason is that the reaction:
Fe(CN)i + leuco dye ? dye + F e ( C N ) r " " + H+
is reversible. The equilibrium of this redox reaction is such that no forma-
tion of the quinoidal dye from the leuco form is discernible. If, however,
mercuric or zinc salts are added, the ferrocyanide is removed as insoluble
anc or mercuric ferrocyanide. Consequently, the Fe (CN )T concentra-
tion is so greatly decreased that, in accordance with the reaction just given,
the dye can be formed in a considerable quantity. Accordingly, the oxida-
tion potential of the ferricyanide is raised (see page 137). This effect can be
made the basis of a sensitive test for ferricyanide in weakly acid, neutral,
or alkaline solution. Under the conditions prescribed, oth'er oxidizing
agents such as nitrate, persulfate, iodate, etc., havenoaction on tetrabase.
On the other hand, chromate, bichromate, and permanganate interfere
since they oxidize the tetrabase.
L. N. Lapin, Chem. Abttracts, 86, 4305 (1941)-.
CHLOIUC ACID 221
IfProcedureOne drop of an alcohol solution of zinc chloride and

tetra base is placed on filter paper. After the solvent has evaporated, the
spot is treated with a drop of the weakly acidified test solution. A blue-
violet fleck or ring appears if ferricyanide is present. The sensitivity of
the test is very much lower in alkaline solution.
Limit of Identification: 0.1 7 Fe(CN)(
Reagent: 2% solution of zinc chloride in alcohol is saturated with an
excess of tetrabase and then filtered
Capillary detection of ions that contain the cyanogen radical'^
It is possible to detect the constituents in one drop of solution that con-
tains Fe(CN)r , Fe(CN)7 , and CNS" ions. Spot reactions are used.
1[ProcedureA strip of filter paper is soaked in a saturated solution
of lead nitrate, and a drop of the test solution is added. Insoluble
PbjFeCCN). is fixed in the middle of the moist fleck. Ferricyanide and
thiocyanate diffuse out through the capillaries, and, after the addition
of a little water, remain in the outer zone. The spot is then moistened
on one side, from a capillary, with iron (III) and on the other with iron (II)
solution. In the presence of the proper anions, a fleck of Prussian blue is
formed in the center, and TumbuU's blue and ferric thiocyanate at the
border. Cyanide ions must be tested for in ^separate sample.
Reagents: 1) Lead nitrate solution (saturated)
S) Dilute ferric chloride solution
3) Dilute ferrous sulfate solution
4. OHher tests for ferrocyanide and ferricyanide. 1. Ferrocyanide can be
detected, in slightly acid solution, with titanium tetrachloride. The reac-
tion is carried out on a spot plate. A yellow to red-yellow precipitate,
TiFe(CN), is formed [7d. LimU: 50 7 KFe(CN)6].
2. Filter paper is impregnated with a freshly prepared, saturated
(70 C.) solution of trithiourea cuprous chloride. A gray to red-violet
fleck of [CuThj ]a [Fe(CN) ] H2O appears when the paper is spotted with a
neutral solution of ferricyanide'* [Id". Limit: 0.9 7 KjFe(CN)].
CHLORIC ACID
Test with manganous sulfate and phosphoric acid." In strong phosphoric
acid solutions, chlorates react with manganese sulfate, on heating, to form
complex manganese (III) phosphate:
a o r -t- 6 Mn++ + 12 POr"" -l- e H + - 6 Mn(P04)r"" -l- Cl- -f 3H,0
A. M. Sohapowalenko, Chem. Abstracts, 34, 3458 (1930).
W. C. Oelke, /nd. Eng. Chem., Anal. Ed., 18, 498 (1940).
" E. Storfer, Mikrochemie, 17,170 (1935).
F. Feigl, Ree. trav. chim., 68, 479 (1939).
222 i n . TESTS FOR ACID RADICALS '
The complex manganese ion has a violet color similar to that of the per-
manganate ion.
Both persulfates and periodates react similarly (see page 224).
Persulfates may be destroyed by evaporating the sulfuric acid solution
with a little silver nitrate. Complete decomposition ensues: HjSjOg +
H2O = 2 H2SO4 + 0. The test cannot be applied in the presence of
periodates.
IfProcedureA drop of the test solution is mixed with a drop of the
reagent solution in a small porcelain dish, and the mixture briefly warmed
over a microbumer, and allowed to cool. According to the chlorate con-
tent, a more or less deep violet coloration results. Very pale colors may
be intensified by adding a drop of an alcoholic solution of diphenylcar-
bazide. A more distinct violet coloration then results, due to the formation
of an oxidation product of diphenylcarbazide.
Limit of Identification: 0.05 y C10
Reagents: 1) Saturated manganous sulfate solution
2) Syrupy phosphoric acid ^
1) and 2) are mixed in equal volumes to form the reagent solution
BROMIC ACID *
1. Test with manganous sulfate and sulfuric acid/' Bromates, when
treated with manganous sulfate and sulfuric acid, first give a red colora-
tion, due to the intermediate formation of Mni(S04)j. On boiling, a brown
precipitate of hydrated manganese dioxide is formed:
HBrO,-f 6MnS04 + 3H,S04 = 3Mn,(SO*), + 3HsO-l-HBr (1)

5 HBr -I- HBrO, = 3 HjO -}- 3 Brj (2)
MniO, -f- H2O + Br, = 2 MnOj + 2 HBr. ^ - ^ _ (3)
Chlorates and iodates, under the same conditions, give neither a red
color nor a precipitate. The test for bromate with manganese sulfate
and sulfuric acid may be carried out as a spot reaction, when it is combined
with the benzidine reaction for manganese given on page 134." '
^ProcedureA drop of the test solution is mixed in a microcentrifuge
tube with a drop of manganous sulfate solution acidified with a little
sulfuric acid, and warmed for 2 to 3 minutes on the water bath. After
cooling, a few drops of an acetic acid-benzidine solution and a few crystals
" D. Vitali, Bull. chim. pharm., 88, 201 (1899); Chem. Zentr., 1809,1. 1083.
" Experiments .with S. Pickholz.
IODIC ACID 223
of sodium acetate are added. A more or less deep blue color results, de-
pending upon the quantity of bromate in the test solution.
Limit of Identification: 40 7 potassium bromate
Concentration Ldmit: 1:2500
Reagents: 1) 2% manganous sulfate solution, acidified with sulfuric
acid
f) Acetic acid-benzidine solution (see p ^ e 135)
S) Solid sodium acetate
IODIC ACID
1. Test ^th hypoidiosphoroas acid.** lodates are reduced by hypophos-
phorous acid, even in the cold, to give iodides. The iodine, which is
liberated as an intermediate reaction product, may be rendered visible by
the starch reaction, and thus provides a useful test for iodates. Bromates
and chlorates do not react under the same conditions. The reactions are:
lOr + 3 BJÔi ^ 3 HjPO, + I- \ .,
5 I- + lOr + 6 H+ = 3 HjO + 3 I* J'"^P*
HJPO, + I2 + H,0 = H,P04 + 2 HI slow
^ProcedureA drop of the neutral test solution is mixed on a spot
plate with a drop of starch solution and a drop of a dilute solution of hypo-
phosphorous acid is added. A transitory blue appears in the presence of
iodates.
Limit of Idenlijicaiion: 1 7 iodic acid
Reagents: 1) Starch solution
2) Dilute solution of hypophosphorus acid
2. Test irith potassium thiocyanate." Alkali thiocyanates react with
iodates in acid solution:
5 CNS- -f 6 lOr -I- 6 H+ 4- 2 H2O == 5 HSOr + 5 HON 4- 3 I2
The liberation of iodine thus indicates the presence of iodate.
IfProcedureA drop of potassium thiocyanate solution, followed by a
drop of the acid test solution, is placed on starch paper. A more of less
intense blue stain indicates the presence of iodate.
Limit of Identification: 4 7 sodium iodate'
Reagents: 1) 5% potassiimi thiocyanate solution
B) Starch paper
> Compare A. Brukl and M. Behr, Z. anal. Chem., 6i, 23 (1924).
N. A. TanaiiMfiF and A. M. Schapowalenko, Z. an<a. Chem., 100, 352 (1935).
3. Test mih pyrogaBol.' In acid solution, iodates pxidize pyrogallol to

purpurogallin. Strong oxidizing agents such as iodine and chromate act
in the same way. Persulfate, nitrate, and bromate give similar colors
which, however, can be distinguished if parallel tests are made.
^ProcedureFilter paper impregnated with i acid pyrogallol is
spotted with a drop of the test solution. A pink to red appears according
to quantity of iodate present.
Limit of Identification: 0.25 y sodium iodate
Reagent paper: Strips of filter paper are bathed in oxalic acid, dried,,
and then bathed in an acetone solution of pyrogallol.
PERIODIC ACID
1. Test with manganoiis sulfate and phosphoric acidJ^ Periodates
react with manganous sulfate, on heating, in strong phosphoric acid
solution, with the formation of complex manganese (III) phosphates,
that have extraordinary tinctorial power. The violet resembles that of
permanganate solutions. The reaction can be represented:
lOr + 2 Mn-H- 4- 4 P 0 7 " " + 2 H+ = 2' [Mn(P04)j] + 107 + H,0
Persulfates and chlorates give a similar effect. Persulfates can be
decomposed by evaporation of the sulfuric acid solution with a small
amount of silver nitrate. The test is not applicable in the presence of
chlorates (see page 221).
IfProcedureÂ drop of the test solution is mixed with a drop of the
reagent solution in a small porcelain dish. (A small crucible stand is very
suitable.) The mixture is warmed briefly over a microbumer and allowed
to cool. A more or less deep violet is formed according to the periodate
present. Very pale colors may be intensified by the addition of a drop of an
alcoholic solution of diphenylcarbazide; a distinct violet appears.
Limit of Identification: 5 7 periodate
Reagents: 1) Saturated manganous sulfate solution
2) Syrupy phosphoric acid
A stable reagent solution is prepared by mixing equal
partsof i ) and;?)
2. Test vith manganese salts and tetrabase.'^ Manganous salts are
oxidized to permanganate on warming with alkali periodates in. acid
solution: .- -
2 Mn++ + 6 lOr + 3 H0 = 2 MnOr + 5 lOr + 6 H+
" A. L. Gottlieb, Chem. Abttracta, 32,4469 (1938).
" F. Feigl and H. E. Ballaban, unpubliebed studies.
PERIODIC ACID 225
This sensitive reaction, which is used for the detection of manganese (see
page 134), may also be used to detect periodates. The identification of
small amounts of permanganate is simplified by the use of Arnold's base
(tetramethyldiaminodiphenylmethane); a blue meri-quinoid oxidation
product of the tetrabase is formed. Chlorates, bromates, and iodates
do not interfere with the test. Persulfates react with-^manganese salts,
giving higher manganese oxides, which also react on Arnold's base. Any
persulfate, however, may be removed by evaporating the sulfuric acid
solution with a little silver nitrate. Colored metallic salts should not be
present if they hide a light blue coloration.
IfProcedureÂ drop of the test solution is mixed with a drop of the
reagent solution. A blue coloration indicates periodate.
Jjimit of Identification: 0.5 y periodate
Reagents: 1) 2 N acetic acid, saturated in the cold with the tetra-
base (for preparation see page 134)
S) 10% manganous chloride solution
Equal parts of solution 1) and S) are mixed before using.
3. Test by the formation of complex copper (III) salts." A dark red color
appears on warming alkaline solutions of copper salts with certain oxidiz-
ing agents (such as persulfate) in the presence of alkali periodate. The
complex anion formed from trivalent copper and the periodate radical is
responsible for the color."
The formation of this colored ion may be used as a spot test for perio-
date [Procedure (a)]. Alternatively, the interference by iodate, with
the catalytic effect of copper (III) salts on the reaction between Mn++
ion and hypobromite may be utihzed [Procedure (b)]. This reaction
normally proceeds with formation of manganese dioxide, but in the pres-
ence of even extremely small amounts of copper salts, permanganate is
formed. An intermediate compound, Cu(III) oxide, causes a further
oxidation from MnOs to MnOr ion, with regeneration of Cu(II) oxide
(see page 133). The formation of the stable complex ion of trivalent cop-
per with periodate, prevents the addition of oxygen to the Mn02 and the
formation of permanganate does not take place.
The production of stable complexes of trivalent copper, under the
given conditions, is limited to periodic acid and telluric acid (see page
267). The test is therefore extremely selective.
^Procedure(a) A drop of copper sulfate solution is added to the
alkaline test solution, followed by a drop of alkaU hydroxide, and finally a
" F . Feigl and R. Uzel, Mikrochemie, 19,133 (1936).
' M . VrtiS, Rec. trav. chim., 44, 429 (1926); L. Malaprade, Compt. rend., 204,
979 (1937).
W
little solid potassium or sodium persulfate. ~The mixture, is boiled. A

yellow color indicates periodic acid.
Limit of Identification: 2 y periodic acid
Reagents: 1) Copper sulfate solution, 1:50,000 1
2) 2 N sodixun hydroxide
S) Potassium persulfate, solid
IfProcedure(b) A drop of the test solution, a drop of the copper-
manganese solution, and a drop of sodium hypobromite are mixed in a micro
test tube. A blank test is carried out simultaneously on a drop of water
and the reagents. Both test tubes are placed for a few minutes in boiling
water, or heated to boiling over a free flame. In the presence of periodic
acid, the solution remains colorless or is slightly yellow, while the blank
clearly shows the permanganate color.
Limit of Identification: 0.5 y periodic acid
Reagents: 1) Coppei^manganese solution. A drop of 4% solution
of CuS04-5 HjO is added to 100 ml. of a 0.04% solution
of MnCl2-4 HjO.
2) Sodixrai hypobromite. A freshly prepared solution of
bromine in 2 AT NaOH
HYDROGEN SULFIDE
1. Test with sodium nitroprusside.'^ Sodium nitroprusside, Na-
[Fe(CN)6N0], in alkaline solution gives a red-violet coloration with
sulfides. The product disappears on addition of acids. For sodimn
sulfide it has the empirical formula Na4[re(CN)N0S]. It is not yet
certain whether an addition compound is formed' from the components,
or whether a complex ion [Fe"(CN)8N"'0S] is produced, with the
reduction of the iron. The latter assumption is the more probable."
^ProcedureA drop of the "alkaline test solution is mixed on a spot
plate with a drop of sodium nitroprusside. A more or less intense violet
color appears, depending on the amount of sulfide present. The spot
test may also be carried out on filter paper impregnated with an am-
moniacal (5%) solution of sodium nitroprusside. ' '
Limit of Identificaiion: 1 y sodium sulfide
Reagent: 1% solution of sodium nitroprusside ,
" H. Kril, Z. anal. Chem., 36, 696 (1897).
Compare K. A. Hofmann, Ann., 312, 1 (1900); J. F. Virgili, Z. anal. Chem.,
W, 409 (1901); G. Scagliarini, Chem. AbairacU, 29. 2872 (1935).
HYDROGEN SULFIDE 227
2. Test by caUdysis of the iodine-azide reaction." The follo^ving test

forsulfides (as well as the tests for thiocyanate and thiosulfate, pp. 212 and
240) depends on the observation that solutions of sodium azide and iodine
do not react together, but that, on the addition of a crystal of sodium sulfide
or sodium thiosulfate, there is an immediate and vigorous evolution of
nitrogen, with consumption of iodine." This reaction, initiated by
sulfides (and also by thiosulfates and thiocyanates), takes place:
2 NaNs + Is = 2 Nal + 3 Nj
Written in this manner, the equation implies that the sulfur-bearing ma-
terial takes no part in the reaction, which may therefore be regarded as
catalyzed. Even traces of sulfides are able to start this reaction, whose
occurrence is easy to see because of the evolution of nitrogen. The effect
on this reaction thus provides a convenient test for sulfide (thiosulfate and
thiocyanate).
The acceleration of the reaction between NaNj and Ij can be explained
as an intermediate reaction catalysis as follows: the iodine is taken up by
the thio compounds to form labile reactive compounds as shown in (1).
These iodine-sulfur compounds react with sodium azide as shown in (2),
whereby the pure sulfur compound, the catalyst, is regenerated unchanged.
Siramiation of (1) and (2) gives the foregoing equation, in which the cata-
lyst, namely, the sulfidic compound, does not appear. This series of reac
tions is repeated until all the iodine or sodium azide is consumed.
. MeS -|- I2 -^ IMeSI.... primary reaction (1)
IMeSI + 2 NaN -^ MeS + 2 Nal -f 3 Nj secondary reaction (2)
2 NaNj -f I2 -* 2 Nal -|- 3 N2 . . . .catalyzed reaction (1) + (2)
(Me = divalent metal)
The reactive intermediate compound given in (1) and (2) is hypo-
thetical. This means that while its postulation satisfactorily explains the
mechanism of the catalysis, its existence has not been proved, since the
compoimd has not been isolated. This is not surprising, because the la-
bility and reactivity of the intermediate compounds of a catalyst are the
very characteristics responsible for the catalytic effect. The compound
IMeSI represents the addition of iodine to MeS to form MeS I2 (com-
pare page 229).
The catalyzed reaction makes it possible to detect extremely email
quantities of sulfides. Furthermore, the effect is strictly specific for sulfide
" F . Feigl, Z. anal. Chem., 74, 369 (1928). Compare L. Metz, ibid., 76, 347
(1929); also Jahresbericht der Chemisch-Technischen Reichsdnstalt, Vol.V, Verlag
Chemie, Leipzig, 1926, p. 143.
" F . R*8cbig, Ber., 48. 2088 (1915).
228 III- TESTS FOR ACID KADICALS
sulfur, both in inorganic and organic form (see page 353). Sulfur com-
bined in other ways (sulfate, sulfite, and free sulfur) has as little effect on
the reaction as selenides and tellurides, which in. other respects are very-
similar to metal sulfides. The fact that soluble as well afe însoluble sulfides
exert this catalytic action is of considerable analytical value.
Test for soluble sulfides.
UProcedureA drop of the sample and a drop of iodine-azide solu-
tion are mixed on a watch glass. An immediate development of gas,
in the form of tiny bubbles rising through the liquid, indicates the presence
of sulfides.
The test is only decisive in the absence of thiosulfates and thio-
cyanates, as these compounds likewise catalyze the iodine-azide rea,ction.
In the presence of interfering sulfur compounds, the sulfide must be isolated
beforehand. This operation is carried out by precipitation with zinc or
cadmium carbonate in an Emich microcentrifuge,tube. After centrifuging
and thorough washing, the sulfide may be detected by the iodine-azide
reaction.
Ldmit of Identification: 0.3 7 sodium sulfide
Reagent: Sodium azide-iodine solution. 3 g. sodium azide are dis-
solved in 100 ml. 0.1 N iodine solution. The solution is
stable
As Uttle as 0.02 7 sodium in one drop can be detected by using as reagent a
solution of 1 g. sodium azide, 1 g. potassium iodide, plus a tiny crystal of
iodine, in 3 ml. water.
Concentration Ldmit: 1:2,500,000"
It is probable that all the tests with sodium azide-iodine solutions, de-
scribed in this text, would exhibit-greater sensitivities if more concentrated
reagent solutions were used.
Test for solid sulfides.
All solid metal sulfides, whether natural or synthetic, and also the
sulfo salts (e.^., 2 HgS-HgCU and similar molecular compounds of sulfides)
react immediately with sodium azide solutions with evolution of nitrogen.
They may thus be detected in the presence of sulfates,' free sulfur, etc.
The test can therefore also be applied in the scheme of systematic
analysis to determine the presence of sulfides in the so-called "insoluble
residue" (see page 301), and also to detect the presence of mercury in the
residue (containing lead sulfate, mercury sulfide, or2"HgS-Hg(N03)2,
and sulfur) left after treatment of the basic sulfides with concentrated
"Studies with R. Schacherl.
HTDROQEN SULFIDE 229
nitric acid. When this test is used to detect mercury sulfide, the solution
in aqua regia, or in hydrochloric acid containing hydrogen peroxide,"
and the subsequent stannous chloride reaction, which are both otherwise
essential, may be by-passed with considerable saving in time and material.
IfProcedureExtremely small amounts of solid sulfides, e.g., in
the dust from a powder, may be detected very simply by placing a drop
of sodium azide-iodine solution either in a capillary or in an Emich micro-
centrifuge tube. A particle of the test substance is introduced on the tip
of a platinum wire bent at 45 (Fig. 44). In the presence of sulfides, the
gas bubbles rise in the capillary or in the constricted part of the conical
tube. They can readily be seen with the naked eye or a lens.
The detection of solid insoluble sulfides through cata-

lysis of the iodine-azide reaction is also remarkable from the
theoretical standpoint because it throws a characteristic light
on the ability of solid materials in general to enter into re-
actions. If, in accord with the classical views of the ionic
theory, it is assumed that chemical reactions in and with
water solutions involve solely ionic and molecular species in
solution, a calculation in the case of copper sulfide reveals
the following-.the solubility (in water) of CuS is 1.9-10"" grams
per liter. One gram mole (95.6 g.) of copper sulfide contains
6.06-10" molecules, so that about 12-10* molecules of CuS are
contained in one liter of saturated solution. If then, one drop
(0.05 ml.) of the reagent is placed on solid CuS, and the y AA. v, t t
iodine-azide reaction is catalytically initiated, then under the testina solids for
(improbable) assumption that the solution is immediately sulfides (' actual
saturated with CuS, it follows that no more than 6 molecules gizg)
of CuS are reacting. Still smaller numbers are obtained if an
analogous calculation is made for HgS or AsiSj, which are even less soluble in
water than CuS. Even the most sensitive chemical reaction (including the
iodine-azide catalysis by soluble sulfides) always involves many millions of mole-
cules. So the assumption is justified that in the case of solid insoluble sulfides the
catalysis is not due to dissolved molecules, whose number is not adequate, but
rather that the effect is due to the metal sulfide molecules still held in the lattice of the
solid phase. In the present instance, it is probable that the first stage consists of the
addition of free iodine to the metal sulfide, forming MeS-Ij. This compound is the
tautomeric form of Me(SI)I which was asstmied (page 227) to be the reactive inter-
mediate compound in the iodine-azide catalysis. The idea that iodine is activated
by addition to metal sulfide is supported by the following: (/) In conformity with the
free surface of solids, large numbers of niolecules must be involved when iodine is
added. {S) Experiments have shown that heavy metal sulfides react in the solid
state with iodine dissolved in organic liquids and produce the corresponding iodides.
I t seems much more likely that the course of these reactions is not direct, but that
they involve the formation of the intermediate compound MeS-Ij. Accordingly,"
MeS + li-* M e S I , -+ Mel, -f S.
" F. Feigl, J. Chem. Education, 20, 177 (1943).

Detection of sulfides in minwals, see page 301. j

Test for alkali hydrosulfides in the presence of alkali sulfides. Both
sulfides and hydrosulfides are oxidized by iodine: I
NasS + I, = 2 Nal + S or NaHS + I2 = Nal + S + HI
The solution of alkali sulfides, which, owing to hydrolysis, originally
had an alkaline reaction, becomes neutral after oxidation by iodine, if
normal sulfides are present, and acid when hydrosulfides are present.
Therefore hydrosulfides laky be detected in the presence of sulfides by the
acid reaction after oxidation with iodine.
If ProcedureA drop of the test solution on a spot plate is treated,
drop by drop, with a 0.1 iV iodine solution Xintil the iodine color is perma-
nent. A drop of carbon disulfide is added and the mixture stirred with a
glass rod. The carbon disulfide dissolves both the sulfur formed in the
reaction, and the excess iodine. The acid reaction of the aqueous solution
can then easily be tested by means of a small strip of htmus paper.
Reagents: 1) 0.1 iV iodine solution
Z) Litmus paper
Test for free alkali in the presence oi alkali sulfides, with thallium nitrate.^"
In order to detect free alkali, in the presence of alkali sulfides, which also
give an alkaline reaction owing to hydrolysis, use is made of the fact that
while thallous sulfide is insoluble, thallous hydroxide is soluble, and is
almost as strong a base as potassium hydroxide. Thus, free alkali may be
detected by adding neutral thallous nitrate to the test solution and then
testing the solution for an alkaline reaction.
^[ProcedureA drop of the test solution is mixed on a spot plate
with 1 or 2 drops of a saturated solution of thalliiun nitrate, and stirred.
A small strip of litmus paper, immersed in the resulting suspension of thal-
lous sulfide, turns blue, if free alkali is present.
Reagents: 1) Thallous nitrate solution (saturated) "^
8) Litmus paper ~
Other tests for sulfides. 1. Hydrogen sulfide can be detected through the
formation of methylene blue.*' This can be carried out as a spot reaction
in the apparatus described on page 31 (Pig. 27). The gas Hberated from
sulfides is absorbed in a drop of dilute NaOH. This is transferred to a
spot plate and treated with a mixture containing 1 drop each of cone. HCl,
0.1 A^ FeCU, and several granules of p-aminodimethylaniUne. Methylene
blue is formed {Id". Limit: 1 7 HjS).
" F. Feigl, unpublished studies.
" E. Fischer, Ber., 16, 2234 (1883).
STTLFUBOUS ACID 231
S. Sulfides may be detected with sodium plumbite solution" {Id'.

Limit: 1.8 7 NajS).
SULFUROUS ACID
1. Test widi sodium nitroprnsside.''
(o) Detection in solutions
Sulfites and firee sulfurous acid, even in concentrated solutions, give
only a pale red with sodium nitroprusside Naj[Fe(CN)6NO]-HsO. The
red color is appreciably deepened by the addition of a saturated solution of
zinc sulfate or nitrate and a few drops of a potassium ferrocyanide solution;
a red precipitate is formed. The chemistry of this change has not been
elucidated. Probably, as in the test for sulfides with sodium nitroprusside
(see page 226),a complex compound is formed,*'* with reduction of the iron.
On the addition of acids, the red color disappears. Sulfates and thiosulfates
do not interfere; sulfides react in alkaline solution to give a violet color.
The reaction may be made somewhat more sensitive by changing the order
of adding the reagents.
f ProcedureA drop of a solution of potassium ferrocyanide is added
to a drop of a cold saturated solution of zinc sulfate (or nitrate) and then a
drop of sodium nitroprusside is added. A white precipitate of zinc ferro-
cyanide Zn2Fe(CN) forms. A drop of the neutral test solution is intro-
duced and the precipitate becomes red if sulfites are present.
Limit of Identification: 3.2 7 sodium sulfite
Reagents: 1) 1% sodium nitroprusside solution
2) 1 N potassium ferrocyanide
S) Cold saturated zinc sulfate or nitrate solution
(b) Test by evolxUion 'of sulfur dioxide
When the moist salmon-colored zinc nitroprusside ZnFe(CN)jNO is
brought into contact with sulfur dioxide, it turns pink to dark red, according
to quantity. The test is more sensitive when the reaction product is held
over ammonia gas, which decolorizes the unused zinc nitroprussiate.**
The composition of the product, which is decomposed both by alkalis and
mineral acids, has not yet been determined. Possibly a loose addition
compoimd is formed between SO* and ZnFe(CN)6Nd. Other rnetal salts
of nitroprussic acid behave similarly to the zinc salt.
X N. A. Tananaeff and A. M. Schapowalenko, Z. ancd. Chem., 100, 346 (1935).
C. Bodecker, Ann., 117,193 (1861).
" G. Scagljarini, Chem. Abttracls, 29, 2872 (1935), has prepared a cadmium
compound with hexamethylenetetramine of the composition
Cd,lFe(CN)tN080,l -12 H,0-2CjauN
and assumes that the complex ion [Fe(CN)(NOS0t]''~*^ is present.
** . Eegriwe, Z. anal. Chem., 66,138 (1924/25).
232 III. TESTS FOB ACTD RADICALS
The test for sulfites is carried out by liberating 14 sulfur dioidde with
mineral acid, and then bringing the gas into c<Htact with Zn [Fe(CN)iNO ].
The apparatus described on page 31 (Fig. 27) is suitf^^.
^ProcedureA grain of the soUd sample or a drop of the test solution
is placed in the reaction bulb. The sulfur dioxide is hberated by means
of a drop of 2 iV hydrochloric or sulfuric acid. The knob of the glass
stopper is covered with a thin layer of the reagent, and the stopper is
inserted immediately before adding the acid. After the SOj has acted,
the stopper is held for a short time over ammonia. A more or Iras deep red
color of the reagent indicates the presence of sulfurous acid.
Limit of Identification: 3.5 Y sulfur dioxide
Reagent: Zinc nitroprusside paste is made by treating sodium nitro-
prusside with an excess of zinc chloride at the temperature
of boiling water. The precipitate, after being filtered and
washed, is kept in a dark glass bottle
.(c) Test for sulfites in the presence of sulfides and thiosulfates
Sulfites cannot always be detected directly in the presence of sulfides
and thiosulfates. The hydrogen sulfide hberated from sulfides by acid
(apart from its reaction with alkaline nitroprusside itself) reacts with any
sulfur dioxide from the sulfite:
2H2S + SOj =2HjO + 3 S .
with precipitation of sulfur, and thus interferes with the nitroprusside test.
Thiosulfates may be mistaken for sulfites since they are decomposed by
mineral acids:
S2O3 + 2 H+ = SO2 + S + HjO
and give sulfur dioxide.
Both thiosulfates and sulfides must therefore be removed from the
solution before carrying out the test. This is conveniently 4one by the
addition of mercuric chloride which reacts with both types of compounds:
S + Hg++ = HgS
S2OF" + Hg++ + H2O = HgS + S O " + 2 H+
with formation of acid-stable mercuric sulfide. The liberation of SO2 from
sulfites by the acid remains unaffected when HgClj is added.
IfProcedureThe apparatus, Figure 27, is used. A drop of the test
solution is mixed with 2 drops of a saturated solution of mercuric chloride.
After a minute, the mixture is acidified with dilute hydrochloric or sulfuric
acid. The test is carried out as described. ^
In this way, 20 7 NajSOs may be identified in "the presence of 900 y
NajSjOj and 1500 y NajS, which r^resents a ratio
NajSOg: NaaSjO,: NajS = 1:45:75
sxniFimous ACID 233
StUl smaller amounts of sulfite can be detected by the test with nickel
hydroxide, following removal of sulfide and thiosulfate.
2. Test by induced oxidatioii of nidiel (11) hydroxide." The aUtoxidation
of sulfur dioxide induces the oxidation of nickel (II) to nickel (III) hy-
droxide.*' This is the more remarkable as this change is otherwise only
effected by strong oxidizing agents (halogens, persulfates, etc.). When,
for example, a dish containing sulfurous acid is placed in a desiccator
together with another dish containing precipitated nickel hydroxide, the
green Ni(0H)2 turns black with the formation of higher nickel oxides.*^-**
This involves an induced reaction whose mechanism probably is: basic
nickel sulfite results from the action of SO2 on Ni(OH)s and is then con-
verted into NiSOi and black Ni(0H)4 by autoxidation:
OH
/
Ni
\
SO, + Oi + H,0 -> NiSO + NiC0H)4
/
Ni
\
OH
This oxidation of Ni(0H)2 by contact with SOj and air may be ap-
plied to the detection of sulfites, as the change of color is very definite if
the experimental conditions are controlled. For very small amounts of
SO2, the formation of benzidine blue from benzidine acetate by means of
higher metallic oxides'* may be utilized (see p. 134), as the reaction suc-
ceeds even with traces of Ni(0H)4.
llProcedureA drop of the test solution (or a little of the solid) is
placed in the bottom of the apparatus described on page 31 (Fig. 27). A
little freshly precipitated nickel hydroxide, that has been washed free fron
alkali, is placed on the glass knob beneath the stopper. After adding 1 or 1*^
drops of hydrochloric acid, the apparatus is closed, and the SOj liberated by
warming gently. According to the amoimt of sulfite present, the green
paste of Ni (OH)s turns gray to black. For veiy small amoxmts of sulfite,
the nickel hydroxide is transferred after the reaction to a quantitative filter
paper, and treated there with a drop of an acetic acid solution of benzidine.
A blue color indicates sulfite.
F. Feigl and E. Frankel, fier., 66, 546 (1932).
C. Wicke, Z. Chem., 8, 89, 305 (1865); F. Haber and.F. Bran, Z. phynk.
Cftem., 36, 84 (1900).
' W. Bottger, Qtuditative Analyse. 4th ed., Engelmann, Leipzig, 1925, p. 138.
" W. Bdttger and E. Thoma, J. prakt. Chem., 147, 11 (1936).
> F. Feigl, Chem.-Ztg., 44,689 (1920).
234 n i . TESTS FOR ACID RADICALS '
Limit of Identification: 0.4 7 sulfur dioxide I

'Concentration Limit: 1:125,000
Reagents: 1) Alkali-free, washed nickel hydroxide, prepared by precipi-
tation of NiCls with NaOH
S) Hydrochloric acid (1:1)
3) Benzidine acetate solution (preparation, see page 135)
The reaction may be used to show that sulfur dioxide is formed by the action
of light on finely divided sulfur. A little powdered sulfur is placed on
moist Ni(0H)2 paper, left in the simlight for a few minutes, and then
treated with the benzidine acetate solution. A bright blue color develops.*"
3. Test by decolorization of malachite green.'^ Neutral sulfites in-
stantly decolorize dilute aqueous solutions of triphraiylmethane dyestuffs
{e.g., fuchsin or malachite green). The addition of aldehydes {e.g., an
aqueous solution of acetaldehyde) to the decolorized solution causes the
color to rea^jpear (see page 339). The action of sulfurous acid on p-fuch-
sin (I) produces the N sulfinic acid of p-fuchsinleucosulfonic acid (11).**
^'^-<Z>\
H, /
C=<
3-^ >=NH
(I)
H,N
\
C< V-NHSO,H
:.N-<3/lSO,H
(II)
The alkali salts of this acid are formed by the action of neutral'sulfites.
When acid sulfites or free sulfurous acid are used, the decolorization
of the solution of the triphenylmethane djrestuff is incomplete. In such
cases previous neutralization with sodium bicarbonate is essential. How-
ever, free alkah also interferes with the decolorization reaction; it must be
removed beforehand with carbonic acid. ' '
Thiosulfates, polythionates, and hydrosulfides are without effect on
solutions of triphenylmethane dyestuffs, but mono- and polysulfides react
the same way as sulfites. ,
" P. Reckendorfer, Z. P/lonzenfcronfc/i. Pânzensc/iute, 45^537 (1935).
" E. Votocek, Ber., 40, 414 (1907).
" H. Wieland and G. Scheuing, Ber., 64, 2527 (1921).
suLFtmous ACID 235
lyProcednreA drop of the dyestuff solution is placed in a depression

of a spot plate, and a drop of the neutral test solution is added. The solu-
tion is decolorized in the presence of sulfite.
Limit of Identification: 1 y sulfur dioxide
Reagent: Malachite green solution: 10 g. malachite green in 400 ml.
water
It must be noted that neutral salts (e.g., zinc, lead, and cadmium salts)
considerably reduce the sensitivity of this sulfite test. Consequently, it
is not feasible" to prevent the interference due to sulfides (and hydroxides)
by the addition of, for instance, ZnSOi.'*
4. Test for small amounts of snlfites in thiosulfate solutions. Alkali
thiosulfates have no action on aldehydes, but neutral sulfites react with
aldehydes to give soluble neutral aldehyde bisulfite compounds, and
liberate an equivalent of alkali:
ECHO + NatSOa + HjO = RCH(OH)SO,Na + NaOH
Thus sulfites can be detected in the presence of thiosulfates by the
development of an alkaline reaction after the addition of an aldehyde.
Formaldehyde acts most rapidly.
IfProcedure"A drop of neutral 1% solution of formaldehyde is
added to 1 or 2 drops of the neutral thiosulfate solution (previously neutral-
ized by treatment with ZnClj, if necessary). The formation of alkali is
tested with phenolphthalein. In this way 0.1 mg. of NaaSOa may be iden-
tified m 0.05 ml. of 0.1 N NasSjOj.
Far smaller amounts of sulfite may be detected in the presence of any
amount of thiosulfate, when free alkali is absent, if use is made of the fact'*
that on oxidizing a sulfite-thiosulfate mixture with iodine:
sor~ -f- Is -1- HjO = sor~ + 21- -1- 2 H+
2s,or" + i2 = S4or" + 2i-
hydrogen ions are formed only in the oxidation of the sulfite. The result-
ing acidity can be revealed by the reddening of litmus paper.
IfProcedureA drop of the neutral test solution is stirred with an
iodine solution, on the spot plate, until the iodine color remains permanent.
A strip of litmus paper is placed in the brown solution, and immediately
afterwards in a thiosulfate solution, to remove the adsorbed iodine. In the
presence of sulfites, the lower end of the litmus paper is reddened.
" L. Rosenthaler, Mikrochemie, 8, 27 (1927).
* Studies with H. J. Kapulitzaa.
236 i n . TESTS FOR ACID RADICALS
Limit of Identification: 5 y sodium sulfite L- î ^ i.

/T If T -t i.innnn i t u n ^ the amount of
CoruxfnlrahonLimit: 1.10,000 j - ' x.. i- ^
(sodium thiosulfate
Reagents: i ) O.I iV^ iodine solution i
S) Litmus paper
S). 0.1 N sodium thiosulfate solution
5. Test for bisnlfites in the presence of sulfites.'^ It is well known that
because of hydrolysis, alkali sulfites, as salts of the weak sulfurous acid,
have an alkaline reaction in aqueous solution; bisulfite solutions act neutral.
In order to detect bisulfite in the presence of sulnte by a spot test, the
interaction of these compounds with bari\un chloride or hydrogen peroxide
may be applied. The reactions are:
SOr~ + Ba++ = BaSO,
HSOr + Ba++ = BaSO, + H+
or
sor" + H,02 = sor~ + HJO
Hsor + HsOj = sor~ + HSO + H+
Therefore, on stirring a drop of the test solution with barium chloride or
neutral hydrogen peroxide, the solution remains neutral when pure sulfites
are present, whereas the litmus shows an acid reaction when bisulfite is
present at the same time.
Reagents: 1) 1% solution of barium chloride, or 3% neutral hydrogen
peroxide, shaken with CaCOs
2) Litmus paper
6. Other tests for sulfites. /. Filter paper impregnated with the green
product of the action of light on 2-benzylpyridine is turned red by sulfites'* ,
(/d". Limit: 7.2 7 NaHSO, in 0.1 ml). GaseousSOj has the same effect, and
also SnCU.
3. Sulfurous acid can be detected through the reduction of
Fe [Fe (CN)] to TumbuU's blue by SO2." The test can be made in a gas
evolution apparatus (Id". Limit: 5 7 SOj).
SULFURIC ACID
1. Test with barium rhodizonate.'^ Barium salts give a red-brown -
precipitate (see page 165) with rhodizonic acid or sodium rhodizonate.
This result produced on paper is stable toward dilute hydrochloric acid,
" A. Villiers, Bull. soc. chim. [3], 47, 546 (1887). ' '
H. Freytag, Ber., 67, 1477 (1934).
" G. B. Hcisjg and A. Lerner, Ind. Eng. Chem., Anal. Ed., 13, 843 (1941).
G. Gutzeit, Helv. Chim. Acta, 12, 736 (1929).
SULFURIC ACID 237
whereas sulfates and sulfuric acid cause immediate decolorization owing to

the formation of the insoluble barium sulfate. This fact can be applied to
give a sensitive and specific test for sulfates.
llProcedureA drop of barium chloride is placed on filter paper fol-
lowed by a drop of a freshly prepared solution of sodium rhodizonate.
The red fleck is treated with a drop of the acid or alkaline test solution.
In the presence of sulfates, the red fleck of barium rhodizonate disappears.
The test can also be made in a depression of a spot plate. A suspen-
sion of colored barium rhodizonate is prepared by bringing together 1 drop
each of dilute barium chloride and sodium rhodizonate solution. The
color is discharged if a drop of a solution containing sulfate is added. A
blank test is necessary when detecting small quantities of sulfate.
Limit of IderUifieation: 5 y sodium sulfate
Reagent: Freshly prepared 0.1% solution sodium rhodizonate
A test for soluble sulfates, even better than the decomposition of
barium rhodizonate, is provided by barium sulfate, which is precipitated,
and then reduced to sulfide with metallic potassium. The sulfide is
detected by the iodine-azide test (see 4). The reduction to sulfide affords
a means of testing for traces of sulfate, as in preparations of pure products
(see page 466). If the sample is in acid solution, a drop should be evapo-
rated to dryness in a hard-glass tube with a drop of barium chloride (sulfate-
free) and the residue then tested as described on page 238.
2. Test with barium carbonate and phenolphthalein.^
Barium carbonate reacts rapidly with neutral alkali sulfates, on
warming:
BaCO, + NajSOi -^ BaSO* + NajCO,
The occurrence of the reaction can be detected by the addition of phenol-
phthalein, which turns red owing to the alkaline reaction of, the sodium
carbonate formed."
Among the other anions only siUcofluorides interfere, as they react
similarly to sulfates. For the test to be successful, the test solution must
necessarily be neutral. When alkaline soda solutions are present, as
when testing a soda extract, it is advisable to acidify a few drops of the
test solution with hydrochloric acid, evaporate to dryness over the water
bath, and then to treat with BaCOa. After this treatment, the limit of
identification is about double that with neutral solutions.
IfProcedureA drop of the neutral test solution is mixed with a drop
of a barium carbonate suspension in a microcrucible and evaporated to
F. Feigl, Rec. trav. chim., 68, 479 (1939).
dryness over, the water bath. A drop of an alcoholic solution of phenol-

phthalein is added. A piak or red color indicates sulfates.
Limit of Identification: 5 y sodium sulfate |
Concentration Limit: 1:10,000 '
Reagents: 1) Pure barium carbonate I
2) 1% solution of phenolphthalein in aqueous alcohol (1:1)
3. Test by precipitation of barium sulfate in the presence of permanga-
nate.""' If Ba++ ions are precipitated from a solution containing potassium
permanganate, by adding SOr~ ions, the barium sulfate adsorbs permanga-
nate or includes it in its lattice. Consequently, the precipitate is violet.
The permanganate thus carried down by bariiun sulfate is quite resistant
to all reducing agents that ordinarily attack it at once."' Accordingly, the
color of the excess permanganate in the liquid can be discharged and the
violet barium sulfate then becomes plainly visible. This adsorption forms
the basis of a test for barium (see page 167), as well as for the following
method of detecting sulfate.
IfProcedureThree drops of the solution to be tested for sulfate are
mixed on a spot plate with 1 drop saturated potassium permanganate
solution. One drop of the mixture is placed on dry filter paper impreg-
nated with .barium chloride, and the paper kept at 70 to 80C. for 7 or 8
minutes in a drying oven. The excess barium chloride is removed by
bathing the paper for about 1 minute in a dish filled with water, and then
rinsing it under the tap. The paper is then placed in 1 iV oxalic acid,
which removes any unused KMn04 as well as the MnOa precipitated in the
paper through the oxidation of the cellulose. A bright violet or pink fleck
or ring remains if barium sulfate is present.
Limit of Identificalion: 2.5 7 sulfuric acid
Reagent: Barium chloride paper. Filter paper is impregnated with
0.5 N BaCU and dried - . .
4. Test for insoluble sulfates.'"' Insoluble sulfates, e.g., alkaliiie earth
sulfates or lead sulfate, can be reduced to sulfides and identified by the
sensitive iodine-azide reaction described on page 227. "The test is specific
when insoluble sulfides or free sulfur are absent. ,
Insoluble sulfates {e.g., PbSO* or BaS04) can be very simply reduced
to sulfides by heating with metallic potassium in a glass capillary. The
details of this reduction, and the subsequent azide reaction can be carried
100 p Feigl and W. Aufrecht, Rec. trav. chim., 68, 1127 (1939).
" ' H. E. Wohlers, Z. anorg. allgem. Chem., 59, 203 (19087-
' " According to experiments carried out with L. Weidenfeld and L. Badian.
BtnjxnRic Acn> 239
out as described on page 314, where the detection of sulfur in organic

compounds is discussed. As little as 0.5 y CaS04 may thus be identified
in a drop of a dilute solution of gypsum. The test is so sensitive that traces
of lead sulfate dissolved in water (1 y PbSO) can be detected. The
resulting sulfide may alternatively be detected with sodium nitroprusside
(see page 226), but since this test for sulfide is less sensitive, larger amounts
of the test substance must be taken for reduction with potassium.
Rather less sensitive, but adequate in most cases, is reduction with
carbon (and sodium carbonate as flux):
BaS04 + 4 C = BaS + 4 CO
f ProcedureA sample (size of a pin head) is thoroughly mixed in a
small mortar with a few splinters of charcoal and four times the amount
of sodium carbonate. A portion of the mixture is fused on a Wedekind
magnesia spoon with a blowpipe, using an alcohol flame. The sulfate is
converted to sulfide. The melt, still wanh, is transferred to a microcentri-
fuge tube, a drop of water is added, and the mixture stirred with a glass
capillary. 1 or 2 drops of an iodine-azide solution are added. If sulfide
was formed by the reduction, the iodine-azide solution is decomposed with
evolution of nitrogen. The small bubbles can easily be seen as they rise
through the Uquid.
Limit of Identification: 36 y barium sulfate^"'
Reagents: 1) Sodium potassium carbonate
2) Charcoal
3) Iodine-azide solution (see page 228)
Another general method of detecting insoluble sulfates is discussed
on page 301.
5. Test for free (anboand) sulAiric acid.'"* Free (unbound) sulfuric acid
can be detected in the presence of (other) volatile mineral and organic
acids, and of mineral salts, by utilizing the dehydrating action of concen-
trated sulfuric acid. Cellulose (filter paper), starch, sugar, and the-like,
char when they are subjected to the removal of water. Charring also
occurs if solutions containing only a little free sulfuric acid are evaporated
to drjmess in the presence of carbohydrates, and the temperature then
raised to 120C. Free phosphoric acid, if present in considerable quantiti^,
exhibits an analogous action. Likewise free hydrochloric acid produces
" ' The limit of identification was determined as follows: a drop of a solution of
NaSO of known strength was placed on filter paper, treated with a drop of BaCIi,
and dried. A little NajCOi was added and the strip of filter paper was rolled, ashed
on a magnesia spoon, and the fusion made as described.
"Studies with N . Braile.
240 n i . TESTS FOB ACID RADICALS
partial charring. However, it can be completely removed by evaporation

with water."^
1[ProcediireSeveral mg. of glucose are placed in a microcrucible,
a drop of the test solution is added, and the crucible is placed in a drying
\
oven heated to 120C. If considerable quantities of free sulfuric acid are
present, distinct charring occurs very soon after the charge has gone to
dryness. With small quantities of acid, a black or brown ring will appear
after the sample has been kept at this temperature for about one hour. A
blank test with glucose will remain unchanged under this treatment.
If hydrochloric acid is present, a drop of the test solution is evaporated
in a microcrucible at 105 to 110C. Then one or two drops of water are
added and the evaporation is repeated. One drop of water and a pinch of
glucose are then introduced and then the test carried out as just described.
Limit of Identification: 8 7 sulfuric acid
THIOSULFURIC ACID
Test by catalysis of the iodine-azide reaction."^ As stated on page 227,
the reaction:
2 NaNs + I2 = 2 Nal + 3 N2
is catalyzed by soluble and insoluble sulfides, and by thiosulfates and
thiocyanates. Extremely small amounts of the sulfur-containing com-
pound may be detected by the evolution of bubbles of nitrogen. The test
is only applicable to the identification of thiosulfates in the absence of
sulfides and thiocyanates.'"'
iota The charring of organic materials by hydrochloric acid presents, at first
glance, a contradiction to the familiar fact that a dilute aqueous solution of this
acid, on concentration, forms an azeotropic mixture containing 20.2% HCl, which
boils unchanged at 110C. This constant-boiling mixture is obtained if the acid is
heated in glass or porcelain. However, hydrochloric acid is adsorbed by paper and
carbohydrates and, when retained in this fashion, gives off water at 120C. and then
dehydrates the adsorbent to replaice this evaporated water. This adsorption-effect
can be demonstrated by placing a drop of hydrochloric acid on filter paper and then
keeping the paper in an oven at 120C. until partial charring has produced a gray
fleck. If moistened congo paper is then pressed against the fleck, the indicator turns
blue. [F. Feigl, J. Chem. Education, 22, 344 (1945).]
" ' F. Feigl, Z. anal. Chem., 74, 369 (1928).
JM According to experiments carried out by H. Hamburg and L. Weidehfeld,
solutions of sulfides (even freshly prepared by mixing NaOH and HjS) always con-
tain some thiosulfate, even though the amount may be very small. This may be
demonstrated as follows: a drop of the solution is placed on a spot plate and a few
small crystals of Cd(N0i)8 are stirred in. A strip of filter paper (0.5 X 4 pm.) is then
dipped in this suspension of CdS. The clear liquid ascends the capillaries of the
paper, leaving the CdS at the lower end of the paper. After-1 or 2 minutes, the filter
paper is removed and the clear portion is cut off from that containing CdS, and placed
on a watch glass. A drop of iodine-azide solution is then placed on the moist paper;
a perceptible development of bubbles of nitrogen results. Some of the bubbles re-
main sticking to the watch glass when the paper is removed.
THIOSULPURIC ACID 241
It is remarkable that a solution of sodium thiosulfate that has been

treated with an excess of iodine, and thus quantitatively converted into
tetrathionate (2 Na2S2p3 + I2 -* 2 Nal + Na2S40), will still react with
sodium azide with discharge of the color and evolution of nitrogen. In
contrast, tetrathionate prepared by other methods of oxidation and then
recrystallized, shows no reaction with azide. Other sulfur compounds,
which can initiate the iodine-azide catalysis and which of themselves can
be ozidized by iodine, behave analogously. Traces of thiosulfate are
probably responsible for this effect; they remain even after the addition
of excess iodine and act as catalyst. This effect can be used as a test for
NajSsOa, though it is admittedly less sensitive. A drop of the thiosulfate
solution is treated in a microcrucible with 0.005 N iodine-starch solution
until the blue persists. One drop of 2% sodium azide solution is added
and the mixture is watched for discharge of color.""
IfProcedtireOn mixing a drop of the test solution and a drop of
iodine-azide solution on a watch glass, a more or less vigorous development
of bubbles ensues, according to the thiosulfate content.
Ldmit of Identificaiion: 0.15 7 sodium thiosulfate
The thiosulfate in a microdrop (0.025 ml.) of a 0.00001 N sodium
thiosulfate solution may be detected as follows.'"' The drop is taken up
in the loop of a platinum wire, evaporated by heating the wire adjacent
to the loop, in a Bunsen flame, and then heated to glowing. The loop of
platinum is then placed in a drop of iodine-azide solution suspended in an
inverted microcentrifuge tube. Tiny bubbles of gas are evolved and collect
in the capillary end of the centrifuge tube (see page 229).
Limit of Identification: 0.025 7 sodium thiosulfate
Reagent: Sodium azide-iodine solution. Solution of I g . sodium azide
in 100 ml. 0.1 N iodine solution
Test for thiosulfates in the presence of sulfides."" Thiosulfates may be
identified in the presence of small amounts of sulfide (see footnote 106,
page 240) by applying the reactions between sulfides and thiosulfates with
mercuric chloride:"'
S + Hg++ = HgS
S2O3 + Hg++ + H2O = HgS + SO4 + 2 H+
Thus, in the presence of thiosulfates, free sulfuric acid is formed; it can be
detected by litmus paper. HgClj itself has an acid reaction, due to hy-
' " Compare R. M. Fanstone, Brit. J. Phot., 76, 714 (1929).
' " Studies with R. Novacek.
' Compare A. Sander, Chem.-Ztg.,Si. 945 (1915).
242 m . TBSTB FOB ACID RADICALS
drolysis. This action with water must be prevented before making the
test for hydrogen ions. Potassium chloride will serve this purpose. The
complex compound KjHgCU is formed. j
f Procedure"'A drop of the test solution and a drop of mercuric
chloride solution are stirred together on a spot plate. If excess HgCU is
present, the white mercuric sulfo salt (2 HgS-HgCU) is formed. A little
potassium chloride is added and mixed in. A small strip of litmus paper
is dipped into the liquid. In the presence of thiosulfates, the paper turns
red.
Limit of Identification: 8 7 sodium thiosulfate I.. ,, , ,
n , f T u i.conn < tunes the amount of
Concentratton Limtt: 1.6200 ,. ,.,
l^sodium sulfide
Reagents: 1) 2% mercuric chloride solution
2) Potassium chloride (solid)
3) Litmus paper
PERSULFURIC ACID
Test with benzidine.'" Neutral or weakly acetic acid solutions of alkaU
persulfates turn blue on the addition of benzidine acetate, due to the forma-
tion of an oxidation product of benzidine (see page 55). Alkali peroxides,
perborates, and hydrogen peroxide do not react with benzidine under these
conditions. ITierefore, persulfates may be detected in the presence of these
other per-compounds.
Chromates, permanganates, ferricyanides, and hypohalogenites should
not be present, as they also oxidize benzidine to benzidine blue. Chlorates,
perchlorates, bromates, iodates, and nitrates do not react under the
conditions of the experiment, but they reduce the sensitivity of the per-
sulfate-benzidine reaction. Periodates give a brown, coloration.
Even more sensitive than bizidine is 2,7-diaminofluoraie"*
NH,
which, however, is mwe diflScult to obtain. This reagent reacts similarly

to benzidine, and may, in general, be substituted for benzidine.
^ProcedureA drop of the neutral or slightly acid (acetic) test
solution and a drop of benzidine acetate are mixed on a spot plate or in a
crucible. In the presence of persulfates, a more, er less intense blue
appears.
" Studies with H. J. Kapulitzas.
"> A. Monnier, Chem. Ahiiracts, XI, 426 (1917).
" J. Schmidt and W. Hindereri Ber., 65. 87 (1982).
NITRIC ACID 243
Limit of Identification: 0.25 7 potassium "1

persulfate ? in neutral solution
Concentration Ldmit: 1:200,000 j
Limit of Identification: 1 y potassium \
persulfate > in acetic acid solution
Concentration Limit: 1:50,000 J
In the presence of 3 mg. potassium bromate, 2.5 7 potassium persul-
fate may be detected; in the presence of 3 mg. potassium iodate, 0.5 7.
Reagent: 2% solution of benzidine in dilute acetic acid
NITRIC ACID
1. Test with ferrous sulfate and sulfuric acid."' When a crystal of ferrous
sulfate is brought into contact with a nitrate solution and concentrated
sulfuric acid added very carefully,*" a brown zone forms around the crystal.
This is due to an addition compound, FeNO SO4, formed from nitric oxide
and ferrous sulfate."' The reactions are:
2 HNO, + 6 FeS04 + 3 H2SO4 = 3 Fej (804)3 + 4 H2O + 2 NO
FeS04 + NO = FeNO-SO*
Nitrites react similarly to nitrates. Iodides and bromides interfere,
owing to the liberation of the halogen. They must therefore be removed
by precipitation of the silver haUdes."' Large amounts of chlorides reduce
the sensitivity. Other interfering ions are: cyanide, ferrocyanide, thio-
cyanate, chromate, sulfite, thiosulfate, and iodate. They react with
ferrous sulfate and concentrated sulfuric acid to give a visible change,
which makes it difficult to see the characteristic FeNO SO4 ring. Tung-
states and molybdates interfere, as they are reduced by FeS04 to colored
lower oxides.
^ProcedureA crystal of ferrous sulfate (pin head) is placed on a spot
plate together with a drop of the test solution. A drop of cone, sulfuric
acid is allowed to run in at the side of the drops. In the presence of nitrate,
a brown ring is formed around the ferrous sulfate crystal.
Limit of Identification: 2.5 y nitric acid
Reagents: 1) Ferrous sulfate (solid)
" Desbassins de Richemont, Chem. Zentr., 1836, 782.
"* The basis of the "ring test" for nitrates is discussed by E. Schroder, Z.
anorg. allgem. Chem., 202, 382 (1931).
' Compare W. Manchot, Ber., 47, 1601 (1914).
" A saturated solution of silver sulfate or acetate may be used. When large
amounts of halides are present it is better to use a solution recommended by M. J.
Murray and A. W. Avens, Ind. Eng. Chem., Anal. Ed., 4, 58 (1932), consisting of 7.8
g. AgjS04 in 25 ml. 4 JV NHI made up to 100 ml. with water.
244 III. TESTS FOR ACID KADICAL8
2. Test with diphenylamine or diphenylbenziSine. Tpie well known

diphenylamine reaction of nitric acid"'' depends on the oxidation of di-
phenylamine (I) through colorless N,N'-diphenylbenzidine (II) to its blue
quinoid imonium salt (III)"*
o--<o> (I)
_ +HN08
-NH
o-
(III)
The oxidation to the blue dye takes place from either diphenylamuie (I)
or from diphenylbenzidine (II). The latter compound has the advantage
that it better utiUzes the oxidizing action of the nitric acid and prevents the
oxidation from stopping at the diphenylbenzidine stage, if an excess of
diphenylamine is used."' The nitric acid test is therefore more sensitive
when diphenylbenzidine is used in place of diphenylamine.
It should be noted that the diphenylamine reaction proceeds especially
well in the presence of chlorides. Probablyfree chlorine is produced. This
in turn, furnishes (Clj + HjO > HCl + HOGl) particularly active
hypochlorous acid.**"
This color reaction is not specific for nitric acid, as other, oxidizing
agents (,e.g., nitrites, chlorates, bromates, iodates, chromates, permanga-
nates, vanadates, molybdates, peroxides, and ferric salts) also give blue
compounds with diphenylamine.
^ProcedureAbout 0.5 ml. of the strongly acid (sulfuric) diphenyl-
amine (or diphenylbenzidine) solution is placed on a spot plate, and a drop
of the test solution dropped in the middle. A blue ring forms as the two
liquids mix. The depth of color depends on the nitrate content.
" ' Compare J. Tillmans and W. SutthofE, Z. anal. Chem., 60, 473 (1911); I. M.
Kolthoff and G. E. Noponen, J. Am. Chem. Soc, 55,1448 (1933).,^
" H . Wieland, Ber., 48, 3296 (1913); 62, 886 (1919).- '
G. W. Monier-Williams, Analyst, 56, 397 (1931).
" Compare G. J. Barannikov, Chem. Abstracts, 33,6196 (1939).
NITRIC ACID 245
(o) With diphenylamine

Limit of Identification: 0.5 7 nitric acid
(6) With diphenylbenzidine

Reagent: Several crystals of diphenylamine or diphenylbenzidine"^
are covered with cone, sulfuric acid. A little water is added;
after solution is complete, cone, sulfuric acid is added.
About 1 mg. diphenylamine or diphenylbenzidine should
be present in 10 ml. of the finished reagent solution
3. Test with brucine.*" Brucine is an extremely poisonous alkaloid ob-
tained from seeds of the Strychnos family. Its constitution has not yet
been completely unravelled. It gives a red color when its sulfuric solution
is mixed with even minute amounts of nitrates. The constitution of the
product has not yet been determined; it is probably a nitration product.
Chlorates and nitrites give a similar color reaction. The removal of
nitrites will be described later.
^ProcedureA few drops of a solution of brucine in cone, sulfuric
acid are mixed on a spot plate with a few drops of the test solution. In
the presence of nitrate, a red color appears. On standing this changes
to yellowish-red.
Reagents: 0.02% brucine solution in sulfuric acid (prepare immedi-
ately before use). Pure cone, sulfuric acid usually
contains a trace'of nitrate or nitrite, and hence gives a
rose-red with brucine. If this acid is diluted with water to
a specific gravity of 1.4 and heated continuously to
boiling in a platinum dish, nitric or nitrous acids are re-
moved completely*"
Test for nitrates in nitrites

The sensitive color reactions for nitrates with brucine or diphenyl-
amine are not applicable in the presence of nitrites, which react similarly.
' " F o r preparation, see G. W. Monier-Williams, Analyst, 66, 397 (1931).
" ' R. Kersting, Ann., 125, 254 (1863).
" ' C. R. Fresenius, op. cit. (this text, page 101), p. 488.
246 HI. TESTS FOR ACID RADICALS'
Therefore all the nitrite must be destroyed beforehahd. Hydraxoic acid

can be used."*
HN, + HNOj = Nj + H,0 + N,0
The removal of nitrite with sodiiun azide is complete in acid solution.
No nitrous acid can be detected even in 0.0001 ^potassium nitrite solution
after this decomposition, when tested by potassium iodide or the naphthyl-
amine reaction.
Therefore, in order to test nitrites for nitrate content, sodium azide
should be added to the test solution, which is acidified and then allowed to
stand for a short time. It is then boiled to complete the reaction and to
remove the excess volatile hydrogen azide. After cooling, any of the usual
procedures may be applied to test for nitrates.
Another and even better method of destroying nitrites depends on
their reaction with aminosulfonic acid (sulfamic acid) :>"
MeNOj + NHj-SOsH = MeHSO* + H,0 + N,
This reaction is very vigorous, and,even at moderate concentrations
of the reacting substances, considerable heat is developed. The reaction
liquid froths up because of the violent evolution of nitrogen. In concen-
trated solutions the reaction is complete in a short time (about 1 minute);
in dilute solutions it is almost instantaneous. The nitrite in a 0.00005 N.
potassium nitrite solution cannot be detected even by the most sensitive
reagents immediately after mixing with aminosulfonic acid (0.5% solution).
Owing to the great velocity of the reaction, there is no need to fear a slight
oxidation of the nitrous acid, formed as an intermediate, to nitric acid,
except in very concentrated solutions.
All the operations for the removal of nitrite, by either sodium azide
or aminosulfonic acid,"' and the nitrate test itself, may be carried out on
a single drop or crystal of the test substance on a watch glass.
Even the purest nitrite preparations always show a slight nitrate
content,"' which must be considered when testing for nitrates in the
presence of nitrites.
4. Test after redaction to nitrite."' Nitrates in acetic acid solution can
be reduced to nitrites by metallic zinc."' They can then be detected by
" F. Sommer and H. Pincua, Ber.. 48, 1963 (1916). J. Thiele, ibid., 41, 2681
(1908).
" P. Baumgarten and I. Marggraff, Ber., 63,1019 (1930). ,
" For preparation, see P. Baumgarten, Ber., 69, 1978 (1926).
' F. L. Hahn and P. Baumgarten, Ber., 68, 3028 (1930).
" J. Blom, Ber., 69, 121 (1926).
" F. L. Hahn and G. Jaeger, Ber., 68, 2335 (1925), discuss the use of meUUic
lead for this purpose.
NITRIC ACID 247
tile very sensitive reaction of Griess (see page 248). Nitrites must be
removed before carrying out the test. The removal is best done with
sodium azide (page 245) or aminosulfonic acid (page 245).
^ProcedureA drop of the neutral or acetic acid test solution is mixed
on a spot plate with a drop of sulfanilic acid and a drop of a-naphthylamine
solution, and a few mg. zinc dust are added. In the presence of nitrates,
a red coloration gradually develops, which is due to .the formation of an azo
dyestuff (see page 248).
CoTicentration Limit: 1: 1^000,000
Reagents: 1) Sulfanilic acid solution \ oô
.; Naphthylamme
;2) XT 1-i.i- 1 solution]
^ J.- ( see page 248.
S) Zinc dust (nitrite- and nitrate-free): zinc dust is heated
on the water bath for an hour with dilute acetic acid ,
after cooling, the liquid is poured off, and the metal is
again stirred up with dilute acetic acid, filtered at the
pimip, washed with water, and dried
5. Test by reduction to ammonia. Nitrates are reduced to ammonia by
zinc or aluminum in alkaline solution, and are then readily detected.
Devarda's alloy, which consists of copper, zinc, and aluminum, may also
be used for the reduction. The ammonia is formed through the action of
nascent hydrogen:
Zn -f 2 NaOH -> Zn(0Na)2 -f 2 H
NOr -f 8 H -* OH- -f 2 HjO -I- NHj
This test is less sensitive than the other tests for nitrates, but it is
specific in the absence of nitrites which behave like nitrates. In the
presence of ammonium salts, (which must necessarily be removed before-
hand by boiling with alkah), only cyanides interfere. Alkali cyanides, on
heating with alkali, are decomposed with the production of formate and
ammonia:
KCN -1- 2 HjO = HCOOK -f NH,
and can, therefore, be mistaken for nitrates. The interference of cyanides
may be prevented by the addition of mercuric oxide (see page 183).
IfProcedweÂ drop of the test solution is placed in the apparatus
(page 31, Fig. 30), mixed with 1 or 2 drops of 10% sodium hydroxide and a
small quantity of powdered Devarda's alloy. A watch glass with a drop
of Riegler's reagent solution (see page 183) on its underside is placed on
the funnel stopper* The ammonia, liberated on warming, is taken up by
the reagent and can be identified by the formation of'a red ring, 10 to 15
seconds after the addition of a grain of calcium oxide.
Ldmit of Identification: 10 y nitric acid !
NITROUS ACID
1. Test with sulfanilic acid and tt-naphthylamine."" Nitrous acid reacts
with aromatic amines in acid solution:
RNH2HCI + HNO2 -> [RN^N]C1 + 2 H2O
with the formation of diazonium salts, which react with a second molecule
of the amine:
[RN=N]C1 + R-NHj - RN=NRNHa-HCl
forming an aminoazo compound.
The intense color of azo dyestuffs formed in this way serves as a test
for very small amounts of nitrite.
The best substance to use for this test for nitrites is sulfanilic acid (I),
SO.H NHj
NH, W
(I) (II) (III)
with subsequent coupling of the resulting diazoniimi compound with

a-naphthylamine (II), giving the red dyestuff (III).
^Procedure-Â drop of the neutral or acetic acid test solution is mixed
on a spot plate with a drop each of sulfanilic acid and of a-naphthylamine.
According to the nitrite content, a red color is formed, either at once or
after standing for a short time."*
Limit of Identificaiion: 0.01 7 nitrous acid
Reagents: 1) Solution of sulfanilic acid in acetic acid. 10 g. sulfanilic
acid are dissolved in 1000 ml. 30% acetic acid, by
warming
" P. Griess, Ber., 12, 427 (1879). Compare F. L. Hajjn and G. Jaeger, ibid ,
58, 2335 (1925) and J. Blom, ibid., 69, 121 (1926).
' " The diazo reaction for nitrite may be carried out as a spot reaction on filter
paper impregnated with sulfanilic acid-a-naphthylamine, when the limit of ide.n-
ttfication is 0.00005 7 NOf. F. L. Hahn, Mikrochemie, 9,31 (1931).
NITROUS ACID 249
2) Solution of a-naphthylamine-acetic acid. 0.03 g a-

naphthylamine is boiled in 70 ml. water; the colorless
solution is decanted from the blue-violet residue and
mixed with 30 ml. glacial acetic acid
2. Test with 1,8-naphthylenediainine.^^' Nitrites react in neutral solu-
tions with 1,8-naphthylenediamine:
+ V > y<( >

^TVT . \ / ^W ^ 2H,0
H
An orange-red precipitate of 1,8-aziminonaphthalene is produced.'"
Only selenious acid, among the other acids, reacts with formation of a
colored precipitate (see page 266); other acids, e.g., sulfuric acid, give
colorless insoluble salts.
IfProcedureÂ drop of the test solution is mixed with a drop of
1,8-naphthylenediamine in a microcrucible. An orange-red precipitate or
coloration appears either iimnediately, or after warming, according to the
nitrite content.
LimH of Identification: 0.1 7 nitrous acid
Reagent: 0.1% solution of 1,8-naphthylenediamine"* in 10% acetic
acid
3. Test by release of iodine on filter paper containing starch."" Nitrites
react with iodides in acid solution:
2 NOr -H 2 1 - -f 4 H+ ^ I2 -f 2 H2O H- 2 NO
If this oxidation is carried out on filter paper that contains a little starch,
even minimal quantities of the resulting blue starch-iodine (see page 198)
are seen easily because of fixation on the surface of the paper, and by
contrast with the white background. Most spot papers contain sufficient
starch. Other oxidizing agents that liberate iodine from iodides in acid
solution must be absent.
KProcedureThe filter paper is tested beforehand for starch. One
drop each of 2 iV acetic acid, test solution, and 0.1 N potassium iodide, are
placed successively on suitable filter paper. According to the quantity of
nitrite present, a blue fleck or ring appears.
" F . Feigl, unpublished studies.
" A. de Aguiar, Ber., 7, 315 (1874).
For preparation, see R. Meyer and W. MttUer, Ber., 30, 775 (1897).
" C. L. Wilson, Chemistry & Industry, 69, 378 (1940).
Ldmit of Identification: 0.005 y nitrous acid I

4. Other tests for nitrites. 1. A freshly prepared alcoholic, acid solution' of
chrysean (aminothioamide of thiazole) gives a red color and subsequently
a dark brown precipitate with nitrites.''" This reaction may b^ applied
as a spot test (/d". Limit: 0.25 y nitrite).
2. A drop each (0.01 ml.) of the test solution and of an acetic acid
solution of benzidine are brought successively on filter paper. A yellow or
brown dye appears, owing to diazotization"^ {Id". Limit: 0.7 y NaNOj).
3. The "ring test" (see page 243), due to the formation of FeNO SO*,
can also be used as a test for nitrite if acetic acid is used in place of sulfuric
acid."' Nitrates give no reaction under these circumstances (7d". Limit:
2 y HNOs).
PHOSPHORIC ACID
Test with anunoniam molybdate and benzidine.''^ Phosphates form
salts of the complex phosphomolybdic acid H7P(M6207) with molybdates
in solutions containing mineral acids. The yellow ammonium salt, owing
to its limited solubility, is often used for the detection and determination
of phosphoric acid. Germanic, arsenic, and silicic acids behavie similarly
to phosphoric acid, and react with molybdates in acid solution to form
germanomolybdic acid HgGe(Mo207), arsenomolybdic acid H7As(Mos07),
and siUcomolybdic acid HSi(Mo207), respectively.
In these polyhetero acids the complex molybdic acid has an enhanced
oxidizing power toward many inorganic and organic compounds, which
are oxidized only slightly, if at all, by free molybdic acid and molybdates.
Thus, iodides are Uttle oxidized by molybdates in acid solution, even on
warming, whereas phosphomolybdic acid Uberats appreciable amounts of
iodine, even in the cold.""
BoizidJne (see page 55), which is unaffected by free molybdic acid
and normal molybdates, is oxidized instantly by phosphomolybdic, acid,
and even by its insoluble ammonium salt in acetic acid solution. This
oxidation is applied in the test for phosphates. The reaction is extremely
sensitive, as two blue products are formed: the oxidation product of benzi-
dine (benzidine blue) and the reduction product of molybdic acid (molyb-
denum blue). Solutions of phosphate which are too dilute to show a
" J. V. Dubsk^, J. Trtilek, and A. Okdc, Mikrochemie, 16, 99 (1934).
" N. A. Tananaeff and A. M. Schapowalenko, Z. anal. Chem., 100, 350 (1936).
" C. J. Engelder, T. H. Diinkelberger, and W. Scbilte'r, Semi-micro Qualita-
tive Analyns. 2nd-ed., Wiley, New York, 1940, p. 183.
" ' F. Feigl, Z. anal. Chem., 61, 454 (1922); 74, 386 (1928); 77, 299 ( 1 ^ ) .
" Further instances are given in Feigl, op. cit. (this text, page 2), p. 62.
PHOSPHORIC ACID 251
precipitate with ammonium molybdate, nevertheless react with molybdate

and benzidine to give a distinct blue.
Arseno- and silicomolybdic acids and their salts react similarly with
benzidine. However, under suitable conditions, phosphate may be deci-
sively detected even in the presence of large amounts of arsenic and silicic
acids.
When the solution contains much hydrogen peroxide, permolybdates
are formed on the addition of ammonium molybdate.*" Consequently,
no precipitation of (NH4)3P04 12 M0O3 occurs. The hydrcên peroxide
must therefore be destroyed before carrying out the test. Similarly,
oxalates and fluorides interfere with the quantitative precipitation of phos-
phate, owing to the formation of stable complex compounds with molyb-
denum.
llProcedureA drop of the acid test solution is placed on quantitative
filter paper, followed by a drop of molybdate and a drop of benzidine.
Then the paper is held over a dish of anunonia. When most of the free
mineral acid is neutralized, a blue stain is formed on the paper, the intensity
depending on the phosphate content.
Limit of Identification: 1.25 7 PjO
Arsenates do not react under these conditions, as the formation
of araenomolybdic acid only proceeds very slowly in the cold. In this
way, 1.5 7 phosphoric acid may be detected in the presence of 1.5 mg.
arsenic acid {Limiting proportion 1:1000).^**
An even greater sensitivity may be attained as follows; a drop of
the ammonium molybdate solution is placed on filter paper (S & S 589)
and dried in an air oven. A drop of the test solution is placed on the
freshly prepared paper, followed by a drop of a benzidine solution, and a
drop of sodium acetate solution. According to the amount of phosphate
present, a blue fleck or ring is formed.
Limit of Identification: 0.05 7 P2O5
Reagents: 1) Ammonium molybdate solution. 5 g. ammonium
molybdate are dissolved in 100 ml. cold water and
poured into 35 ml. nitric acid (sp. gr. = 1.2)
S) Benzidine solution. 0.05 g. benzidine or benziduje
hydrochloride is dissolved in 10 ml. cone, acetic
acid and diluted with water to 100 ml.
"' F. Feigl, op. cit., page 62.
" laterference due to AsiOi can be prevented, by wanning the teat solutioa
with HjSOi; AsiOj is formed by reduction and this does not react with molybdate.
It is advisable to remove excess HiSOi by addition of an alkali nitrite to the acid
solution. See N. A. Tananaeff and C. N. Potschinok, Z. anal, Chem., 88, 273 (1932)'.
252 III. TESTS FOB ACID RADICALS
S) Saturated sodium acetate solution

4) Ammonia
Test far phosphoric acid in the -presence of silicic add^*^
Soluble silicates also react with molybdic acid, under the above
conditions, forming a soluble silicomolybdic acid. This product, in its
turn, reacts with benzidine similarly to the phosphoric acid compound,
thus impairing the decisive nature of the test for phosphate.
It is possible, however, to detect phosphoric acid in the presence of
silicic and arsenic acids by utilizing the fact that, under suitable conditions,
the formation of silicomolybdic and arsenomolybdic acids may be pre-
vented by tartaric acid. This masking depends on the formation of a
stable complex compound of molybdic and tartaric acids, in which the
molybdic acid does not react with arsenic and silicic acids, but is not
masked toward phosphoric acid.
IfProcedureA drop of the test solution is placed on filter paper fol-
lowed by a drop of a tartaric acid-molybdate solution. The paper is held
over a hot wire gauze to accelerate the reaction. A drop of benzidine
reagent is then added, and the paper is developed over anwnonia.
Ldmit of Identification: 1.5 y'PiOi fin the presence of 500 times
Concentration Limit: 1:33,000 \the amount of silicic acid
Reagent: Tartate-ammonium molybdate solution. 15 g. crystalline
tartaric acid are dissolved in 100 ml. of the usual nitric
acid-ammonium molybdate solution. Other reagents as in
the previous test
Test for phosphate in minerals and rocks, see page 471.

SILICIC ACID
Test with ammoniTim molybdate and benzidine."* Soluble silicates form
the complex silicomolybdic acid ll4Si04-12Mo03-aq, when treated with
molybdate in acid solution. Its ammoniimi salt differs from the ammonium
salts of the analogous phosphoric and. arsenic acid compounds in that it is
soluble in water and acids and gives a yellow solution."* The silicomolyb-
dic acid, like the corresponding phosphomolybdic acid (see page 250),
oxidizes ben2!idine in acetic solution to a blue meriquinoid product, and
simultaneously the molybdenimi is reduced to "molybdenum blue."
" ' F . Feigl, Z. anal. Chem., 77, 299 (1929).
" ' F. Feigl and P. Krumholz, Mikrochemie (Pregl-Festschrift), 1929, 82.
" ' The detection of silicic acid in drinking water by the formation of the sol-
uble, yellow silicomolybdate was first described by A. Jolles and F. Neurath, Z.
angevi. Chem., 11, 315 (1898).
SILICIC ACID 253
As the silicomolybdic acid is only formed sufficiently rapidly and com-

pletely at higher temperatures, the silicate solution must be gently warmed,
either in a small crucible or on filter paper, after the addition of the molyb-
date. When heated in a crucible, care must be taken that the liquid does
not boil, as this might cause traces of silicic acid to dissolve out of the
porcelain. The test then would lead to false conclusions.
Phosphoric and arsenic acids form compounds similar to siUcomolyb-
dic acid; they also give a color reaction with benzidine. These acids
must therefore be removed before the test. Regarding other interferences,
see page 251.
fProcedure(a) A drop of the test solution and of the molybdate
solution are placed on filter paper and gently warmed over a wire gauze.
A drop of benzidine solution is added and the paper is developed over
ammonia. A blue color indicates silicic acid.
Ldmit of Identification: 1 y Si02
(b) A drop of the slightly acid test solution (the acidity should not
exceed 0.5 N) is placed in a microerucible, mixed with a drop of molybdate
solution, and carefully warmed over a wire gauze imtil bubbles form.
After thorough cooling, a drop of benzidine solution is added, and then a
drpp of sodium acetate. A blue color indicates silicic acid.
Limit of Identification: 0.1 y Si02
The crucible must be tested for resistance to acids before it is used.
A drop of water and a drop of molybdate solution are mixed in the crucible,
warmed, and treated as described. Only those crucibles which give no
trace of blue after addition of the benzidine and sodium acetate are suitable
for carrying out the test.
Reagents: As for the phosphoric acid test, page 251
Test for silicic acid in the presence of phosphoric acid
When silicic acid is to be detected in the presence of much phosphoric
acid, the test must be carried out in the filtrate, after precipitation with
ammonium molybdate. The detection of silicic acid is simplified by
the addition of oxalic acid, which causes decomposition of small amounts of
(NH4)3P04'12Mo03, whereas silicomolybdic acid is stable toward oxalic
acid.
IfProcedureA drop of the test solution (the PjOs content should not
exceed 0.1 mg.) is mixed in a microcentrifuge tube with 2 drops molybdate
solution, and centrifuged. The supernatant liquid is transferred to a
microerucible by a capillary tube, and gently warmed. After cooling, 2
drops of 1% oxalic acid is added to destroy remaining traces of ammonium
254 III. TKSTS FOR ACID RADICALS
phosphomolybdate. A drop of benzidine and a few drops of sodium acetate

are then added. A blue color indicates silicic acid. . ,
Limit of Identification: 6 y SiOs fin the presence 'of 250 times
Concentration Limit: 1:8300 \the amount of PJOB
Reagents: Those listed (page 251) and 1% oxaUc acid solution
Test for silicic acid in minerals and rocks, see p ^ e 469.
CARBONIC ACID
Test vith sodium carbonate and phenolphthalein.'*^ It is a well known
fact that solutions of carbonates, because of hydrolysis, react alkaline
toward phenolphthalein. A solution of sodium carbonate colored red by
phenolphthalein is decolorized by free carbon dioxide. The latter reacts
with the carbonate to form bicarbonate:
NajCOa + CO2 + H2O = 2 NaHCO,
In the presence of a small excess of free carbon dioxide (3 to 5%), such
solutions have an acidity which is above the change point of phenol-
phthalein.
A rather sensitive test for carbonates is based on this fact. The car-
bon dioxide is liberated by dilute acid and taken up in a drop of sodium
carbonate solution colored red with phenolphthalein. The gas is definitely
identified by the decolorization which takes place.
The concentration of the reagent solution must be so selected that
it is not decolorized, imder the conditions of the experiment, by the carbon
dioxide in the air.
IfProcedureThe gas apparatus described on page 30 and shown in
Figure 27 is used. In it, 1 or 2 drops of the test solution or a pinch of the
solid is treated with 3 drops of 2 iV^ sulfuric acid. A drop of a solution of
sodium carbonate, reddened with phenolphthalein, is put on the knob of
the stopper, which is then placed in position. The drop is decolorized
either instantaneously, or after a short time, according to the amount of
carbon dioxide formed. In order to avoid false conclusions due to the
carbon dioxide in the air, a blank test should be carried out in a duplicate
apparatus.
Limit of Identifixxttion: 4 y carbon dioxide (in 2 drops of solution)
Reagents: 1) I ml. of a 0.1 iV sodium Carbonate solution mixed
with 2 ml. 0.5% phenolphthalein and 10 ml. water
8) 2 N sulfuric acid -" '
F. Feigl and P. Krumholz, Mikrochemie, 8, 131 (1930).
CARBONIC ACID 265
Sulfides, sulfites, thiosulfates, cyanides, fluorides, acetates, and ni-

trates interfere. The respective volatile acids, liberated on acidifjong,
also decolorize the drop of phenolphthalein-soda. Under suitable condi-
tions, however, the carbonate test may be carried out successfully even in
the presence of large amounts of the materials listed.
Test for carbonates in the presence of cyanides, azides, sulfides, sulfites,

thiosulfates, fluorides, and nitrites'^*''
Cyanides and azides may be converted into insoluble silver cyanide or
azide by the addition of a few drops of a saturated solution of silver liitrate.
Limit of Identification: 5 y CO2 in the f2500 times the amount of
presence of \ K C N or NaNa
Sulfides, sulfites, and thiosulfates can be quantitatively o x i d i ^ to
sulfates by hydrogen peroxide; they do not interfere then.-
20,000 times the amount
of Na2SjOj, 10,000 times
Limit of Identification: 5 7 CO2 in the
the amount of KjS, 10,000
presence of
times the amount of
NajSOs
Fluoride interference may be prevented by formation of the complex
^ZrF^" ions by adding a concentrated solution of zirconium chloride.
Limit of Identification: 5 7 GO2 in the presence of 1000 times the
amount of K F
Nitrites may be rendered harmless by treatment with aniline hydro-
chloride; the aniline is diazotized and the nitrous acid is consumed.
Limit of Identification: 5 7 CO5 in the presence of 1000 times the
amount of KNO2
UProcedureÂll the substances necessary to prevent interference
may be added before the evolution of the carbon dioxide, if necessary, in
the apparatus in which the test is carried out. The rest of the procedure
is as described.
Another method for removing anions (including acetate and formate)
that interfere with the test for carbonate, is to precipitate the latter by
adding calcium chloride. The precipitation, washing, and isolation of the
CaCOj can be accomplished in the bulb of the gas evolution apparatus, if
the latter is placed in a centrifuge tube.
Test for bicarbonate in the presence of carbonate
Calcium hydrogen carbonate, Ca(HC03)2, in contrast to CaCOa, is
soluble in water, and on the addition of ammonia is converted into CaCOj.
" F. Feigl, unpublished studies.
256 in. TESTS FOR ACID RADICALS
Therefore, when testing for bicarbonate in the presence of carbonate,

1 or 2 drops of the solution (for very small amounts of bicarbonate, about
1 ml.) is placed in an Emich microcentrifuge tube, or even a larger cen-
trifuge tube, and precipitated with an excess of calcium chloride solution.
After centrifuging, a drop of ammonia is added to the clear liquid. In the
presence of calcium bicarbonate, a turbidity of calcium carbonate appears.
Instead of precipitating the carbonate with ammonia, the clear
bicarbonate solution, obtained as described, may be tested for carbon
dioxide in the apparatus used in the previous procedure.
BORIC ACID
1. Test with tincture of curcuma."* Free boric acid gives a deep red prod-
uct when evaporated with tincture of curcuma (turmeric). The boric
acid brings about the change of the yellow curcumin (diferuloylmethane)
CHs [C(>-CH=CHCeHs (0H)0CH3 ]i
into the isomeric red-brown rosocyanine."' A loose addition product of
boric acid and curcumin is formed as an intermediate product. The
rosocyanine is turned blue to greenish-black by alkalis, and the original
brown-red color is restored by acids.
Iron (III), molybdenum, titanium, niobium, tantalum, and zir-
conium compounds also turn curcumin red-brown. However, the color
produced by these compounds, unlike that due to boric acid, does not
change to blue or green with alkalis.
The curcuma reaction is hindered by oxidizing substances (hydrogen
peroxide, chromates, nitrites, chlorates, etc.) and by iodides. Conse-
quently, these must be decomposed or removed before carrying out the
reaction.
IfProcedui-e^^(a) A drop of the test solution acidified with hydro-
chloric acid is placed on a strip of curcuma paper ( 3 X 7 mm.), and dried
at 100 C. A red-brownfleck,which turns blue to greenish-black on treat-
ment with 1% sodium hydroxide, indicates the presence of boric jicid.
Limit of Identification: 0.02 y boron
(b) A drop of the test solution is placed on a naicroscope slide and
acidified with a drop of hydrochloric acid. A thread of silk impregnated
with curcuma^*" is placed in the solution, which is then evaporated by
warming gently. In the presence of boric acid, the thread is colored pink-
violet, and on treating with 1% sodium hydroxide, the color '^changes to
" F. W. Daube, Ber., 3, 609 (1870).
"9 M. E. Schlumberger, Bull. soc. chim. [2] 5, 194 (1866); L. Clarke and C. L.
Jackson, Am. Chem. J., 39, 696 (1908).
" E. M. Chamot and H. J. Cole, Ind. Eng. Chem., 10, 38 (1918).
BORIC ACID 257
that of Prussian blue. Molybdenum, titanium, zirconium, and tantalum

salts do not interfere with the test carried out in this way. The sensi-
tivity is decreased by free phosphoric and silicic acids.
Reagents: 1) Tincture of curcmna. 20 g. curcuma are boiled
with 50 ml. alcohol, filtered, and the extract diluted
with 50 ml. water
2) Curcuma paper. Quantitative filter paper is soaked
in the tincture of curcuma and dried
3) Curcuma silk. Threads of viscose silk are soaked in
the tincture after the addition of alkali (1 ml. 10%
NaOH per 100 ml. tincture). The wet threads
are heated until the mass becomes syrupy. The
threads are then immersed in 0.5% alcohol, pressed
between tklter paper, then immersed in dilute sulfuric
acid, and finally washed with water, and dried
2. Test with hydroxyanthraquinones.^^' Many hydroxyanthraquinones
dissolve in concentrated sulfuric acid with intense color formation. With
bone acid these solutions give characteristic color changes which may be
appUed also in the detection of anthraquinones."^ These changes of color
are apparently due to the formation of inner complex boric acid esters
involving the OH groups in the -peri position:
O OH
+ B(OH). + HjO
For the detection of boric acid, the best of these compounds are
1,2-dihydroxyanthraquinone sulfonic acid (alizarin S), 1,2,4-trihydroxy-
anthraquinone (purpurin), and 1,2,5,8-tetrahydroxyanthraquinone (quin-
alizarin).
f ProcedureÂ drop of the slightly basic test solution is evaporated
to dryness in a microcrucible, treated with 2 or 3 drops of the reagent solu-
tion, and gently warmed. The evaporation must take place in the pres-
" F . Feigl and P. Krumholz, Mikrochemie (Pregl Festschrift), 1929, p. 77.
' " Compare J. Houben, Das Anthrazen und die Anthrachinone. Thieme,
Leipzig, 1928, p. 343.
ence of alkali, in order to avoid loss of boric acid in jthe steam. In the
presence of boric acid, the following color changes will be seen:
Alizarin S: yellowish-red to red ,|
Limit of Identification: 1.0 7 boron '
Purpurin: orange to wine red '
Limit of Identification: 0.6 7 boron
Quinalizarin: violet to blue
Limit of Identification: 0.06 y boron
Fluorides and oxidizing substances (nitrates, ferricyanides, etc.)
interfere with the reaction. The latter are easily removed by igniting the
dried residue.
Reagents: 1) 0.2% solution aUzarin S L eoncentrated sulfuric
2) 0.5% solution purpunn loc'd
S) 0.01% solution quinalizarin [
3. Test with jp-nitrobenzeneazochromotropic acid.^" The addition of
borates to the blue solution of p-nitrobenzeneazochromotropic acid, in
concentrated sulfuric acid, causes the color to change to greenish-blue.
The reason, for the change of color is probably analogous to that in the
reaction of boric acid with hydroxyanthraquinones (Test 2), in which an
inner complex ester of boric acid is formed. The reagent (chromotrope
2B) has two OH groups in peri position:
OH OH
I T
HO3SvJ\yL-SO,H
The detection of boron by this color reaction is adversely affected by

oxidizing agents and fluorides. The former give a red or yellow color
with the reagent, whereas fluorides prevent the formation of the'colored
ester, due to the formation of fluoboric acid or boron fluorides. Under
certain conditions, however, boron can be detected in the presence of these
compounds, but the sensitivity of the test is lower.
IfProcedureA drop of the slightly alkaline test solution is evaporated
to dryness in a porcelain dish. The residue, while the dish is still warm, is
stirred with 2 or 3 drops of the reagent. After cooling, the color is ob-
served. In the presence of boric acid, the color changes from blue-violet
to greenish-blue. A blank test is necessary only when very small amounts
of boric acid are involved.
"A. S. Komarowsky and N. S. Poluektoff, Mikrochemie, 14, 317 (1933/34).
BOBIC ACID 259
Limit of Identification: 0.08 y boron (in 0.04 ml.)

Reagent: 0.005% solution of chromotrope 26*'* in cone, sulfuric acid
Test in the presence of oxidizing agents or fluorides
Nitrates and chlorates (and probably other oxidizing compounds)
may be rendered innocuous by evaporating with solid hydrazine sulfate
(reduction). Fluorides may be removed by evaporation with silica and
sulfuric acid (volatilization of SiF).
IfProcednre1 or 2 drops of the test solution are treated, in a porce-
lain crucible, either with a little solid hydrazine sulfate, or a very small
quantity of silica and 1 or 2 drops of cone, sulfuric acid. The contents of
the crucible are carefully heated until fumes of sulfuric acid are evolved.
The warm residue is treated with 3 or 4 drops of the reagent solution, and
any color change noted after cooling.
in the presence of 13,000
times the amount of potas-
sium nitrate
Limit of Identificaiion: 0.25 y boron I
in the presence of 11,600
times the amount of potas-
sium chlorate
0.5 y boron in the presence of 2700 times the
amount of sodium fluoride
Test for boron in rocks, minerals, etc., see page 470.
4. Test by decomposition of methyl borate witli alltali flaoride."" Boric
acid reacts with alkali fluorides:
B(OH), -F 4 KF = KBF4 + 3 KOH
The free alkali hydroxide can be detected by the formation of a black
precipitate (2 Ag-MnOj) on treatment with silver-manganous reagent.
The reaction is discussed on page 42. In this way, the presence of boric
acid is confirmed.
Usually, either acid or alkaline solutions of borates are to be tested,
so the boric acid should be ccHiverted beforehand to its volatile methyl
ester, b.p. 65 C. This is distilled into the fluoride-containing reagent
solution. The ester is then saponified:
B(OCH,), -h 3 H2O = B(OH), -f 3 CH,OH
regenerating free borie acid that attacks the fluoride, with production of
OH- ioDB.
"* For preparation, see A. S. Komarowsky and N. S. Poluektoff, loc. cii.
F. Feigl and L. Badian, unpublished studies.
260 m . TESTS FOR ACID RADICALS
^ProcedureThe distillation can be carried out in the apparatus

described on page 32 (Fig. 33). A porcelain crucible, paraffined inside,
serves as receiver and should contain about 1 ml. rjeagent solution. A
drop of the test solution (plus a drop of alkah if the solution is acid) is
placed in the distillation apparatus, and evaporated to dryness. Five drops
cone, sulfuric acid and 5 drops methyl alcohol are then added, and, after
stoppering the apparatus, it is heated to about 80 C. in a water bath.
The volatile methyl borate distills into the receiver and undergoes saponifi-
cation. The resulting alkali causes the formation of a black precipitate.
For very small amounts, it is advisable to add a few drops of an acetic acid
solution of benzidine to the microcmcible. Traces of MnOa are revealed
by the blue color (see page 135).
Ldmit of Identification: 0.01 7 boron
Reagents: 1) Cone, sulfuric acid
2) Pure methyl alcohol
3) Acetic acid-benzidine solution (for preparation see
page 135)
4) Manganese-silver solution containing fluoride. 2.87 g.
Mn(N03)2 and 1.69 g. AgNOs are dissolved in 100 ml.
water, a drop of dilute alkali added, and the solution
filtered from the black precipitate. A solution of
3.5 g. potassium fluoride in 50 ml. water is added
to the filtrate; a white precipitate forms; on heating
it turns gray. The mixture is filtered, and the clear
solution used as the reagent
5. Other tests for boric acid. 1. The increase in acidity with organic
polyhydroxy compounds may be applied as a test for boric acid.*^' On
mixing equialkaline solutions of boric acid and a polyhydroxy compound
that can combine with boric acid, the pH of the mixture is lowered,- owing
to the production of a stronger acid than the boric acid. This increase in
acidity may be detected by the use of suitable indicators. It is advisable
to use bromothymol blue as indicator, and to treat the test solution with
acid or alkali, as required, until the indicator turns green; if mannite is
then added, the color turns yellow in the presence of boric acid. For
detecting extremely small amoimts and low concentrations of boric acid,
the mannite should be recrystallized beforehand from a solution neutralized
to bromothymol with base, washed with pure acetone, and dried on the
water bath. The test solution, prepared as described, ts divided into two
" F. L. Hahn, Com-pt. rend., 197, 762 (1933). Compare also A. S. Dodd, Ana-
lyst, 54, 282 (1929).
PERMANGANIC ACID 261
portions. To one, mannite is added, jand then the color of the two por-
tions is compared. The color change is appreciable down to concentrations
of 0.02 7 per ml. Two drops of solution on a spot plate are sufficient for
the test (Id". Limit: 0.001 y B).
B. A color change from red to blue results on the addition of 0.05%
solution of canninic acid, in cone, sulfuric acid, to solutions containing
small amounts of B2O3 (/d". Ldmit: 0.1 7 B in 0.03 ml.)."'
S. One drop of the test solution, one drop cone, sulfuric acid, and 5
drops methyl alcohol are mixed in a porcelain crucible. Thef mixture is
wanned and the resulting volatile methyl borate set on fire. It bums with
a green flame.^"*
P E R M A N G A N I C ACID
Test for permanganate in the presence of chromate^^^
If no other colored ions are present, permanganate is easily recognized
because the violet Mn07 ions are quite visible even at high dilutions. The
detection of permanganate in the presence of much chromate or bichromate
is of practical importance since the intense color of the CrOr" or Cr207"~
ions may blanket the violet color of the MnOr ion.
The method given here depends on the fact that a rapid oxidation of
cellulose occurs when a drop of permanganate solution is placed on paper.
Within a few minutes finely divided Mn02 is formed and remains as a
circular fleck. Its color is dark to light brown depending on the extent
of the reduction of the permanganate. Even very dilute pennanganate
solutions act on cellulose and the resulting slight precipitate of Mn02
is distinctly visible because of localization of the MnOj as well as by
contrast with the white paper. Under similar conditions alkali chromate
is practically without action on filter paper, even at high concentrations.
Cellulose is oxidized by chromate only very slowly; brown, difficultly
soluble chromic chromate is produced. If a solution contains both
chromate and permanganate, only the permanganate reacts at first. The
MnOj formed is retained as a central fleck, while the chromate migrates
through the capillaries and forms a concentric yellow ring around the
fleck of MnOj. The greater part of the chromate can be washed away
by adding water drop by drop, or by soaking the paper in this solvent.
Thus, even traces of permanganate can be detected by the production of
MnOj. It is necessary to wash away the chromate only when traces of
permanganate are involved. Normally the fleck of Mn02 is distinctly
visible, even on filter paper colored yellow by chromate.
1" F . P. Sorkin, Chem. Zentr., 1937, H, 632.
" W. Stahl, Z. anal. Chem., 101. 342 (1935).
" F . Feigl and H. A. Suter, Chemist-Analyst, 32,4 (1943).
It should be noted that the fleck of MnOj formed frpm a very dilute
solution of pure permanganate is less intense than a fleck produced from
the same permanganate solution to which alkali chromatejhas been added.
Moreover, when using solutions of pure permanganate, the limit of visi-
bility of MnOa lies at much higher concentrations than in solutions which
also contain chromate. This observation probably arises from the fact
that permanganate produces disintegration products of cellulose which
are then oxidized by the chromate. The resulting brown chromic chro-
mate strengthens the color of the MnOj fleck. Consequently, this height-
ened sensitivity involves an oxidation by the chromate, a result induced
by the preliminary reaction of the permanganate.
^ProcedureA drop of the neutral or slightly acid test solution is
allowed to soak into thick filter paper (S & S 601). If permanganate is
present, a dark to light brown central circular stain appears, surrounded
by a yellow zone. In the abseace of permanganate, only a yellow circular
spot forms. When very small amounts of permanganate are suspected,
it is best to carry out a blank test with a solution of pure chromate. The
paper is bathed in water to reveal the slight stain of MnOj left on the yellow
spot, or on the washed paper. If a drop contains less than 5 7 of KMnO*,
it is best to wait about 3 minutes after applying the test solution before
making the comparison, and washing out the chromate. All of the per-
manganate will have reacted by this time
Identification Limit: 0.3 y KMn04 in presence of 20,000 y KjCrOi
CHROMIC ACID*
Test for chromates in the presence of permanganates^''
The sensitive diphenylcarbazide reaction for chromates (p. 128) is
not directly applicable in the presence of permanganates, because of their
intense violet color; but the different behavior of these compoundstowatd
hydrazoic acid may be applied to prevent interference of permanganates
in detecting small amounts of chromate. Hydrazoic acid has little appreci-
able effect on chromic acid, while permanganates are readily reduced at
room temperature to manganese (II) salts. (The reaction is not sufliciently
imderstood to be expressed by an equation."*) Manganous salts do not
interfere with the diphenylcarbazide test for chromates. In this way, a
* See also chromium (pages 128 et eq.).
" F. Feigl, Mihrochemie {Emich Festschrift), 1930, p. 127. ^
>" Compare P. Rasohig, Schwefel und Sticketoffstudien, 3''eriag Chemie, Leip-
zig, 1925, p. 201. About one-seventh of the hydrazoic acid is oxidized to nitrogen;
at the same time nitrate is formed, and possibly NjO. Compare also H. H. Willard
and Ph. Young, / . Ind. Eng. Chem., 4,187 (1932).
SELENIOUS ACID 263
trace of chromate may be detected even in a saturated solution of perman-

ganate.
IfProcednreA drop of the test solution is mixed on a spot plate
with a drop of cone, sulfuric acid. Small particles of sodium azide are
added, while stirring with a glass rod, imtil the color of the permanganate
has disappeared. A few mg. sodium azide suffice to immediately reduce
considerable amounts of permanganate with effervescence (evolution of
nitrogen). The permanganate-free solution is then treated with a drop of
an alcoholic solution of diphemylcarbazide. A more or less intense blu^-
violet to red color is formed according to the amount of chromate present.
T- u oft Identification:
hvmd Tj f f r0.5
K y xrr._/^
KiCr04 f/,.
^' ^ ^^ ,, presence ôf ,6000
n , . T ; i.tnnnrtn itunes the amount of
Concentration Limit: 1:100,000 j ^ ^ ^^
Reagents: 1) Cone, sulfuric acid
S) Sodium azide (solid)
S) 1% alcoholic solution of diphenylcarbazide
SELENIOUS ACID
1. Test with hydriodic acid.'*' Selenious acid is reduced by iodides,
in acid solution, to elementary seleniiun; free iodine is also formed:
SeOr~ + 4 I- -f 6 H+ -> Se + 3 HjO + 2 I2
The color of the iodine is removed by adding thiosulfate, and the selenium
is left as a red-brown powder. Tellurous acid reacts, under the same
conditions, with hydriodic acid, forming the complex anion TeI7~ which is
red-brown. This tellurium compound can, however, be decomposed and
decolorized by sodium thiosulfate. Selenium can thus be detected success-
fully, even in the presence of considerable quantities of tellurium
IfProcedureÂ drop of cone. HI (or KI solution plus a drop of cone.
HCl) is placed on filter paper and a drop of the acid test solution is placed
in the middle of the moist fleck. The black-brown fleck that develops is
completely decolorized by a drop of sodium thiosulfate if no selenium is
present; otherwise a red-brown fleck of selenium is left.
Limit of Identification: 1 y ^lenixun (0.25 ml.).
Limit of Identification in the Presence of Tellurium: 2.5 7 Se
Proportion Limit) Se:Te = 1:615
Reagents: 1) C!onc. hydriodic acid or cone, potassium iodide solution
plus cone, hydrochloric acid
2) 5% sodium thiosulfate solution
" N. S. Poluektoff, Mikroehemie, IB, 32 (1934).
2. Test with pyrrole.^** Under suitable conditions, pyrrole is oxidized by

selenious acid to "pyrrole blue," a blue dyestuff of unknown constitution.
Iron salts do not interfere; they actually accelerate the iceaction when it is
carried out in phosphoric acid solution. Selenic acid does not react;
neither do tellurous and telluric acids. The test can thus be used to dis-
tinguish between selenic and selenious acids.
TfProcedureÂ drop of a solution of ferric chloride and 7 drops of
syrupy phosphoric acid are added to a drop of the test solution. The mix-
ture is well stirred. A drop of the pyrrole reagent is then added and the
mixture stirred again. A green-blue color indicates the presence of seleni-
ous acid. A blank test should be carried out when looking for small
amounts of selenious acid.
Limit of Identification: 0.5 7 selenium
Reagents: 1) 5% ferric chloride solution
B) Syrupy phosphoric acid (sp. gr. = 1.75)
3) 1% solution of pyrrole in aldehyde-free ethyl alcohol
3, Test with asymmetric diphenylhydrazine."* Selenious acid is readily
reduced to elementary selenium and therefore can oxidize numerous
organic compounds. In common with a number of other oxidizing
agents,**' it reacts with asymmetric diphenylhydrazine (I) and produces,
along with colorless compounds, violet quinoneanildiphenylhydrazone (II).
\
NNH2 / \_N==/ \==NN
(I) (11)
The action of other oxidizing agents may be prevented by suitable

precautions; oxygen compounds of tellurium are without effect. -This
reaction may therefore be applied as a sensitive and specific test for sele-
nium, either in the form of the element, selenide, selenite, or selenate, since
all these materials are readily converted to selenious acid.
^ProcedureFour drops of a solution of asym. diphenylhydrazine in
glacial acetic acid are mixed with a drop of dilute hydrochloric acid and
a drop of the test solution on a spot plate. In the presence of selenious
acid, a red color appears at once and soon changes to a bright red-violet.
" ' R. Berg and M. Teitelbaum, Mikrochemie (Emich Festschrift), 1030, p. 23.
"< F. Feigl and V. Demant, Mikrochim. Acta, 1, 322 (1987T.
6H. Wieland, Ber., 43, 3260 (1910). Compare also J. J. Postowaky, ibid.,
69, 1913 (1936).
SELENI0U8 ACID 265
When extremely small amounts of SeOj are present, the color appears only
after a few minutes, and a blank test is advisable.
lAmit of Identification: 0.05 y SeOj
Reagents: 1) 1% solution of asym. diphenylhydrazine in glacial
acetic acid A freshly prepared solution is advisable
when testing for small amounts of SeOa
Selenic acid also gives a red color under the same conditions, {limit
of identification is 100 7). However, since selenates are converted to seleni-
ous acid by heating with cone. HCl, it is preferable to heat a drop of
the test solution with cone, hydrochloric acid in a microcrucible and test
with asym. diphenylhydrazine after cooling. In this way, as little as 1 7
selenic acid may be detected.
Interference with the reaction due to the presence of other oxidizing
agents, which may also cause the formation of the dyestuff (11), may be
prevented as follows: the solid test substance or a drop of the test solution
is heated with a few drops of cone, hydrochloric acid in a microcrucible to
destroy oxidizing oxy-acids (e.g., HIOs, HBrOa, HCIO3, HMnOi, etc.)
and peroxides. Tungstates, molybdates, Fe(III), and Cu(II) salts are
not affected by this treatment. If any of these are present, oxalic acid
should be added to the hydrochloric acid. Complex oxalates are formed
which do not react with asjon. diphenylhydrazine.
Commercial preparations of tellurous acid and alkali tellurites usually
give a weak reaction, due to the presence of a trace of SeOj. A content of
0.001% Se02 in Te02 may be detected by means of the reaction just de-
SQfibed. After strong ignition, TeOj containing SeOz no longer gives a
positive reaction, as the SeOz is volatilized.
Test for selenium in minerals, see page 464.
4. Other tests for selenious acid. 1. Free red selenium is precipitated from
selenite by adding solid thiourea'** {Id". Limit: 2 y Se). Nitrites interfere
as do large amounts of copper; Te, Hg, and Bi form yellow precipitates.
5 7 Se is detectable in the presence of 25 y Te.
2. A red-bluefluorescingprecipitate is produced by mixing 1 drop of
test solution with 1 drop of 10% thiourea solution."' Heavy metals do
not interfere {Id". Limit: 5 y Se).
3. Selenites in solutions of the mineral acids may be detected by
reduction*'* to Se with FeSO^ {Id". Limit: 10 y Se).
" P. Falciola, Chem. Abstracts, 21, 3580 (1927). Compare N. S. Poluektoff,
Mikrochemie, 15, 32 (1934).
" ' M. H. Evans, Chem. Abstracts, 32, 8299 (1938).
" ' F. Feigl, unpublished studies.
266 III. TBSTS FOR ACID RADICALS
4. A brown compound is formed by the reaction between selenitee

in acetic acid solution and 1,8-naphthyIenediamine*" (Id'. Limit: 1 y
SeOs). !
TELLURIC (TELLUROUS) ACID I
1. Test wifli hypoôsphorous acid."" Tellurites and tellurates are
reduced to the element on evaporation with hypophosphorous acid:
TeOr~ + HsPOr = Te + P07~~ + HjO
or 2 TeOr' + 3 HjPOr = 2 Te + 3 POr~~ + 2 HjO + 2 H+
In the absence of Pt, Cu, Ag, Au salts, and sdenious acid, which
are also reduced by hypophosphorous acid to the metal or selenium re-
spectively, the test is decisive. If necessary, selenious acid can be reduced
to the element by heating the cone, sulfuric acid solution with sodium
sulfite, as this procedure leaves tellurium compounds unaffected. The
tellurium can then be identified in the filtrate after removing the sulfur
dioxide.
1fProcedure---A drop of the test solution containing mineral acid and
a drop of hypophosphorous acid are mixed in a porcelain microcrucible
and evaporated almost to dryness. According to the amount of tellurium
present, either black flakes or a gray color will appear. For very small
amounts of tellurium, a blank test should be carried out.
Ldmit of Identification: 0.1 y tellurous acid
0.5 7 telluric acid
Concentration Limit: 1:600,000 or 1:100,000, respectively
Reagent: 50% hypophosphorous acid
2. Test with alkali stannite.*^^ Tellurites and tellurates are reduced to
tellurium by alkaU stannites in alkaline solution:
Te07~ + 2 SnOr~ + H2O = 2 SnOr~ + Te + 2 0H-\
TeOr~ + 3 SnOr" + H,0 = 3 SnOT~ + Te + 2 OH"
The element separates into black flocks. Alkali stannites are without
effect on the analogous seleniiun compounds so that tellurium may be
detected in the presence of selenium. As silver, mercury, copper, bismuth,
and antimony salts are also reduced to the metal by stannites, it is ad-
visable always to carry out the detection of tellurium in the soda extract.
^ProcedareA drop of a solution of stannous chloride, a drop of 25%
sodium hydroxide, and a drop of the alkaline test solution are mixed
on a spot plate. A black precipitate or gray color-appears, according to
" F. Sachs, Ann., 366,150 (1909); O. Hinsberg, Ber., 62, 21 (1919).
^" Unpublished studies with L. Badian.
" N . S. Poluektoff, Mikrochemie, 16, 32 (1934).
TEItLURIC (TBLLUROUS) ACID 267
the amouDt of tellurium present. For very small amounts, the color
develops only af tr 1.5 to 2 minutes. In such cases a blank tst is necessary.
Limit of Identification: 0.6 y tellurium (0.025 ml.)
Concentralion Limit: 1:41,000
Limit of Identification in the Presence of Selenium: 0.8 7 tellurium in
the presence of 100 times this amount of selenium
Reagents: 1) Stannous chloride. 5 g. crystalline SnClj are dissolved
in 5 ml. cone. HCl and made up to 100 ml. with water
3. Test by formatioii of a complex copper (III) salt."' If alkaline solu-
tions of copper with certain oxidizing agents {e.g., persulfate) are warmed
in the presence of an alkali tellurate, a dark red-brown color appears.
It is due to a stable complex anion formed from trivalent copper and the
tellurate radical."'
The formation of the colored anion itself may be applied as a spot test
for tellurates [Procedure (a) ]. Alternatively, the impeding by tellurate
of the catalytic effect of copper (II) salts on the reaction between Mn++
ions and hypobromite may be used [ft-ocedure (b) J. This latter reaction
normally proceeds with the formation of manganese dioxide, but in the
presence of even very small amounts of copper salts, permanganate is
formed. The higher oxide of copper arising as an intermediate, brings
about the further oxidation of MnOj to MnO*, with re-formation of Cu(II)
oxide (see page 133). The formation of a stable complex ion of trivalent
copper with tellurate, prevents the addition of oxygen to MnOj, and thus
the permanganate formation does not take place.
The formation of a stable complex of trivalent copper under the given
conditions is limited to telluric acid and periodic acid (see page 226). The
test is consequently extremely selective.
Using procedure (a), 1 -y Te may be detected in the presence of 500
times the amount of Se (as selenic acid). Selenious acid interferes with the
tellurium test, so that any SeOj "present must be oxidized to SeOi (with
bromine) before the reaction. Using procedure (b), 2.5 7 Te may be.
detected in the presence of 20,000 times the amount of Se (as selenic acid).
IfProcedore(a) A drop of copper sulfate and a drop of alkaline
hydroxide is added to a drop of the alkaline test solution and finally a little
solid sodium or potassium persulfate; the mixture is boiled. A yellow
color indicates telluric acid.
Limit of Identification: 0.5 7 telluriimi (as HTeO)
" F. Feigl and R. Uzel, Mikrochemie, 19,133 (1936).
" B. Brauner and B. KuJma, Ber., 40, 3362 (1907).
268 m . TESTS FOB ACID RADICALS
Reagents: 1) Dilute copper sulfate solution (1:50,000)

2) Potassium persulfate (solid)
KProcedure(b) A drop of the copper-manganese solution and a
drop of sodium hypobromite solution are added to a drop of the test solu-
tion in a micro test tube. A blank test on water and the reagents is set up
simultaneously. Both tubes are heated for a few minutes in boiling
water, or are heated to boiling over a flame. In the presence of telluric
acid, the test solution is colorless or slightly yellow, while the blank test
assumes the permanganate color.
Limit of Identification: 0.2 y tellurium
Reagents: 1) Copper-manganese solution. A drop of a 4% solu-
tion of CuS04-5 H2O is added to 100 ml. of a 0.04%
solution of MnCl2-4 H2O
^) Sodium hypobromite. A freshly prepared solution of
bromine in 2 iV NaOH
4. Other tests for telluric and tellurous acid. Alkali tellurites and tel-
lurates may be reduce#to the element tellurium by heating with a solution
of FeS04 containing some syrupy phosphoric acid (l:l)i'* (Jd". Limit:
0.5 y Te). Selenites and selenates are reduced by FeS04 in the absence
of phosphoric acid. In the absence of these compounds, or after removal
of Se by precipitation, the test by reduction with Fe(II)-P206 is specific
for tellurium. Se is removed first by heating with FeS04 in acid solution.
The heating can then be continued after adding H3PO4 to the filtrate or
centrifugate.
HYDROGEN PEROXIDE
1. Test with lead sulfide."' Lead sulfide reacts with hydrogen peroxide:
PbS -I- 4 H2O2 = PbS04 -f 4 H2O
The black sulfide is thus converted to white lead sulfate. When finely
divided lead sulfide is used for the reaction, the decolorization is almost
instantaneous. This is particularly true if paper impregnated with PbS
is spotted with hydrogen peroxide or solutions of alkali peroxides. Lead
sulfide papers of varying strengths can be used, depending on the quantity
of hydrogen peroxide expected. Only when much of this material is
present and when strongly impregnated PbS paper is used, m'ay the test
"* F. Feigl and R. Seboth, unpublished studies.
" R. Kempf, Z. anal. Chem.;69, 88 (1933).
HTDROGBN PBKOXIDB 269
solution contain small quantities of mineral acid. Consequently, the

absence of free acid should be established because lead sulfide, when
highly dispersed in the capillaries of paper, is much more reactive than
compact PbS. The latter is known to be completely resistant to dilute
acids.
^ProcedureÂ drop of the test solution, which should be almost
neutral or only slightly acid, is placed on filter paper impregnated with
PbS. A whitefleckor-circle is formed on the light brown paper, depending
upon the hydrogen peroxide content.
Liimit of Identification: 0.04 y hydrogen peroxide
Reagent: Filter paper (S & S 601) is soaked in a 0.5% solution of
lead acetate, H2S blown on to the surface, and dried in a
vacuum desiccatpr. The paper will keep in stoppered
bottles
2. Test with ferric-ferricyanide."* The brown acid solution of ferric
chloride and potassium ferricyanide (ferric-ferricyanide) reacts with
reducing agents (SnCU, NajSOa, Na2S203, etc.) with the formation of Prus-
sian blue or a mixture of Prussian blue and Tumbull's blue. Hydrogen
peroxide likewise reduces ferricyanide:
2 [Fe(CN)8] + H2O2 = 2 [Fe(CN)6] + 2 H+ + O2
The resulting ferrocyanide reacts with the ferric chloride in the solu-
tion and forms Prussian blue."^
If Procedure"' A drop of the reagent solution and a drop of water
are placed on a spot plate; in an adjacent depression a drop of the reagent
solution and a drop of the test liquid are used for comparison. A more or
less intense blue color or precipitate is formed, depending on the hydrogen
peroxide content.
Limit of Identification: 0.08 7 hydrogen peroxide
Reagents: A mixture of. equal parts of 0.4% FeCU and 0.8%
KaFeCCN),
3. Test by reduction of higher nickel oxides.*" Hydrogen peroxide is
catalytically decomposed by nickel hydroxide. Nickel (II) oxide or
' " C. F. Schonbein, / . prakt. Chem., [1], 79, 67 (1859). Compare also F. Feigl
'and E. Frankel, Mikrochemie, 12, 309 (1932/33).
" ' According to a communication from M. Kohn, the insoluble, yellow-green
Cu(II) ferricyanide is also reduced by small amounts of H1O2 in the presence of eo-
,dium acetate, forming the brown Cu(II) ferrocyanide (Id". Limit: 17 HjOj).
' " F. Feigl and E. Frankel, Mikrochemie, 12, 304 (1932/33).
270 n i . TESTS FOR ACID RADICALS
hydroxide is re-fonned from the action of hydrogen pproxide on the higher

nickel oxides."'
NisO, + H2O2 = 2 NiO + H2O +!0s

I
The disappearance of the black color of the higher nickel oxides on treat-
ment with hydrogen peroxide affords a means for its detection. It is
best to use a mixture of nickel (III) hydroxide and an indifferent colorless
substance, made into paste, {e.g., NijOs plus BaSO*)
IfProcedureSeveral small dabs of NijOj paste are placed in each
of 2 adjacent depressions of a spot plate. Water is added to one; a drop
of the neutral or slightly acid test solution to the other. According to the
amount of peroxide present, the precipitate turns paler or becomes colorless.
Limit of Identification: 0.01 7 hydrogen peroxide
Reagents: Preparation of the paste: Baryta water is mixed with
bromine water, and the resulting barium hypobromite
is mixed with nickel sulfate and warmed. The proportions
of Ba and Ni should be ô arranged that a gray precipitate
is formed. It is filtered and well washed. The wet
precipitate is put into a weighing bottle, with a well-fitting
stopper. The paste can be kept for a long time
4. Test by catalyzed oxidation of phenolphthaliii.^^ If a red alkaline
solution of phenolphthalein is \ârmed with zinc, reduction to colorless
phenolphthalin occurs.^'' The reaction is discussed on page 219. The
colorless solution of phenolphthaUn gradually turns red on standing in
contact with the air, regenerating phenolphthalein. The reoxidation is
more rapid if strong oxidizing agents are added. Hydrogen peroxide by
itself acts quite slowly, but its action is speeded up if copper salts are,
present."' This effect is the basis of a test for peroxides, which is specific
provided other weak oxidizing agents are absent.
UProcedureOne drop each of the test solution, 0.01 JV copper sul-
fate solution, and reagent solution (for preparation, see page 220) are
brought together on a spot plate. A pink to red coloration indicates the
presence of peroxides.
Limit of Identification: 0.04 7 hydrogen peroxide in 0.04 ml.
"9 F. Feigl, K. Klanfer, and L. Weidenfeld, Z. anal. Chem., 80, 5 (1929). .
" O. Schales, Ber., 71, 447 (1938).
" ' A. V. Baeyer, Ann., 202, 80 (1885).
P. Thomas and G. Charpentier, Compt: rend., 173,1082 (1921).
HTDBOGEN PEBOXIDE 271
5. Other tests for hydrogen peroxide. 1. HjOj may be detected by the

reduction of a neutral 0.01% solution of AuClj to free gold'" {Id''. lAmit:
0.07 7 H,0).
B. A yellow-red precipitate is formed with acid solutions of alkali
thiocyanatesi" (0.7 y HjOj).
S. Freshly prepared colorless solutions of potassium cerous carbonate
[a solution of 62(804)3 mixed with excess K2CO3] are converted to the
yellow or brown-yellow potassium perceric carbonate with HjOj"* {Id".
Limit: 0.01 y H2OJ).
4. When a mixture of equal parts of 1% alkaline o-tolidine solution,
sodium acetate buffer (pH = 4), and 1% FeS04, are treated with a drop
(0.025 ml.) of a solution containing HjOj, a blue color appears.^''
5. An intense chemiluminescence is produced by oxidizing "lirniinol"
(3-aminophthal hydrazide) with HjOa in the presence of hemin.'*' Sev-
eral drops of reagent solution (0.1 g. luminol and 2 mg. hemin in 100 ml.
20% sodium carbonate) are mixed with one drop of the test solution on a
spot plate {Id". Limit: 0.012 y HjOj).
6. Chromates are reduced by H2O2. Consequently, the color pro-
duced by the sensitive CrOr~-diphehylcarbazide reaction (see page 128)
is discharged by H2O2 and peroxides.'" If very dilute K2Cr04 solutions
are used, and a comparison test run, it is possible to detect 0.5 y H2O2.
" F . Feigl and E. Frankel, Mikrochemie, 12, 304 (1932/33).
"* E. Plank, Z. anal. Chem., 99,105 (1934).
" L. Kul'berg and L. Matwejew, Chem. Abstracts, 30, 7492 (1936).
" W. Langenbeck and U. Ruge, Ber., 70, 367 (1937).
" ' L . N. Lapin, Chem. Abstracts, 36, 1727 (1941).
IV. TESTS FOR FREE ELEMENTS
Since the great majority of all natural and artificial products consist of
chemical compounds or of mixtures of compounds, the qualitative analysis
of a sample very seldom requires a direct search for free, i.e., uncombined,
elements. Consequently, a sample can usually be sufficiently characterized
by the statement that certain elements, or their ions, or certain insoluble
compounds are present. This information generally is all that is needed to
determine what quantitative determinations are necessary. Accordingly,
any chemical analysis should be made only after the sample has been treated
with water or acids, and the solution, as well as any insoluble residue, tested
for the materials contained in them.
In certain cases, however, particularly when technical materials are
being examined, information about the presence of free elements can be of
value. The examples given in the following sections (see also Chapter VII)
demonstrate the use of spot reactions for this purpose.
A. FREE METALS AND ALLOYS

Metallic appearance, luster, color, hardness, and sometimes magnetic
properties, are characteristic of metals and alloys. However, certain
metalloids, or semimetaJs {e.g., As, Sb, Se, Te) look like metals, and certain
compounds of metals (FeS, FesOj, Fe304, for instance) are magnetic.
Neither the solubility of metals in dilute acids, nor the deposition of a
metal from the solution of a salt by introducing a less noble metal, consti-
tutes a decisive general test for free metals. For example, metals that
precede hydrogen in the electromotive series, in other words, that are less
noble, are expected to be soluble in nonoxidizing acids, while the metals
nobler than hydrogen ought not to dissolve. However, the facts are some-
times not in accord with these expectations. Metals less noble than hydro-
gen are sometimes quite resistant to acids or go into solution very slowly.
Examples are Al, Fe, Zn (of high purity), and Pb. On the other hand,
more noble metals (Cu, Co, Hg, etc.) are markedly attacked by dilute,
nonoxidizing acids. The causes of these anomalies are invisible layers of
oxides, passivity, deposition of salts on the surface of the metal, excep-
tionally high purity of the metal, and sequestration 6f the metal ions pro-
duced, if they form complexes with the anions of the dissolving acid. The
same causes also operate in cases of apparent departures from the usual
rule of the oxidation of less noble metals by ions of more noble metals
(cementation). .' "
Two methods will be given for detecting free metals and alloys.
They are based on redox reactions. The tests are decisive, provided they
272
FREE METALS AND ALLOTS 273
are applied in the absence of sulfides, and of insoluble compounds of metals

at lower valences (cuprous halides, HgaCU, etc.), which also act as re-
ductants. Digestion of the sample with water will definitely and easily
insure the absence of soluble reducing compounds.
1. Test with phosphomolybdic acid.' A water solution of the complex
phosphomolybdic acid H3P04-12 MoOs-aq, may dissolve metals and alloys
first of all because of the H+ ions contained in the solution. In addition,
phosphomolybdic acid, like ijitric acid, also acts as an oxidizing acid.
The reason is that the Mo (VI) or M0O3 molecules of the complex acid are
more readily reduced than when they are present in normal molybdic acid.^
Consequently, when metals or alloys are attacked by phosphomolybdic
acid, "molybdenum blue" is always formed. It is a mixture containing
varying proportions of the oxides of Mo (VI), Mo(V), Mo (III). The
solution of divalent metals by phosphomolybdic acid, with production of
MojOs as the essential constituent of the "molybdenum blue," can be
expressed as follows:
Me" + 2 H+ -* Me++ + 2H
2 M0O3 + 2 H' ^ H2O + MoA
Me" + 2 M0O3 -^ MeO + MoA
MeO + 2 H+ -^ Me++ + HjO
The color of molybdenum blue is extraordinarily intense. Consequently,
even a slight dissolution of metal is made clearly evident and the presence
of free metal is estabhshed.
1[ProcedureA small quantity of the sample is added to 1 or 2 drops
of a saturated water solution of phosphomolybdic acid contained in a de-
pression of a spot plate. If necessary, a drop of dilute sulfuric acid is then
added. A blue or green color appears if free metal or an alloy is present.
The reagent solution keeps if it is stored in a tightly stoppered brown bottle.
Test for free metals in oxides, printing on paper, etc., see page 449.
2. Test with ferric ferricyanide. When a ferric solution is mixed with a
solution of potassium ferricyanide, a brown color appears. The solution
contains water-soluble ferric ferricyanide, PeFe(CN)6. This compound
reacts not only with soluble reducing agents,' but also with those that do
not dissolve in water. A blue color or precipitate appears (Prussian blue
and Tumbull's blue). Ferric ferricyanide jaelds the ions Fe"*"*^ and
' F. Feigl and G. Dacorso, Chemist-Analyst, 32, 28 (1943).
2 Compare F. Feigl, op. cit. (this text, page 2), page 62.
' C. F. Schonbein, J. prakt. Chem., [1], 79, 67 (I860).
274 IV. TESTS FOB FREE ELEMENTS
Fe(CN)r , and when it reacts with metals or alloys, two different reac-
tions may occur. Ferric ions may be reduced:
2 Fe++++ Me"-> Me+++ 2 Fe++ ' (I)
or ferricyanide ions may be reduced:
2 Fe(CN)r~" + Me" -^ Me++ + 2 F e ( C N ) r ~ " (2)
Both Fe++ ions and Fe(CN)r are produced and, in their turn, react
with the ions of ferric ferricyanide to produce ferrous ferrocyanide (Turn-
bull's blue) and ferric ferrocyanide (Prussian blue). Accordingly, either
type of reduction of ferric ferricyanide leads to a blue reaction product.
This fact is responsible for the high sensitivity of this test for metals.
It gives positive results even with metallic silver, and in a lesser degree,
but in a still more visible form, even with metallic platinum.
KProcedoreThe sample is treated, in a depression of a spot plate,
with one drop each of ferric solution and potassium ferricyanide solution.
On stirring with a glass rod, a blue to green coloration is seen if metals or
alloys are present. In some cases (silver, for instance) the metal acquires a
blue coating.
Reagent: Freshly prepared mixture of equal volumes of 0.4% FeClj
and 0.8% K3Fe(CN)6 solutions
MERCURY(MERCURY VAPOR)
t
1. Test by redaction of palladiom chloride/ The detection of metallic

mercuiy, particularly when present as vapor, is an important item in spot
test analysis. This test has considerable practical significance because
often it is important to be able to establish quickly the presence of amal-
gams and mercury compounds. These, without exception, are decomposed
by heat Avith evolution of mercury vapor. Identification of mercury vapor
need not be attempted when the sample consists of water- or acid-soluble
inorganic mercury salts, because Hg++ ions can be detected by the usual
tests, whose sensitivity and reliability are adequate. However, some
organic mercury derivatives do not respond to the Hg reagents. This is
especially true of compounds that contain mercury directly linked to car-^
bon. The organic components of such materials must be decomposed
before proceeding with the test for mercury. This is easily accomplished
by adding some copper oxide and then igniting. The cupric oxide hastens
the complete combustion, and prevents the formation of carbon monoxide
and tar. Mercury vapor is given off during this combustion and the subse-
quent ignition. . - "^
* F. Feigl, unpublished studies; see also G. Gaglio, Chem. Zentr., 1894, II, 452.
MBRCxmy (MBKCURT VAPOB) 275
Metallic mercury, and consequently also its vapor, reacts with pal-
ladium chloride:'
PdCls + Hg -^ Pd + HgClj
When mercury vapor comes in contact with PdCU paper, the light brown
paper turns deep black (deposition of finely divided palladium). It must
be noted that mercury vapor reacts with, greater sensitivity when the pal-
ladium chloride paper is dry. This is an advantage in the test described
here.
IfProcediireSeveral mg. of the sample are placed in a small porce-
lain crucible and mixed with 4 to 6 times as much powdered copper oxide.
The mixture is covered with a layer of CuO, and the crucible covered with
a small disc of the reagent paper. The crucible is heated gently at first,
\dth a microflame whose tip is directed against the bottom of the crucible.
This starts the combustion. Later, the temperature is raised until the
bottom of the crucible is red. If mercury is present, the exposed paper
will be gray or black. The stain can be made more visible if the paper is
held briefly over concentrated ammonia water. The light brown paper
loses its color [formation of Pd(NH3)4Cl2] and the gray fleck of metallic
palladium is then easily seen against the white paper.
Reagent: Filter paper moistened with 1% solution of PdCla and then
dried
The test for mercury vapor through reduction of PdCU is so sensitive
that it will even reveal the minute traces of mercury that enter the air when
the metal stands room temperatures. This can be demonstrated by merely
allowing a drop of mercury to reraain in a microcrucible, covered with a
sheet of the reagent paper. At 25 to 30 C , the deposition of palladium is
quite distinct, even within ten minutes; on longer standing the light gray
stain gradually blackens.
The presence of intermetallic mercury compounds (amalgams) can
.also be established by this test for mercury vapor. Several mg. of the
sample, in a microcrucible, are kept at about 100 C. (diying oven or hot
plate) for 30 to 60 minutes. The crucible is covered with PdClj paper.
This treatment is sufficient to volatiHze enough mercury to" affect the paper,
even though amalgams have a lower mercury tension than the free metal.
Selenium sulfide, SeSs, is a sensitive reagent for mercury vapor.
Black HgSe and HgS are formed rapidly even by traces of mercury.*
The reagent paper is prepared by bathing filter paper in a water solution
of aelenious acid, then exposing it to hydrogen sulfide, washing and drying.
' B. W. Nordlander, Ind. Eng. Chem., 19, 518 (1927).

276 IV. TESTS FOB TREE BLEMBNTS
It is still better to prepare particularly active SeS2 by a special procedure,

and then rub the dry material on filter paper.* j
Tests for metallic paUadimn, salver, copper, etc., see Chapter YII.
B. FREE NON-METALS
FBEE HALOGENS
1. Test with fluorescein.* It is conunon practice to test for free halogens
(CI2, Bra, Is) by means of paper impregnated with starch and potassiimi
iodide. It turns blue when exposed to a free halogeii. Free iodine forms
the blue starch-iodiae complex directly; chlorine and bromine react with
the iodide in the paper, liberating iodine which then forms the blue complex
with starch. However, this test is not specific for free halogen, because
many other oxidants (H2O2, per-salts, HNO2, KMnO*, etc.) likewise set
iodine free from the iodide of the reagent paper, and thus produce blue
starch-iodine.
Fluorescein provides a specific reaction for bromine and iodine; chlo-
rine can also be detected if the other halogens are absent. The yellow dye
reacts with free bromine to prqduce red eosin (tetrabromofluorescein);
whereas iodine yields red-yellow erythrosine (tetraiodofluorescein) (see
paê 194). Chlorine is without direct action on fluorescein. If, however,
a mixture of potassiiun bromide and fluorescein is used, the bromine set
free by the chlorine immediately forms eosin. Thus fluorescein also
provides a test (indirect) for chlorine. All these tests can be carried out as
spot reactions on fluorescein and fluorescein-potassium bromide paper.
IfProcedureA drop of the neutral test solution is placed on flu-
orescein paper. If a red spot appears, free bromine or iodine is present.
It is not possible to differentiate between these halogens by this means.
If the reaction is nâtive, a drop of the test solution is placed on
fluorescein-potassium bromide paper. If chlorine is present, a red spot
results.
Limits of Identification: 1 7 chlorine
2 y bromine
6 y iodine
Conc^tration Limits: 1:50,000
1:25,000
1:8300
Reagents: 1) Fluorescein paper. Strips of filter (S & S 598g) are
bathed in a saturated water solution of fluorescein and
dried """ -
Z) Fluorescein-potassium bromide paper. Strips of filter
paper (S & S 598g) are bathed in a very weakly alkaline
solution containing 0.1 g. fluorescein and 0.5 to 0.8 g.
KBr and dried
' O. Frehden and C.-H.Huang,Mikrochemie Ver. Mikrochim. Acta, 26,41 (1939).
FBBB STJLFTJB 277
FREE SULFUR
1. Test by formation of thallium polysnlfideJ If black thallous sulfide,
finely dispersed in the capillaries of filter paper, comes in contact with
a solution of sulfur, a red-brown polysulfide (2 T12S-T12S3) is quickly
formed. When considerable amounts (over 50 7 in drops) of sulfur are
brought into reaction, the red-brown compoimd is clearly visible on the
black paper, after the solvent has evaporated. The polysulfide differs
from TI2S not only in color but also in its chemical behavior. At room
temperature it is not attacked by dilute mineral acids and hydrogen
peroxide; in contrast, thallous sulfide dissolves ahnost at once, because it
forms a soluble thallous salt by direct action of the acid, or because of oxi-
dation to soluble TljSOi. Accordingly, if black tHallous sulfide paper is
spotted with a drop of a solution of sulfur, dissolved in colorless (NH4)2S
or an oifganic solvent, and then bathed in dilute acid or hydrogen peroxide,
the paper will not be completely decolorized. A red-brown fleck will
remain where the drop was applied. The stain will be brown if only small
quMitities of sulfur were present. Selenium behaves analogously (see
page 279).
The imion of free sulfur with thallous sulfide can be used as a rapid
method of detecting the former. However, the test cannot be made in a
test tube; it succeeds only as a spot test on filter paper impregnated with
thallium sulfide. The reason is that two effects are utilized in the spot
reaction; they are connected with the capillary and surface action of the
paper. One of these effects is the rapidity with which the thallous sulfide
dispersed in the capillaries of the paper reacts with sulfur or selenium.
This enhancement of reaction rate is a consequence of the extensive free
reaction surface. The second effect is the envelopment of the highly
dispersed thallous sulfide by the polysulfide (or selenide) formed on its
surface. This coating protects the underlying, still unaltered, thallous
sulfide against the solvent action of acids or hydrogen peroxide (see page
106). The consequence of this protective layer effect is that the color of
the polysulfide (or selenide) formed at the site of the spot is reinforced
by the color of the protected thallous sulfide. With very dilute solutions
of sulfur or selenium, it is probable that the acid-stablefleck,consists prac-
tically of nothing but unchanged thallous sulfide. This is shielded from
the solvent action of acids or peroxide by a quantity of polysulfide, that, of
itself, is too slight to be visible.
The detection of sulfur, or selenium, by a spot reaction necessitates a
preliminary extraction of the sample with an organic solvent. Since only a
drop of the extract is needed, minute amounts of the sample suffice (micro-
extraction apparatus). As a rule, carbon disulfide is used; it dissolves
' F. Feigl and N. Braile, Chemitl-Analytl, 32,76 (X943). #
278 IV. TESTS FOB 7RBB ELEMENTS
all crystallioe modifications of sulfur, but not the amorphous varieties.*

Pyridine is a more reliable extractant; its solvent powers are lower, but all
modifications of sulfur are soluble in this liquid.' Pyridine dissolves about
4% of sulfur at room temperature, and about 25% at' the boiling point
(114" C ) .
^ProcedureFreshly prepared thailous sulfide paper is spotted with a
drop of the solution to be tested for sulfur. The solvent (carbon disulfide,
pyridine, etc.) is allowed to evaporate at room temperature or is removed
by a blast of heated air. The spotted paper is then placed in 0.5 N nitric
acid and swirled around. If no sulfur (or seleniiun) is present, the whole
paper turns white in about 30 seconds; a brownfleckis left if these elements
are present. The intensity of the color gives an index of the quantity of
sulfur. It is well to place the paper in water after thefleckhas developed;
any further action of the acid and a gradual fading of the spot are thus
prevented.
Parallel tests with solutions of known sulfur content can be used to
tell whether the unknown contains a trace, or considerable amounts of the
free element. The flecks can be preserved if the developed paper is thor-
oughly washed with water and then dried.
Limit of Identification: 3 y sulfur
Thailous sulfide paper is prepared by bathing filter paper (S & S
589 or Whatman 42) in 0.5% solution of thailous carbonate or acetate for
several minutes. The liquid is allowed to drain off and the paper dried in a
blast of heated air. Thailous sulfide is deposited by placing the paper
across a beaker containing ammonium sulfide solution warmed to 80 C.
The conversion into TUS requires only a few minutes; the paper turns per-
fectly black on the ade exposed to the fumes. Cut into strips, it is ready
for immediate use. It is best always to use freshly prepared reagent
paper when testing for sulfur. On standing, the paper deteriojates because
the sulfide is partially oxidized. ~^ -
Test for free solfor in inorganic and organic products (see pages 480 and 481).
2. Test by conversion into tliiocyanate.io Free sulfur is converted into
sulfide, polysulfide, and thiosulfate by boiling with alkali hydroxide.
Evaporation of the two latter sulfur compounds with a solution of potas-
R. Edge, Ind. Eng. Chem., Anal. Ed., i, 371 (1930), states that amorphous
sulfur can be quantitatively converted into the crystalline form by keeping the
saniDle for several hours at 105C. "^
H. Sonuner, Ind. Eng. Chem., Anal. Ed., 12, 388 (1940).
E. Grtinateidl, Z. anal. Chem., 77, 283 (1929).
FREE'SELENnm 279
num cyanide produces thiocyanate, which is easily recognized by its reac-

tion with ferric chloride to form red solutions. The underlying equations
of this sulfur test are:
4 S + 6 NaOH = 2 NajS + Na,S,0, + 3 HjO
S + NasS = NajS,
NajSj + KCN = KCNS + Na,S
NasSjO, + KCN = KCNS + NaiSO,
Fe+++ + 3 CNS- = Fe(CNS)3
Free sulfur, as well as that loosely combined in sulfides, hom substance,
egg yolk, etc. may be detected by this conversion into thiocyanate.
IfProcedureA few mg. of the test substance are placed in a micro-
porcelain crucible together with a few drops of sodium hydroxide. The
contents are cautiously evaporated to drjoiess over a very small flame, and
the evaporation is repeated after the addition of a few drops of a dilute
potassium cyanide solution. The dry residue is taken up with dilute sul-
furic acid and ferric chloride is added. In the presence of sulfur, a distinct
red color appears.
Limit of Identification: 5 y sulfur
Reagents: 1) Dilute sodium hydroxide
2) 0.1% potassium cyanide solution
S) Dilute sulfuric acid
4) Dilute ferric chloride solution
3. Test by conversion to thiosulfate." When free sulfur is to be detected
in a mixture of other solids, it can be extracted with carbon disulfide.
After evaporation of the disulfide, the sulfur can be detected in the residue
by conversion into sodium thiosulfate by warming with alkali sulfite.
The thiosulfate is revealed by using the sensitive iodine-azide reaction
(see page 272).
The carbon disulfide used must be absolutely sulfur-free. As even
"pure" or carbon disulfide "for analysis" very often contains sulfur, it is
necessary to purify it before the test by shaking with mercury (HgS pro-
duced) and then distilling. '
Another method of detecting sulfur dissolved in carbon disulfide is
discussed on page 482.
FREE SELENIUM
1. Test through addition to thallous sulfide.'^ Selenium, like sulfur, when
dissolved in organic liquids or in colorless ammonium sulfide, reacts with
" Studies with L. Weidenfeld, Dissertation, Vienna, 1930.
" F. Feigl and N. Braile, Chemist-Analyst, 82, 76 (1943).
280 IV. TESTS FOR FREE ELEMENTS
thallous sulfide paper (see page 278). An addition comjpound is fonned.

The first stage probably is the formation of thallous selenide:
TljS + Se ^ TlsSe + S
I
The free sulfur then unites with the selenide to produce a polysulfide-like
complex. This is resistant to dilute acids and hydrogen peroxide. Since
it is black, it cannot be seen on the black thallous sulfide paper, in contrast
to the analogous red-browTi compound formed by considerable quantities of
sulfur. However, the unaltered thallous sulfide can be dissolved off the
paper by bathing it in dilute acid or hydrogen peroxide solution, and the
spot at which the drop of selenium solution was applied then shows up as a
dark brown to black fleck. This consists of the selenide-sulfur complex,
or of thallous sulfide "protected" from the action of the solvents by a
coating of the complex.
This method of detecting free selenium is decisive only when free
sulfur is absent. Selenium, like sulfur, exists in several allotropic modifi-
cations. The usual red ;8-form, obtained by reducing a solution of seleni-
ous acid, is soluble in carbon disulfide. The more stable, dark a-form,
obtained by heating the red modification, is almost insoluble in this solvent.
^ProcedureUse the method given on page 278.
Limit of Identification: 1 y selenium
Reagents: See page 278
2. Test by formation of silver selenide.'' Selenium dissolved in carbon
disulfide reacts almost instantly with metallic silver:
2 Ag + Se -AgjSe
Black silver selenide is formed. Solutions of sulfur in this solvent also

react with metallic silver and produce AgjS, but the sulfideîs produced
very slowly, even though much sulfur is available. It is easy therefore
definitely to identify selenium in the presence of considerable quantities
of sulfur.
^ProcedureThe surface of a piece of silver foil 'is roughened with

fine emery paper. The metal is then thoroughly cleaned. A drop of the
test solution is placed on the foil and the solvent (CSa) allowed to evaporate.
A gray or black gray fleck of silver selenide appears.
Limit of Identification: 6 y selenium ^
" F. Feigl, unpublished studieB.
FBEE CABBON 281
Solutions of sulfur in pyridine, benzene, and toluene react quickly

with silver foil, despite the fact that sulfur is much less soluble in these
liquids than it is in carbon disulfide.**
FREE CARBON
4
1. Test by oxidation. Free carbon need only be looked for in a solid,

insoluble sample, that has a dark color. Its presence is indicated if the
sample glows, gives off sparks, or bums when it is heated with access to air.
A more sensitive test is to drop a portion of the sample into molten alkali
chlorate; oxidation to carbon dioxide with decrepitation ensues. Both
tests (see page 308 for procedure) are also applicable to organic, i.e., car-
boniferous, compounds in general. It is possible to isolate uncombined
carbon by treating the sample in turn with acid and alkah. These dissolve
basic and acidic inorganic and organic constituents. The residue is
washed, dried, and then extracted with ether and carbon disulfide. Gra-
phitic and carbide carbon are too resistant to be revealed by this
procedure.
Limit of Identification: approximately 50 y carbon
If other modifications of carbon are absent, and if no organic com-
pounds are present, it is possible to detect graphitic carbon (e.g., in iron
or steel) and carbide carbon (in siHcon carbide, etc.). The method is
based on the formation of potassium cyanide, which then is decomposed
to produce hydrocyanic acid.'* The latter can be detected by the proce-
dure given on page 208. Cyanide results if several mg. of the sample are
mixed with 20 times as much potassium azide and then cautiously heated
in a small hard glass test tube (goggles). The heating is moderate at first;
finally the mixture is strongly ignited for 2 minutes. The potassium azide
decomposes (2 KNj > 2 K + 3 Nj); probably some potassium nitride is
also produced and this unites directly with the carbon of the sample to
form potassium cyanide. The test is more sensitive if some potassium
(freed of adhering petroleum) is added to the mixture before heating.
The metal probably facilitates the formation of nitride and consequently
tilso the production of cyanide.
All natural varieties (hard coal, brown coal), as well as all artificial
carbons, invariably contain mineral constituents. These are responsible
for the basic ash that remains after the carbon has burned away (see
page 465).
" F. Feigl, J. Chem. Education, 20, 300 (1943).
E. Mailer, / . prakt. Chem., 208, 53 (1917).
V. THE SYSTEMATIC ANALYSIS OF MIXTURES
BY SPOT REACTIONS
The convenience and value of spot tests for identification purposes
are well established by the foregoing discussions and procedures. The
sensitivity, selectivity, specificity, and particularly the simplicity of many
spot reactions make it appear likely that considerable advantage will
result if their systematic use is substituted for some of the ordinary analj^ti-
cal procedures. It will then be possible to avoid, to a considerable degree,
the special separations and operations (precipitation, filtration, solution,
etc.) that are so time-consuming when operating with larger amounts of
the sample. In other words, spot methods make it possible to accomplish
qualitative analyses with great saving in time and material.
There are, as yet, very little data available on the use of spot reactions
for the systematic analysis of all cations and anions of a mixture.* At
present, not enough is known about the limiting proportions and concen-
tration limits of the spot analysis of mixtures to make a critical evaluation
or recommendation of any particular procedure. Statistical evidence and
details as to the time and materials consumed and comparisons of these
figures with those of the usual methods of analysis are greatly needed. If
such particulars were available, they would be extremely valuable in
showing how errors can be discovered and avoided. They would also
stimulate improvements in the present methods and lead to the develop-
ment of new spot methods. The aim of an analytical scheme composed
entirely of spot tests is not merely to perfect methods for the decisive
detection of the constituents of a solution when the concentrations are
average and of about the same order. A further objective is the selecting
and testing of such spot reactions as can be successfully applied to give
unequivocal detection of the materials in the presence of others when the
concentrations range over wide ratios. This is of paramount importance
in actual practice. , Spot tests allow a much greater elasticity in this
respect than do the usual methods because many sources of error, such as
adsorption of cosolutes on the large bulk of a precipitate, losses by induced
precipitation, etc., are avoided.
Several schemes of analysis employing spot methods have been recom-
mended. The procedures described on pages 289, 291 and 298 have been
tested by the author and found reliable.
It should be noted that spot reactions are particularly useful in
carrying out preliminary tests (see page 294) and in the exanfination of
acid-insoluble residues (see page 300). . -^ T
' The first reference to this use for spot teslis is contained in a paper by
E. Hauser, Z. anal. Chem., 60, 88 (1921).
282
OUTZEIT'S ANALYTICAL SCHEME 283
Gutseit's Analytical Schem^

1. Test on the Original Substance
Ammonium: The substance is heated in a crucible with NaOH. A
piece of black filter paper moistened with Nessler's reagent is held over the
crucible. TheVNHs is identified by the appearance of a yellow color.
The spot t ^ t can also be carried out using logwood extract. A drop
of the reagent is placed on filter paper and this is held over the opening
of the reaction vessel (crucible, etc.). A red color indicates NHj.
Carbonate: The sample is heated^ with chromic and acetic acids. A
glass rod holding a drop of freshly prepared baryta water is held over
the crucible. A white cloudiness indicates COr~.
Cyanide: The sample is heated in a crucible with cone, acetic acid.
A piece of filter paper is moistened with a solution of hydrocSrulignone
IHOCHs(OCH3)]2 and copper acetate. A purple color indicates CN~.
Sulfide: The sample is treated with cone, acetic acid. Any HjS is
identified by the orange color on filter paper moistened with SbCU held
over the crucible.
Chloride: The sample is heated, in a crucible with KjCriOr or lOVlnO*
and cone. HjS04. A thin glass rod holding a drop of NaOH is held over
the crucible. It is then dropped into a test tube containing aniline-
phenol water. A blue color after boiling indicates Cl~.
Bromide: The substance is treated as in the Cl~ test. A filter paper
moistened with a drop of reduced fuchsin solution is held over the crucible.
Bromide is revealed by the violet color.
Fluoride: The sample is placed in a lead crucible, moistened with a
drop of water and heated with a few drops of cone. HsS04. Filter paper
moistened with Brazil wood extract is laid on the crucible. A red color
indicates F~
2. Test in the Carbonate Extract

Acetic acid is added to the carbonate extract until there is no further
COj evolved.
Iodide: A drop of a 1% PdClj solution, a drop of dilute HCl, and
finally a drop of the test solution are placed on filter paper. A brown
fleck indicates I".
Sulfide: A drop of 20% solution of sodium nitroprusside is placed
on filter paper followed by a drop of the test solution. Sulfide sulfur'
produces a violet color.
Sulfite: A drop of 3% solution of Solid blue R (Meldola blue) is
< G. Gutzeit, Helv. Ckim. Acta, IS, 820 (1929).
284 V. 8T8TBMATIC ANAI<TSIB OF MKTXniESi
placed on filter paper and dried. A little powdered CdCOi is placed in

the middle of the fleck; then a drop of the substance to be analyzed. The
paper is held over fuming HCl. A color change from blue to yellow indi-
cates sor~- '
Sulfate: A drop of a fresh solution of sodium rhodizoiiate is placed on
filter paper and treated with BaCU and then with dilute HCl. The red
fleck is treated with the test solution. If the color of thefleckis discharged,
SOr~ is present.
Nitrite: A drop of naphthylamine-sulfaniUc acid reagent is placed
on filter paper, treated with dilute H2SO4, and then a drop of the test
solution added. A red-brown color indicates NOj".
An alternative method is to spot filter paper with benzidine solution.
A drop of the test solution is added, followed by a drop of an aqueous
solution of )3-naphthol. After development over ammonia, a violet color
appears.
Nitrate: A drop of the test solution is placed on a varnished micro-
scope slide, acidified with CH3COOH, and treated with a 5% solution of
nitron formate. A precipitate indicates the presence of NOr.
An alternative test is: a drop of the test solution and a drop of a
sulfuric acid solution of 1,5-dihydrooxyanthraquinone are placed on a
watch glass. A "violet color indicates NOr.
Phosphate: A drop of the test solution is placed onfilterpaper, spotted
with ammonimn molybdate, and dried. After treating with benzidine
acetate, a drop of cone. NHj is added. A blue color indicates POr .
Borate: A piece of filter paper is moistened with turmeric solution.
A drop of the test solution and a drop of cone. CH3COOH are added.
A red fleck, that turns blue-black with NajCOs, indicates BOr .
Silicate: Three drops of an ammonium molybdate solution are placed
on a watch glass, followed by a drop of the test solution, and a drop of
alkali stannite solution. A blue color indicates Si07 t.
Cyanide: An aqueous solution of pyramidone containing pyridine is
treated with a drop of the test solution. A blue color indicates CN~.
Ferroqjanide, Thiocyanate, Thiosulfate: A large drop of FeClj solution
is placed on filter paper and almost dried. The fleck is spotted with HCl
and then with the test liquid. After a short time different colored rings
are observed, due to capillary separation. These are (from the center
outward): Fe(CN)r , blue fleck; SsOr~, white ring; CNS", red ring.
3. Test in the Nitric Acid Extract /
Silver: A drop of the test solution is spotted on filter paper with a
drop of a hydrochloric acid-stannous chloride solution, and then with a
solution of chromotropic acid. A black fleck is formed when silver is
present.
Q U T Z B I T ' S ANALTTICAIi SCHEHB 285
Alternatively, a drop of the test solution is treated by cohc. NHs,

and then spotted with a drop of cone, potassium chromate solution and a
drop of cone, acetic acid. A red fleck indicates Ag.
Lead: A drop of dilute sulftiric acid is placed on filter paper, then a
trace of cone, potassium cyanide solution and a drop of the test solution
are added. A 2 per cent solution of diphenylthiocarbazone in CSj is
placed in the middle of the fleck. A red stain disappearing on the addition
of cobalt nitrate indicates Pb.
Another spot test is to stir a drop of the test solution with a drop
of dilute H2SO4 and develop over NHj. The middle of the fleck is treated
with a 3% solution of HsOj, dried, and the edge of the fleck spotted with
an alcohol-acetic acid solution of tetramethyl-p-diaminodiphenylmethane.
A blue color indicates Pb.
Mercury: A drop of the test solution is placed on filter paper. A drop
of water and then a drop of a 1% alcoholic solution of diphenylcarbazide
are added. After developing over NHj a blue color appears. If the stain
dissolves in benzene, monovalent Hg is present.
4. Tests in the Aqua R e ^ Extract
Bismuth: (i) A drop on filter paper is spotted with tetraacetyl-
ammonium hydroxide. A red fleck indicates Bi.
(S) A drop of cinchonine-potassium iodide reagent is placed on filter
paper followed by a drop of distilled water and a drop of the test solution.
In the presence of Hg++, Pb++, and Cu++, as well as Bi''-^+, a series of con-
centric rings (capillary separation) form. From the outside toward the
center these are: copper = brown ring; lead = canaiy yellow ring; bismuth =
orange ring; mercury = pale yellow ring.
Copper: (1) A drop is placed on a varnished microscope slide, treated
with a drop of tartaric acid solution and then with a drop of an alcoholic
solution of benzoin oxime. A pale green precipitate indicates Cu.
(S) One drop is treated on filter paper with 2% alcoholic solution
of l,2-diaminoanthraquinone-3-sulfonic acid. A dark blue stain indi-
cates Cu,
(S) A spot test on filter paper with tincture of guaiacum followed b^
KCN solution gives a blue fleck, if Cu is present.
Cadmium: (1) A drop of diphenylcarbazide-thiocyanate reagent is
placed on filter paper, treated with a drop of the test solution, and devel-
oped over NH3. A violet stain indicates Cd.
(2) A drop of the test substance is treated with NaOH and then
with a 5% solution of thiosinamine. A yellow color indicates Cd.
Arsenic: (J.) Two or three drops of the solution on a watch glass, are
rendered alkaline with NaOH, heated to boiling, and 2 drops of HjOj
added. With a capillaiy pipet, 2 drops of the filtered liquid are transferred
286 V. SYSTEMATIC ANALYSIS OF MIXTURKS
to filter paper. The moist spot is treated with acetic ^cid and then with
AgNOi solution. A brick red color indicates As.
(2) The moist spot [see {!)] is developed over cone. HCl and treated
with an alcoholic solution of S-hydroxyquinoline, and then with FeCl
solution. A blue-green color indicates As.
Antirrumy: Two drops are heated to boiling on a watch glass and a few
crystals of Na2S203 are added. A vermilion precipitate indicates Sb.
Tin: Two or three drops are heated on a watch glass with Mg powder,
and 2 drops of the clear solution are transferred with a capillary to filter
paper and treated with gold chloride. A brown-black color indicates tin.
Iron: On treatment with a 20% alcoholic solutiop of 2,4-dinjtroso-
resorcinol, a pale green color develops. Further tests include treatment
with a solution of 1,2,5-sulfosalicylJc acid (violet color) or K4Fe(CN)6
(blue color).
Chromium: Two or three drops on a watch âfls are rendered alkaline
with NaOH, heated to boiling, and treated with HjOa or NajOj, and filtered.
Three drops of the solution are acidified on filter paper with HCl, and spot-
ted with an alcoholic solution of orcinol. A brown color develops. Alter-
natively, spotting with a-naphthylamine causes a violet coloration.
Manganese: A drop of the test solution is treated on filter paper with
NaOH. A drop of tartaric solution is placed in the middle of the moist
spot, followed by an acetic acid solution of benzidine. A blue color indi-
cates Mn.
Nickel: A drop of a cone. (NH4)jHP04 solution is placed on filter
paper, treated with the test solution, and the moist spot edged with a
2% alcoholic solution of dunethylglyoxime, and developed over NHj.
A red stain forms. Other spot tests use oxalenediuramineojdme (orange
color) and a-benzildioxime (red color).
Cobalt: Filter paper is moistened with an acetic acid solution of /3-
nitroso-a-naphthol and dried. A drop of (NH4)HP04 solution is placed
on the spot followed by the test solution. A rosc'red border forins-if Co
is present.
Zivfi: A drop of the solution is placed on a watch glass and heated
with NaOH, and filtered. The filtrate is acidified on a varnished watch
glass with acetic acid, and then treated with antipyrine-thJocyanate reagent.
A white precipitate forms if Zn is present..
Aluminum: A drop of a solution of K4Fe(CN) is placed on filter
paper and dried. The test solution is added, followed by dilute NHs, and
finally by an alcoholic solution of alizarin. The fleck is developed over
NHs, and dried. A rose-red color encircles the spot-iTAl is present.
Barium: A few drops of the solution are made alkaline with NH| on
a watch glass, heated to boiling, filtered, and transferred to filter paper.
HEU.ES AND KRUMHOLZ SCHEME 287
The moist fleck is treated with freshly prepared alcoholic solution of

sodium rhodizonate and then with dilute HCl. A red stain indicates Ba.
Strontium: A drop of KjCrO* solution is placed on filter paper, dried,
and spotted with a drop of the test solution, and then acetic acid is added.
The fleck is treated with sodium rhodizonate and developed over NH3.
A rose-red border is formed around the drop.
Calcium: A drop of the test solution is acidified with HCl on a slide,
evaporated to dryness, and the residue treated with an ammoniacal solution
of phenol. A blue-green color forms if Ca is present.
Magnesium: A drop of the test solution is treated on filter paper with
NaOH, then with tartaric acid, and an alcoholic solution of quinalizarin.
After drying, a bluefleckis formed with dilute HCl, A spot test with dehy-
drothio-p-toluidine sulfonic acid, results in an orange-red color if Mg is'
present.
Sodium: Three drops of the solution are mixed on a watch glass with 2
drops NH and 2 drops (NH4)2C03, and filtered. A drop of potassiiun-
cesium-bismuth nitrite reagent is placed on black filter paper and a drop
of the test mixture added. A yellow stain forms if Na is present. The
test solution forms a pale yellow precipitate, visible on a varnished slide,
when treated with zinc uranyl acetate.
Potassium: A spot test with sodium bismuth thiosulfate carried out on
black filter paper produces a vellow stain if K is present.
Analysis Scheme According to Heller and KrumhoW
These authors utilize spot methods to identify elements within the
familiar groups of the systematic scheme of analysis. Therefore a pre-
liminary separation of the mixture by precipitation with HCl, H2S, and
(NH4)2S is necessary. These requisite operations can be carried out in a
very short time and on small amounts of material by using the centrifuge.
The identification of the individual ions is carried out by means of spot
tests, not only on paper, but also on a porcelain spot plate.
Cations of the HCl group. Silver: The mixed precipitate of silver,
mercurous, and lead chlorides thrown down by HCl is covered with 5%
KCN solution A drop of the filtrate is treated on a spot plate with an
alcoholic solution of p-dimethylaminobenzylidenerhodanine. In the pres-
ence of silver, a red color forms (see page 43).
Cations of the H2S group. The sulfide precipitate is treated with
yellow ammonium sulfide (residue I, solution I). Residue I is treated
K. Heller and P. Krumholz, Mikrochemie, 7, 213 (1929). The statements of
these writers have been amplified and completed in some places. Compare W. C.
Davies, J. Chem. Education, 17, 231 (1940) regarding a similar scheme of qualitative
analysis employing spot tests.
288 V. SYSTEMATIC ANALYSIS OF MIXTURES
with HNOj (sp. gr. = 1.2) (residue II, solution II). Solution II is diluted
with water and tested for Cu, Pb, Bi, and Cd. i
Copper: A drop of solution II is mixed on a spot plate with a drop
of a 1% zinc acetate solution and a drop of (NH4)jHg(Cl*JS)4 solution. In
the presence of copper, the precipitate is colored violet! (see page 73).
Lead: The authors include no tests for lead. It may, however, be
decisively detected as follows: A few drops of solution II are heated with a
drop of cone, sulfuric acid in a microcrucible until sulfuric acid fumes
are evolved; after cooling, water is added. A white precipitate indicates
lead. If the contents of the crucible are transferred to a microcentrifuge
tube, ver^' small amounts of PbSO* are visible. The rhodizonate test for
lead (page 56) or the dithizone test (page 57) can also be used.
Bismuth: A drop of solution II is treated on the spot plate with a
drop of a saturated solution of lead chloride, and 2 drops of a mixture
of equal parts of a 5% SnClj solution in 0.5 N HCl, and 25% NaOH.
If the solution contains copper, a drop of 2 iV NaOH and a drop of 5%
KCN are added before adding the stannite. When large amounts of bis-
muth are present, a black precipitate forms at once. For small amovmts
the precipitate appears after a few minutes.'^ A blank test is necessary in
this case (see page 60). ,
Cadmium: Solution II is precipitated with ammonia. A drop of
the filtrate is mixed on a spot plate with a drop of each of the following:
10% NaOH, 10% KCN, 0.1% alcoholic dinitrodiphenylcarbazide, and
finally treated with 3 or 4 drops of formaldehyde. In the prissence of
cadmium, a blue precipitate or color forms, which should be compared with
a blank test applied to NH (see page 76).
Mercury: Residue II is dissolved in cone. HCli+ H2O2. A drop of the
solution is mixed on the spot plate with a drop of an alcoholic solution
of p-dimethylaminobenzyUdene rhodanine and solid sodium acetate.
A red color indicates mercury (see page 61).
Solution I is acidified with HCl. The precipitate of the acid "sulfides
is treated with HCl (1:1) (solution III, residue III).
Antimony: A drop of solution III, diluted with water, is placed on
filter paper, treated with phosphomolybdic acid and steamed. A blue
color indicates antimony (see page 84). ;'
Tin: Solution III is reduced with metallic magnesium and a drop
placed on ammonium phosphomolybdate paper (see page 86). In the
presence of tin, a blue color forms. /
Arsenic: As the authors give no arsenic test, the procedui-e described
on page 79 may be applied.
Catioiis of the (NH4),S group. The precipitate of sulfides is dissolved
in dilute HCl + H0,.
KRUUHOIiZ SCHEME 289
Nickel: A drop of the test solution is mixed on a spot plate with

a drop of 3 % HjOj, a drop of saturated sodium tartrate solution, 2 drops
of a saturated sodium carbonate solution, and a drop of an alcoholic
dimethylglyoxime solution. In the presence of nickel, a red precipitate
forms; it diffuses to the edge of the liquid.
Cobalt: A drop of sodium phosphate solution, one of the test solution,
and one of -nitroso-/8-naphthol, are placed on filter paper, which is held
over ammonia and spotted with 2 N H2SO4. A permanent brown color
indicates cobalt.
Iron: A drop of the solution is treated on a spot plate with a drop
of a 1% KCNS solution. A red color indicates iron.
Chromium: A drop of the test solution is mixed on a spot plate with a
drop of bromine water, and 2 or 3 drops of 2 A'^ NaOH. A crystal of phenol
is added, and a drop of 1% alcoholic diphenylcarbazide; 2 A^ H2SO4 is
added drop by drop until the red color of the diphenylcarbazide due to
alkali disappears. In the presence of chromium, a violet color remains
(see page 128).
Manganese: A drop of the test solution is placed on filter paper and
spotted with a drop of a KOH solution containing tartrate, and a drop
of benzidine solution. A blue color indicates manganese (see page 134).
The solution of the sulfides is treated with an excess of 2 iV^ NaOH
and the filtrate tested for zinc and almninum.
Zinc: A drop of the solution, on a spot plate, is rendered just acid
with 10% acetic acid and then mixed with a drop of a 0.1% copper sulfate
solution, and a drop of a solution of 8 g. HgCU and 9 g. NHCNS in 100 ml.
water. In the presence of zinc, a violet precipitate is formed.
Aluminum: A drop of the solution is treated on a spot plate with
1 drop of a 0.5% solution of alizarin sulfonic acid and then 2 JV acetic acid
is added until the violet color disappears. One more drop of acetic acid is
then added. A permanent red color indicates aluminum.
Spot tests for the alkali and alkaline earth metals are not included
by the authors.
Analysis Scheme According to Krumhplz*

(Detection of Hg, Bi, Pb, Cu, Cd, As, Sn, Co, Ni, Fe,.Cr, Mn, Al, Zn)
About 20 to 50 mg. of the solid sample are heated with 0.5 ml. cone,
hydrochloric acid and 2 ml. bromine water, evaporated to about 0.5 ml.,
then diluted with 2 ml. water and separated from any insoluble matter by
filtering or centrifuging.
The following reactions can be carried out directly on the solution:
* P. Krumholz, unpublished studies.
290 V. STSTEMATIC ANALYSIS OF MIXTUBBS
. Mercury: A drop of the solution is placed on a spdt plate and stirred

with 5 drops 10% sodium phosphate, and then a drop ,of dimethylamino-
benzylidenerhodanine is added. A red color indicates Hg (see paê 51).
Bismuth: A drop of the solution is mixed on a spot plate with a drop
of a 5% solution of sodium potassium tartrate, a drop of 1% lead acetate
solution, and 3 to 5 drops of sodimn stannite (equal volumes of 5% stan-
nous chloride in 5% hydrochloric acid and 25% sodiimi hydroxide).
A brown to black color indicates Bi (see page 60). A blank test is neces-
sary when testing for small amounts of bismuth.
When mercury is present, a drop of the solution is ignited in a micro-
crucible; the residue is dissolved in 2 JV HCl and tested as directed.
Arsenic: A drop of the solution is mixed in a microcrucible with 3
drops cone, hydrochloric acid and a little stannous chloride, and warmed.
A brown color indicates As (see page 79).
* When mercury is present, a drop of hydrogen peroxide and ammonia
are added, then a little magnesium sulfate. The mixture is evaporated
to dryness, ignited, and the residue is tested as directed.
Nickel: A drop of the sdlution is mixed on a spot plate with a drop
of each of the following: hydrogen peroxide, 5% sodium potassium tar-
trate, dimethylglyoxime, and sodium carbonate. A red precipitate indi-
cates Ni (see page 115).
Iron: A drop of the solution is mixed on the spot plate with a drop
of potassiiun thiocyanate. A red color indicates Fe (see page 124).
Chromium: A drop of the solution is mixed on a spot plate with a
drop of 2 N sodium hydroxide, one of bromine water, and one of phenol
water. The mixture is acidified with 2 drops of 2 AT hydrochloric acid,
and a drop of diphenylcarbazide is added. A violet color indicates Cr
(see page 128).
Manganese: A drop of sodium potassium tartrate, one of the test
solution, and one of sodium hydroxide are placed on filter- paper. The
moist fleck is treated with an acetic acid solution of benzidine." A blue
color indicates Mn (see page 134).
Tin: Two drops of the solution are mixed with 3 drops of cone,
hydrochloric acid in a micro test tube and a little zinc (turnings) added.
The mixture is boiled for 1 minute, then filtered through a sintered glass
filter stick onto a spot plate, and tested with cacotheline. A violet color
indicates Sn (see page 87).
The rest of the solution is mixed with 25% sodiimi hydroxide until a
permanent precipitate forms. Then 5 to 6 more drops-of alkali are added,
the mixture is boiled for 1 minute, cooled and centrifuged. The solution
is tested for zinc, aluminum, and lead.
SPOT ANALYSIS OF ALLOTS 291
Zinc: Two drops of potassium ferricyanide and diethylaniline solu-

tion are mixed on a spot plate and a drop of the test solution added. A
brown color forms, sometimes only on long standing. A blank test is
necessary (see page 137).
Aluminum: A drop of the solution is placed on a black spot plate and
3 drops of 2 N acetic acid and a drop of morin solution are added. A
green fluorescence is formed, which should be compared with a blank test
on 2 i\r sodiimi hydroxide (see page 142).
Lead: A few drops of the solution are treated on a spot plate with a
drop of potassium cyanide to prevent interference from any copper that
may have gone into solution. Then a drop of ammonium sulfide is added.
A brown color indicates Pb.
The precipitate obtained with sodium hydroxide is dissolved in a few
drops of cone. HCl. The solution is treated with excess anamonia, cen-
trifuged, and the solution tested for copper, cobalt, and cadmium.
Copper: A drop of the solution is placed on spot paper, gently warmed
and treated with benzoin oxime. A green color indicates Cu (see page 65).
Cobalt: A drop of the solution is stirred on a spot plate with 2 drops
of 2 iV hydrochloric acid, 1 drop of 10% potassium iodide, and then treated
with a little solid sodium sulfite. A drop of a-nitroso-/5-naphthol and 2 to
3 drops of sodium acetate are added. A brown color indicates Co (see
page 111).
Cadmium: The rest of the solution is treated with a few drops of 10%
potassium cyanide in a micro test tube. The mixture is heated to boiling
and a drop of ammonium sulfide added. A yellow precipitate or turbidity
forms if Cd is present.
Spot Analysis of Alloys According to Heller^
About 0.01 g. of the nitric-acid-soluble sample is evaporated to dryness
on the water bath with a few drops of cone, nitric acid. The residue is
taken up with a httle 2 ISf nitric acid, filtered, and washed (Solution I,
Residue I). Alloys not attacked by nitric acid are dissolved in bromine-
hydrochloric acid, and the solution taken to fumes with nitric acid.
Residue I is tested for tin and antimony. A few drops of cone,
hydrochloric acid are run through on the filter, and Sb identified in 1 or 2
drops of the filtrate. The rest of the filtrate and the residue are treated
with zinc and tested for Sn.
A drop of solution I is tested for silver, and the rest is heated with a
few drops of sulfuric acid until white fumesare given off, then taken up in
about 2 ml. water, filtered, and washed (Precipitate II, Solution II). Con-
' K. Heller, Mikroehemie, 8, 33 (1930).
292 V. STSTBMATIC ANALYSIS OF UIXTUBIIS
centrated potassium hydroxicie is poured over the precipitate and lead

identified in the filtrate.
HjS is led into solution II and the acid sulfides (Precipitate III) are
separated from solution III. Precipitate III is dissolved in hot 2 AT
HNOj. The clear filtrate is tested for copper, bismuth,' apd cadmium.
Solution III is ojddized with bromine. The excess is removed by
concentrating to 2 ml. and this solution is tested for Fe, Ni, Co, Cr, and Mn
by suitable spot tests. The rest of the solution is treated with 2 N KOH.
AJ and Zn are to be identified in the cone, filtrate.
This separation with potassium hydroxide introduces a high content
of alkali salts. These reduce the sensitivity of the tests, both on the spot
plate and on paper.
The individual cations can be detected by the following reactions:
Silver: Test with p-diaminobenzyhdenerhodanine on the spot plate
(see page 43).
Lead: Test with benzidine, on paper (see page 55).
Tin: Test with ammonium phosphomolybdate paper (see page 86).
Antimony: Test with phosphomolybdic acid paper (see page 84).
Capper: Test by formation of copper zinc mercury thiocyanate, on
a spot plate (see page 73).
Cadmium: Test with dinitrodiphenylcarbazide, on a spot plate (see
page 77).
Bismuth: Test with alkaline stannite solution and lead chloride, on
the spot plate (see page 60).
Iron: Test with potassium thiocyanate, on the spot plate (see page
124).
Chromium: Test with diphenylcarbazide, after conversion into
chromate, on the spot plate (see page 128).
Cobalt: Test with a-nitroso-/3-naphthol, on filter paper (see page 110).
Nickel: Test with dimethylglyoxime, on the spot plate (seepage 114).
Manganese: Test with benzidine, on the spot plate. A drop of
saturated sodium tartrate solution, one of potassium hydroxide, and one of
benzidine are added to a drop of the solution (see page 135).
Zinc: Test by formation of zinc copper mercury thiocyanate, on the
spot plate (see page 140). f
Aluminum: Test with alizarin sulfonic acid, on the spot plate (see
page 143).
Table 5 shows the percentages of the constituents of the alloys ex-
amined by Heller. _-
The figures enclosed in parentheses indicate "percentages of metals
present, but not revealed, by this procedure. "0" indicates that a metal
was found present, although it was not given as a constituent of the alloy.
SPOT ANALYSIS OP ALLOYS 293
TABLB 5. ALLOTS ANALYZED BT HELLBB
I Pb,% Sn,% Sb, Cu, Cd, Fe,

% a. Ni,% Mn,% Zn, Other
constit-
i
% % uents
10 63 17 13 7.6
10 64 13 21 1
10 33 62 C, Si,
S,P
Up 22 77 C.Si,
S,P
10 14 76 3.3 0
10 100
10 16 83 C.Si,
S.P
8 10 64 13 23
9 10 26 13 12 49
10 10 99.9
11 10 7 86 1 2.1 4
12 10 2 81 11 6 .0.1 0
13 10 76 10 12 0.1 0.6
U 10 0.04 32 67 (0.06) C,Si,
S,P
15 10 28 72 (0.1) C,Si,
S,P
16 10 3.5 C,Si,
S.P
17 10 99 (0.6) C,Si,
S,P
18 10 66 0 10 24
19 10 95 3.5 C,Si,
S,P
20 10 0.8 99
21 10 96 0.5 (0.5) C,Si,
S.P
22 10 62 1.3 0.9 0
23 10 0.7 21 78 0.2
24 10
3.4
3.8 16 0 78 0.3
25 10 0.2 11 87 1.3 (0.8)
26 10 0.6 2.2 (0.3) 96 0.3 1.6
27 10 0.3 99.6 0.08 (0.2)
28 10 61 0.4 15 (0.2) 24
29 10 1.2 (0.3) 0 98
30 20 1.2 (0.3) 0 98
31 10 0.9 (0.6) 0 98
32 20 0.9 0.6 0 98
33 10 0.6 22 77 0.8
294 V. SYSTEMATIC ANALYSIS OF AnXTUBES
TABI/E 6. Continued 1
M
a i
a I
Cu, Cd. Bi, Fe, Other

1 *^' Pb.% Sn,% Sb,
% % % % %
Al, Cr. Co, Ni;% Mn,%
% % % 1
Zn,
%
constit-
uents
a
.9
i
34 10 0 94 1.1 3.4 (0.5) C,Si,
S,P
36 10 50 (0.1) 0 10 40
36 10 (0.6) 54 7 2.1 36
37 10 0.7 1.4 62 1.6 (35)
38 10 2.5 5.6 0.2 16 75
39 10 2.6 (8.9) 0.9 82 0.6 4.8
40 10 3.7 5.9 0.7 84 0.6 0.4 4 p
41 10 12 6.7 79 0.4 2.1
42 10 0.6 63 0.5 36
43 10 0.9 22 (0.7) 68 0.1 0.9 4.7
44 10 3.2 12 0.5 81 4.2 0.6
45 10 1.1 (0.1) 68 0.2 (0.07) 40-
46 60 1.1 0.1 68 0.2 0.07 40
47 10 1.9 81 10 5.8 0.1
48 10 0.7 1.4 69 0.2 0.4 29
49 10 5.7 6.6 79 4.5 4.4 0.9 1.2
50 10 (0.03) (0.15) (0.2) 99 0.27 As
61 50 0.03 0.15 0.2 99 0.27 As
According to Heller, the examination can be accomplished with one-fiftieth

of the quantity of sample required for macroanalyses, and the procedure
consumes only one-fourth as much time.
Application of Spot Tests in Preliminary Examination

Before proceeding to the systematic analysis in the wet way, it is
always advisable to carry out prehminary tests to obtain general informa-
tion as to the nature of the sample. The results of this examination are
often important in establishing the presence or absence of certain sub-
stances, in making an intelligent choice of solvents, etc. A small sample,
about the size of a millet seed to a grain of com, is usually sufficient for the
preliminary analysis. Solid samples should be very finely ground and well
mixed; liquid samples should be evaporated to.dryness and the tests carried
out on the residue. During evaporation of the liquid the sample should be
observed for loss of volatile matter. Spot reactiona.can often be success-
fully applied directly to the solid sample or to" the evaporation residue.
Various methods of testing, characteristic of certain groups, will be given.'
See the extensive treatment in Bottger, op. cit. (this text, page 183), and in
C. R. FreseniuB, op. cit. (this text, page 101). ''
APPUCATION OF SPOT TESTS 295
1. Heating on a Magnesia Spoon or in a Porcelain Dish

The sample remains unchanged: no oiânic matter is present or com-
pounds containing water of crystallization; no volatile comjiounds are
present (with exception of carbonates).
The sample fuses: presence of alkali salts.
The sample changes color: presence of compounds of the heavy metals.
Darkening indicates formation of oxides from salts (e.^., Cu++ CuO,
Fe"*"*+ FejOj, etc.). Lightening indicates decomposition of higher oxides
(e.g., Pb02 '-^ PbO) or oxidation of sulfides (cgr., PbS - PbSO*). Certain
metal oxides exhibit different colors at room temperature and on ignition
ie.g., ZnO, CdO, NiO, etc.). The color invariably is deeper at the higher
temperature. The metal is deposited from carbonates or oxides of the
noble metals, and from salts of organic acids with readily reducible metals.
The sample partially or wholly chars: presence of organic compounds.
Metallic salts of the organic acids (with the exception of formic) produce
carbonates (detection, see page 254).
2. Heating in an Ignition Tube

The sample gives off vxiter: presence of salts containing water of
crystallization; moist substances; hydroxides, and ammonium salts. Test
for acid or alkaline reaction in the water condensed on the cold part of the
tube.
A white sxiblimate: NH4 salts; AsjOj; Sb208; many Eg salts; OJcalic
add; benzoic acid.
A yellow sublimate: AsSi, aJid AsjSs; Hgis; free sulfur, or sulfur'from
polysulfides or heavy metal thiosulfates. Yellow Hglj is transformed to
the red modification if rubbed with a glass rod.
A gray sublimate:finelydivided mercury from Hg compoxmds; free
arsenic from As compounds in the presence of reducing substances; free
iodine from iodides in the presence of oxidizing substances.
Add vapors (litmus paper): volatile acids from acid salts; S0| from
sulfates of thfe heavy metals; SOa from sulfites or sulfur with access to air
or in the presence of oxidizing agents.
Brown vapors: bromine from bromides in the presence of oxidizing
agents; nitrous oxides from nitrites or nitrates; CrOjCU if both bichromate
and water-containing chlorides are present.
Violet vapors: iodine from iodides or iodates.
Colorless vapors: CO2 from carbonates and salts of organic acids;
(CN)s or HON from decomposable cyanides, e.g., Hg(CN) or Prussian
blue; HjS from water-bearing sulfides or thiosulfates; NH from NH salts
or thiocyanates.
296 V. SYSTEMATIC ANALYSIS OF MIXTXIRBS
3. Tests on the Aqueous Solution or Suspension.'

One or two drops of the aqueous solution, or water suspension, of a
solid sample are tested with the following reagents either on a spot plate
or in a microcrucible. Very small quantities of the .solid may also be
tested directly.
Indicators:^ An acid reaction with litmus paper indicates free acid,
or acid salts, or hydrolyzed salts of weak bases. An alkaline reaction
indicates alkali or alkaline earth hydroxides, carbonates, or sulfides, or
hydrolyzed salts of sti'ong bases. If an acid reaction is obtained, the solu-
tion is tested with congo paper. A blue color (pH g 3) indicates strong
acids. When an alkaline reaction is given with litmus, the solution is
further tested with thymolphthalein. A blue color (pH ^ 10.5) indicates
the presence of ammonia, or alkali salts of very weak acids. If tropaolin
O is colored orange-brown (pH = 12), then free alkali or alkaline earth
hydroxides are present.
Sulfuric acid-j)otassium iodide solution: Liberation of iodine indicates
the presence of oxidizing agents. When hydrogen peroxide or peroxides
are suspected it is advisable to add a small amoimt of ammonimn molybdate
as catalyst to hasten the hberation of iodine, since this action is quite slow
otherwise.
Acetic acid-4odine-j)otassium iodide solution: Decolorization indicates
the presence of reducing substances. ,
Another spot test for detecting soluble reducing substances is carried
out on paper impregnated with manganese dioxide.' A drop of the solu-
tion, acidified with acetic acid, is placed on the paper, which is then dried
in a blast of heated air. Consumption of MnOj leaves a lighter area or a
white spot on the paper. The reagent paper is prepared by bathing strips
of filter paper in a weakly basic dilute solution of KMn04, washing, and
drjong. ITie MnOj produced by the reducing action of the cellulose
remains homogeneously dispersed ia the capillaries of the-^paper. The
color of the prepared paper ranges from brown to barely visible "yellow,
depending on the concentration of the permanganate solution "and the
duration of its action. The reaction of small^ quantities of reduciog
materials (use hght-colored MnOs paper) can be made easily visible, if,
after reduction, the paper is bathed in an acetic acid solution of benzidine.
The unused Mn02 produces a deep blue surface, against which the white
MnOj-free areas appear in sharp contrast.
Dilute sulfuric acid: Liberation of colorless gases (a), or colored gases
(6); ^^ '
' In part, from F. Feigl, unpublished studies.
' According to W. D. Treadwell, Tabellen zur qtuditativen Analyse. 13th ed.,
Deuticke, Vienna, 1932, p. 78.
F. Feigl, Chemistry & Industry, 67, 1161 (1938).
APPLICATION OF SPOT TESTS 297
(a) CO2 from carbonates; HCN from cyanides; .HjS from sulfides;
SO2 from sulfites and thiosulfates; acetic acid from acetates; oxygen from
peroxides.
(b) Brown, yellow, or violet gas: nitrous oxides from nitrites; chlorine,
bromine, or iodine from halides in the presence of oxidizing agents.
Cone, sulfuric acid: As with dilute sulfuric acid but more vigorous;
also HCl from chlorides; oxygen from chromates, permanganates, and
peroxides; HF from fluorides and fluosilica'tes.
Hydrogen sulfide water acidified with hydrochloric acid: A colored
precipitate indicates metals of the H2S group.
Ammonium sulfide solution: A colored precipitate indicates basic
sulfides. When the H2S test was negative, then sulfides of Co, Ni, Fe,
Mn, Tl, and U may be present.
Alkali hydroxide: A black color indicates mercurous salts, or the
simultaneous presence of salts of one or more noble metals (Au+++, Ag+,
Pt++, Pd++ ions) and a salt of these metals capable of forming higher
insoluble oxides (Mn++, Co++, Fe++, Ce+++ ions)"; a black color may also
be formed by the simultaneous presence of Sn(II) salts and Bi salts (deposi-
tion of free bismuth).
Alkaline hydrogen peroxide: Bleaching indicates sulfide (sulfate
formation); darkening of color indicates formation of higher oxides of
Mn, Co, Fe, Ce, Pb.
The following procedure can be used to establish the presence of metal
ions, which form higher oxides (Mn, Ce, Co, Ni, Pb, Bi, Tl). A drop of
freshly prepared NaOBr solution is placed on filter paper. Before the
hypobromite has entirely soaked in, a drop of the test solution is added.
Higher oxides are formed. The excess NaOBr is decomposed by repeated
application of ammonia water. After drying, the paper is spotted with an
acetic acid-benzidine solution. A blue color results if higher oxides are
present.
Hydrogen peroxide containing, hydrochloric acid: Bleaching or solution
of a dark powder indicates higher oxides (Pb02, Mn02, etc.) or sulfide
(conversion to sulfate).
Ammoniacal silver solution: In the absence of halogen, ions, a black
color indicates Mn(II), Te(II), Co, Ce(in), or Cr(III) salts."
Phosphoric acid-ferrous sulfate: A dark color or precipitate indicates
noble metals, selenium, or tellurium, released by reduction.
Sodium azide-dodine solution: Decolorization of the neutral test
'" A reaction of the following type occurs:
2 Ag+ + Mn++ + 4 OH- = 2 Ag + MnOj + HjO
The adsorption compound of the noble metal and higher metallic oxide causes the
black color (see page 42).
" See preceding footnote.
298 V. STSTEUATIC ANALYSIS OF MIXTTJEES
material with evolution of gas (nitrogen) indicates the presence of sulfides,

thiosulfates, or thiocyanates.
Alkaline sodium nitroprusside solution: A few grains of the powdered
sample are warmed with sodium hydroxide. (Sulfo salts are formed from
acid sulfides). After cooling, sodium nitroprusside is added. A red-violet
color indicates sulfides of As, Sb, Sn, W, or Mo, since they alone dissolve
in NaOH to produce sulfo salts.
Ferricyanide-ferric chloride: A small portion of the sample, freed of
soluble reducing materials by thorough extraction with water, is treated on
a spot plate with 1 drop each of dilute solutions of K3Fe(CN)6 and FeCU.
A blue color or precipitate indicates the presence of uncombined metals or
alloys. (Au, Pt, Pd are exceptions.)
Silver ferrocyanide paper and ferric sulfate:^^ A green that turns into
blue indicates the presence of CI", Br~, I~. The test is based on the
formation of Prussian blue by reaction of Ag4Fe(CN)6 \vith the halide
ions, in the presence of a ferric salt. The reagent paper is prepared as
follows: Photographic silver-citrate paper is bathed for 10 minutes in 1%
K4Fe(CN)6 solution. It is then washed with water, dilute silver nitrate,
and again with water. It is then immersed in 10% ferric sulfate, and dried.
Scheme of Analysis for Anions in a Mixture^^

No completely satisfactory scheme for the systematic detection of all
inorganic and organic anions has been developed. An orienting, prelimi-
nary examination for those anions that occur most commonly is described
here. The procedure is based on the division of anions into two groups by
the action of zinc nitrate. Spot tests for particular anions are made on
the precipitate and with the filtrate.
If the original material does not consist of alkali salts, the sample is
boiled with strong sodium carbonate solution, or it is fused with sodium
potassium carbonate in a platinum spoon. Heavy metal 'fealts..are thus
converted into insoluble carbonates. After adding water and filtering,
and filtering, any ammonium ions are removed by boiling with sodium
hydroxide. Nitric acid is then added, but not sufficient to neutralize the
solution. (In this way CuO can also be precipitated, if the carbonate
solution was blue, owing to complex copper carbonate.) The weakly
alkaline solution is then treated with zinc nitrate, added either as a con-
centrated solution or as a solid. The mixture is warmed and filtered.
There resultsT ^
" C. Duval and G. Mozara, Compt. rend., 207, 862 (1938>: Statements regard-
ing the differentiation of Cl~, Br", I~ iona are given there.
" Compare F. Feigl., Z. anal. Ckem., 67,135 (1918).
ANALYSIS FOB ANIONS IN A mXTTTinE: 299
(A) A precipitate of the zinc salts of S, As07 , AsOJ , POr~~,

B O r " , F-, FeCCN)!""", Fe(CN)r~", CN", VOr~~, MoOr-, and
WOr~ (Treatment I).
(B) A solution containing the anions: CNS~, Cl~, Br~, I", ClOr, SOr~,
SjOr", SOr~, CrOr~, and NOi" (Treatment II).
I. Small portions of the well washed precipitate A are transferred to
filter paper or a spot plate and spotted, or treated as prescribed, with
solutions 1 to 10, in succession:
/. Acid lead nitrate solution: black or brown color indicates S .
2. Acid solution of ferrous salt: blue color indicates Fe(CN6) .
S. Acid solution of fenic salt: blue color indicates Fe(CN6) .
4. Stannous chloride solution: yellow to brown color indicatesMoO?" or
wor".
5. Hydrochloric acid-potasaum xanthate solution: violet color indicates
MoOr" (see page 93).
6. Ammonium molybdate solution, benzidine, and ammonia: blue color
indicates POr (see page 250).
7. A little of the precipitate is dried and ignited. The ignition residue is
subjected to the Gutzeit test for arsenic (page 80). A positive result
indicates AsOr or AsOr .
8. A portion on curcuma (turmeric) paper treated with HCl. On
drying, a reddening that turns a dirty blue with KOH indicates
BOr . A little of the precipitate may also be warmed in a micro-
crucible with 3 drops of 0.01% solution of quinalizarin in cone,
sulfuric acid. A color change (violet-blue) indicates BjOj (see page
267).
9. If no sulfide ions are present, a portion is spotted with mercurous
nitrate: a blackening indicates CN~. When sulfides are present,
and complex iron cyanides are absent, the procedure on page 209
may be used. Alternatively, a little of the precipitate may be
digested with ammonia water. This dissolves Zn(CN)s. The
ammoniacal filtrate is tested for cyanide as described on page 208.
10. A small amount of the precipitate is stirred with BaClj on a spot platte,
and a drop of a hydrochloric acid-zirconium-alizarin solution is
added. After a short time the color changes from red to yellow in
the presence of F" (see page 202).
II. The following spot tests on filter paper or on a spot plate are
carried out with single drops of solution B:
J. Acid ferric chloride solution: a red color indicates CNS~.
300 V. SYSTEMATIC ANALYSIS OF MIXTUHES
S. Diphenylcarbazide in sulfuric acid solution: a vidlet color indicates

CrOr~ (see page 128).
S. Barium rhodizonate suspension: decolofization of the'red-fleck indicates
S07~ (see page 236). i
4. Aniline sulfate and cone, sulfuric acid: a blue color indicates ClOr.
5. Palladium chloride solution: blackening indicates I"" (see page 197).
6. Fuchsin-bisulfite solution: blue color indicates Br~ (see page 196).
7. Dilute iodine-potassium iodide solution: decolopization indicates SOF"
and SjOr". The decolorized solution tested with htmus paper is:
neutral if SjOF" is present; acid if SOr~ is present.
8. A portion of the solution B is precipitated hot with Pb(N03)2 and the
precipitate spotted with AgNOs: a brown color indicates SjOr".
Nitrates and nitrites may be detected directly in the sodium carbonate
or sulfuric acid extracts of the sample (see pages 243 and 248).
Identification Tests for Substances Insoluble or

Sparingly Soluble in Acids^*"Insoluble Residue"
The examination of certain solids requires consideration of the fact
that they are more or less insoluble in the usual solvents (water, dilute and
concentrated acids, and also agua regia). In order to detect the con-
stituents of acid-insoluble residues they are usually subjected to attack
by special reagents, which convert them into compounds soluble in the
usual solvents (water, acids, alkalis). After they are dissolved, they can
be identified without further diflBculty by the aid of suitable reagents.^'
If the insoluble residue is not a single substance, this method of
attack is unsuited to small amounts of material, as it may be necessary,
according to the nature of the residues, to use a number of different open-
ing-up agents in order to reach a decision more quickly.^'
The use of suitable spot methods makes it possible tO' detect quickly
and easily numerous compounds, that may constitute an insoluble residue.
Not more than a small portion is required. In order to identify "the com-
pounds given here in a mixture (containing 0.01 njole of each constituent),
1 or 2 mg. is sufficient. Sometimes even much less of an acid-free, washed
sample may be used.
" F . Feigl, Mikrochemie, 20, 198 (1936).
"Compare W. Bottger, op. oil. (this text, page 183), p. 532 ff; C. R.
Fresenius, op, cil. (this text, page 101), p. 671. ,
" E. R. Caley and M. G. Burford, Ind. Eng. Chem., Anal. Ed., 8, 63 (1936),
showed that certain insoluble compounds, such as SnOj, PbSOj.JBaSOj, CaFj, and Ag
halidea, can be converted into water-soluble iodides or double iodides by heating
with hydriodic acid, (sp.gr. 1.7). '
IDENTIFICATION OF INSOLtlBLB SUBSTANCES 301
1. Insoluble Sulfides
Sulfides of mercury (or mercury sulfo salts) and arsenic may be pres-
ent, also naturally occurring sulfides, such as the minerals: pyrites, molyb-
denite, galena, etc.
The catalytic acceleration of the reaction between sodium azide and
iodine (see page 228) is the best test for sulfides. It gives a positive result
with even traces of sulfide sulfur. It is sufficient to place a grain of the
powdered sample on a small watch glass and add 1 or 2 drops of iodine-
azide solution. The formation of small bubbles of nitrogen on the surface
of the solid indicates the presence of sulfides.
2. Insoluble Sulfates
PbSbi, BaS04, SrSOi, and CaS04 come under this category.
A general test for slightly soluble sulfates is to treat a little of the
material on a watch glass with a drop of an acid solution of mercuric nitrate
[10 g. Hg(N0s)2 plus 1 ml; cone. HNOj, in 100 ml. water]. Yellow basic
mercuric sulfate is formed." CaSOi and PbS04 respond at room tempera-
ture; SrSO* and BaSO* must be warmed before the yellow develops. If
sulfides and halogen compounds are absent, the test is decisive. The test
material must be colorless; otherwise the yellow cannot be seen.
When neither sulfides nor elementary sulfur are present, it is possible
to reduce insoluble sulfates to potassium sulfide by fusion with metallic
potassium (see page 238). The sulfide may then be identified either by
the iodine-azide reaction, or by the sodium nitroprusside reaction (see page
226). Because of the extreme sensitivity of the iodine-azide reaction,
a fraction of a milligram of sample is sufficient for the detection of
sulfate. The nitroprusside test is less sensitive, but it is quite satisfactory
for many purposes. A larger sample is required in this case.
Lead sulfate may be detected in the presence of alkaline earth sulfates
as follows: A sample of the order of 1 mg. is stirred in a microcrucible with
a warm mixture of acetic acid and ammonium acetate. The lead sulfate
goes into solution owing to the formation of slightly dissociated or complex
lead acetate. A strip of filter paper is dipped in the suspension and left
for 10 minutes. The lead salt rises with the solvent and lead may then be
detected in the paper several millimeters above the surface of the liquid.
Lead sulfide is produced, either by blowing hydrogen sulfide gas against the
paper or by applying a drop of hydrogen sulfide water or ammonium
sulfide. 'f
A quicker, surer, and more sensitive direct test for lead sulfate in an
" G . DenifSs, Bull. toe. chim., 28, 36 (1918).
302 V. STSTEMATIC ANALYSIS OF MIXTCBES
insoluble residue is provided by spotting with a fresh 0.2% solution of

sodium rhodizonate." A blue-violet color appears, \v:hich turns scarlet
when spotted with acetic acid. The color is due to thd formation of lead
rhodizonate (see page 56).
When lead has been found to be absent from an insoluble sulfate
residue, then barium sulfate (or strontium or calcium sulfates) are likely to
be present. The alkaline earths may be detected as follows: A small
sample is mixed with 3 to 4 times its bulk of sodium potassium carbonate
and fused in a loop of platinum wire. The melt is heated with water in a
microcentrifuge tube and theu centrifuged. After pouring off the super-
natant liquid, the residue is washed several times \vith water and collected
by centrifuging. Finally the solid is dissolved ux dilute hydrochloric acid
and tested for alkahne earths by the flame color.
3. Silver Halides
Agl, AgBr, AgCl, AgCN, AgCNS, and AgNj may be present.
A good and rapid test for the presence of silver halides is based on
their ready solubility in alkali cyanides, with formation of complex alkali
silver cyanides. When the cyanide is used in the form of a solution of
potassium nickel cyanide, nickel cyanide is liberated:
AgHal + KjNi(CN)4 = KA.g(CN)s + Ni(CN)s + KHal
The nickel cyanide reacts with dimethylglyoxime with formation of red
nickel dimethylglyoxime. Since, at room temperature, K2Ni(CN)4 reacts
with dimethylglyoxime hardly at all, a stable mixed solution of the two
compounds may be prepared. It inamediately produces nickel dimethyl-
glyoxime when brought into contact with silver halides.*'
The nickel cyanide formed by the foregoing reaction only reacts
slowly with dimethylglyoxime in the cold, but on the addition of ammonia,
which dissolves the nickel cyanide, the reaction is quite rapid." A solution
of KjNiCCN)^ ammonia, and dimethylglyoxime, therefore reacts almost
instantaneously with all silver halides (whether freshly precipitated or
aged by drying for several weeks). Red nickel dimethylglyoxime is
formed.
" F. Feigl and H. A. Suter, Ind. Eng. Chem., ATMI. Ed., 14, 840 (1942).
" A. R. Ubbejohde, Analyst, 69, 339 (1934), was the first to recommend a solu-
tion of complex nickel cyanide and dimethylglyoxime as reagent for met&l ions that
form undissociated cyanides (Ag+, Pd++, Hg""^).
" The sluggish reaction of Ni(CN)j with dimethylglyoxime is due to the fact
that nickel cyanide should be viewed as Ni[Ni(CN)4l. Accordingly, only one-half
of the nickel, the cationic part, reacts, and then only slowly-be'cause of the slight solu-
bility of the salt. This dissolves in ammonia to form [Ni(NHi)2] [Ni(CN)4] and
the Ni(NHj)j** ions then react at once with dimethylglyoxime. Compare P. Feigl
and co-workers, BuU. Lab. Prod. Mineral, Minist. Agricultura Brazil, 1944.
IDENTIFICATION OF INSOLUBLE SUBSTANCES 303
To detect the presence of a silver halide in an "insoluble residue," it is

only necessary to place a trace of the sample on a white spot plate and add
1 or 2 drops of reagent. A bright red color or precipitate indicates AgCl,
AgBr, Agl, AgCNS, AgNj, or AgCN. Silver iodide reacts a little more
slowly, owing to its small solubility product, but even with this compound
the reaction is complete in one^half minute.
The reagent is best prepared by boiling freshly precipitated and
washed Ni(CN)j with KCN solution, using a deficit of the latter so that
not all of the Ni(CN)j goes into solution. The K2Ni(CN)4 solution
obtained by filtration will keep. Immediately before the test, a few
milliliters of this solution are mixed with a few drops of ammonia, and a
few drops of a saturated alcoholic solution of dimethylglyoxime, and fil-
tered, if necessary.
The silver halides may be partially differentiated by their behavior in
an ignition tube. AgCl and AgBr melt without decomposing; AgCN and
AgCNS, after the ignition, leave metallic silver, which may be dissolved in
warm dilute nitric acid and (after filtration, if necessary) identified by the
sensitive reaction with p-dimethylaminobenzylidinerhodanine (red precip-
itate, see page 43).
Silver iodide can be detected by means of palladium chloride." A
few mg. of the sample are spread on a strip of filter paper, moistened with
a drop of water, and held over a small beaker containing boiling water.
After 1 or 2 minutes, the spot is treated with a drop of a 1% PdClj solution.
On further steaming, the surface of the silver iodide is colored brown-black
due to the production of pdlj.
4. Ferric Oxide
t
Ignited FeaOs and iron oxide ores are soluble in acids only with great
diflSculty. In order to convert the iron into the form of the soluble red
iron (III) thiocyanate, a special fusion is unnecessary. It is sufficient to
treat a small sample of the residue with a sulfuric acid solution of potassium
or ammonium thiocyanate and warm gently in a microcrucible. The
original colorless reagent solution turns blood red or pink, according to the
quantity of iron involved. Even a trace of iron in alumina may be rapidly
detected in this way.
5. Aluminum Oxide
To detect ignited AljOj in a residue, it is essential to fuse the sample
with alkali pyrosulfate or bisulfate in a platinum spoon, in order to obtain
soluble A1,(S0),.
w N. Orlow, Chem. Zentr., 1906,11, 630.
304 V. SYSTEMATIC ANALYSIS OF MIXTURES
(
The following tests may be applied to the aqiieous extract of the
fusion mixture. Any other metals present are precipitated with excess
alkali hydroxide and the hydroxides are separated from the aluminate by
centrifuging. The aluminate solution is acidified with acetic acid and
mixed with a few drops of a saturated solution of morin in methyl alcohol.
A green fluorescence forms in the presence of aluminum (see page 142).
Alternatively, the aluminate solution may be treated with a drop'of an
aqueous solution of sodium alizarin sulfonate and then acidified with
acetic acid. The red color of the aluminum alizarin lake indicates alumi-
num (see page 143).
6. Titanium (IV) Oxide

Titanic acid anhydride, Ti(0H)4-aq and basic titanium salts in the
presence of hydrogen peroxide dissolve readily in warm dilute sulfuric acid
giving a yellow color (pertitanic reaction, see page 150). Ignited TiOa.
must be treated with alkali pyrosulfate or bisulfate, as described in 5above,
before adding the sulfuric acid and hydrogen peroxide. It is simpler to
heat the sample with concentrated sulfuric acid until white fumes appear.
After cooling, the residue is treated with solid chromotropic acid (see page
151). A violet color indicates TiOj.
7. Chromium (III) Oxide and Anhydrous Chromium (III) Chloride

These two compounds, which are very difficultly soluble in acids,
are not hard to detect even in relatively small amounts though mixed
with other substances. Their vivid colors (CraOa green, CrCU violet) are
quite characteristic. To detect chromium decisively it is sufficient [even
with dark gray acid-insoluble chrome iron ore (chromite) FeCr04 ] to take a
little of the powdered sample and fuse it in a platinum spoon or a porcelain
microcrucible with a mixture of sodium carbonate and podium peroxide
(1:1). The cooled melt is dissolved in a few drops of concentrated sulfuric
acid, and 1 or 2 drops of a 1% solution of diphenylcarbazide solution are
added. A violet color indicates chromium (see page 128).
Mercury salts and molybdates in acid solution also give violet colors
with the diphenylcarbazide reagent. When the/ insoluble residue is
assimied to contain mercury salts {e.g., HgS), they must be completely
eliminated by long ignition before the carbonate-peroxide fusion. Alterna-
tively, hydrochloric acid may be used in place of sulfuric acid to dissolve
the melt, so that nonreacting HgC17~ ions are formed. The'reaction with
mplybdate may be masked by the addition of a-fewTdrops of a saturated
aqueous solution of oxalic acid, to form the complex molydenum-oxalic
acid (see page 130).
IDENTIFICATION OP INSOLUBLE SUBSTANCES 305
8. Lead Chromate
Yellow precipitated lead chromate, either wet or dried, is readily
dissolved or decomposed by dilute mineral acids. In contrast, lead chro-
mate that has been fused (m.p. 844C.) is red-brown and is quite resistant
even to concentrated mineral acid^. Accordingly, PbCr04 may be con-
tained in an insoluble residue.^^ l
Fused lead chromate may be detected by the fact that dilute sulfuric
acid extracts from it, even at room temperatures, sufficient chromic acid
to respond to the very sensitive diphenylcarbazide test (page 128). It is
better to subject the finely powdered sample to the combined action oi 5 N
sulfuric acid and 1% alcohol solution of the reagent (2 drops of each). An
intense violet will appear in a few minutes.
Strongly ignited, acid-soluble molybdenum trioxide also gives a
violet color vnth diphenylcarbazide. In case its presence is suspected, a
saturated solution of oxalic acid should be used in place of the 5 A'' sulfuric
acid. Oxalic acid masks the M0O3 by forming complex molybdic-oxalic
acid and thus prevents the MoOa-diphenylcarbazide reaction.
9. Manganese Dioxide and Lead Peroxide

The mineral pyrolusite (MnOa) is very resistant to even hot strong
acids, while Pb02 is similarly resistant towards fairly dilute hydrochloric
and nitric acids. Both oxides may, however, readily be brought into
solution by treatmênt with dilute nitric acid and hydrogen peroxide, even
at room temperature.^' Therefore, if a very small sample of a dark insolu-
ble residue is treated on a spot plate with a drop of 2 iV nitric acid and a
drop of 3 % hydrogen peroxide, decolorization indicates the presence of
Mn02 or Pb02, or a naixture of these oxides.
Both these oxides also react with an acetic atld solution of benzidine
and produce a blue color due to oxidation products of benzidine (see pages
55 and 134). It is sufficient to take a little of the sample (which may with
advantage be streaked on quantitative filter paper) and treat it with a drop
of benzidine acetate solution. The blue color appears at once.
Chromate is formed by heating a small sample containing PbOj or
MnOa in a microcrucible with a solution of Cr2(804)3 in strong.sulfuric acid.
"2 After fusion, lead chromate no longer corresponds exactly to the formula
PbCrO. Some of the salt decomposes,when it melts (4 PbCrO^ > 4 PbO + 2 CrjOj
-1- 3O2). Consequently, only precipitated lead chromate dissolves completely in
sodium hydroxide [PbCrO, -1- 4 NaOH -< Pb(ONa), + Na,CrO, + 2 HjO] whereas
the melted salt always leaves a considerable residue of green CrjOs.
" Whereas neutral hydrogen peroxide is catalytically decomposed on the
surface of the manganese dioxide, with evolution of oxygen, the following reaction
occurs in the presence of acids: MnOj -|- 2 H+ -{- HjOj = M n ^ + 2 HjO -f- Oj. Lead
peroxide and other higher metallic oxides behave analogously.
306 V. SYSTEMATIC ANALYSIS OF MDCTIJHES
The product may be identified, after cooling, by the viplet color formed on
the addition of a drop of a 1% alcoholic solution of diphenylcarbazide.
The Crs(804)2 solution used must be chromate-free (blank test), otherwise
it must be boiled with H2SO3 before the test.
It is easy to distinguish between MnOa and PbOj. A few grams of
the sample are spotted with freshljf prepared sodium rhodizonate solution
and dilute acetic acid. Red lead rhodizonate is formed (see page 56).
10. Tungsten (VI) Oxide
Tungstic anhydride gives a bright blue color when warmed with a
solution of stannous chloride in strong hydrochloric acid. Insoluble, lower
oxides of tungsten are formed. It is advisable, especially in the detection
of WO3 in minerals, first to open up the sample by fusing with sodium
peroxide in a microcrucible, and then to spot the melt with a strongly acid
solution of stannous chloride. It should be noted that, under these
conditions, a blue color is produced also by MoOj. This "molybdenum
blue" is a mixture of soluble lower molybdeniun oxides.
11. Metallic Tungsten and Molybdenum
Wire (electric bulb filaments, etc.), highly alloyed steels, or concen-
trates mth a high tungsten or molybdenum content, may be converted to
alkali tungstates or molybdates by adding the sample to fused potassium
nitrite. The fusion may be carried out in a porcelain crucible. Metallic
tungsten and molybdenum are dissolved in a few minutes mth evolution
of much heat, while other metals remain as oxides. After the melt has
cooled, it is leached with water,'and the solution tested directly for tungsten
and molybdenum. The xanthate test (see page 93) is advised as the most
rapid, sensitive and decisive test for molybdeniun. The acid molybdate
solution is treated with potassium xanthate. The soluble violet compound
formed may be extracted with chloroform. " .
12. Silica (Silicates), Silicon (Silicides), and Borides

Si02 and silicates can be converted to alkali silicates by fusion with
sodimn-potassium carbonate in a loop of platinmn wire or a platinum
spoon. The melt is disintâted with a hot nitric acid solution of am-
monium molybdate (preferably in a platinum crucible). A yellow solution
of sihcomolybdic acid is thus obtained if silica or silicates are present. A
yellow crystalline precipitate in a colorless solution indicates'the presence
of phosphates. Traces of silicomolybdic acid (dowiTto 0.1 7 Si02) may
be detected by the blue color obtained by spotting with an acetic acid
solution of benzidine (see page 252).
IDENTIFICATION OF INSOLUBLE SUBSTANCES 307
To convert silicon and silicides to silicate, it is necessary to fuse the

sample with a mixture of sodium carbonate and sodium peroxide (1:1)
on a piece of silver or nickel foil. The melt, after cooling, is dissolved in
nitric acid in a platinum crucible, and tested for silicomolybdate as just
described.
Borides are opened up in the same way as silicon compounds. The
boric acid formed may be detected by color reactions (see page 257).
13. Antimony (V) Oxide

Ignited antimony pentoxide, which is difficultly soluble in acids, may
be detected by spotting with a solution of potassium iodide containing a
mineral acid and starch. The following reduction occurs, with liberation
of iodine:
SbiCk + 4 HI = SbiO, + 2 HiO + 2 li
In the presence of higher metallic oxides (e.g., MnOj or PbOj) the
test is, of course, not applicable directly. The higher orides must be
dissolved away with hydrogen peroxide and acid (see 9) and the test then
carried out on the washed residue.
14. Insoluble Fluorides

CaFs and ThF4 are in this category.
The best reaction for the detection of insoluble fluorides rests on the
fact that a violet hydrochloric acid solution of zirconium alizarinate turns
yellow in the presence of fluorides, because of the formation of ZrF7~ ions
and alizarin (see page 154). A very small sample of the insoluble residue
is mixed with 1 or 2 drops of the reagent (ZrCU solution in hydrochloric
acid mixed with excess sodium alizarin sulfona'e), gently heated, and
observed for any color change from violet to yello"/.
Alternatively, the sample may be heated with quartz sand and cone
sulfuric acid; SiFi is liberated. This may be hydrolyzed to silicic acid,
which is identified by the sensitive silicomolybdate reaction (see page 252).
15. Metastannic Acid and Tin (IV) Phosphate

A small sample of the insoluble residue is covered with about 6 ml.
cone, hydrochloric acid in a evaporating dish. A few small pieces of a
pure zinc rod are added to liberate hydrogen, and the mixture is stirred with
a small test tube filled with cold water. The test tube is then removed
from the liquid and the portion that was immersed placed m the non-
luminoua portion of a Bunsen flame. A characteristic blue mantle of
flame forms around the tube in the presence of even extremely small
308 V. SYSTEMATIC ANALYSIS OP MIXTTJUES
amounts of tin. As this flame coloration (luminescenbe reaction) is an"

extremely sensitive test (see page 88) only a trace of sample is necessary
for the detection of stannic oxide in an insoluble residue. Tin in glass may
be detected by this test.
Alternatively, a few milligrams of the residue may be fused with
potassiiun cyanide. The resulting metalUc tin is dissolved in hydro-
chloric acid. The stannous chloride is then identified by the red color
that develops when a drop of the solution is placed on filter paper impreg-
nated with cacotheline (see page 87).
If SnOa is mixed with 15 times its weight of N H J and then heated to
500C., the tin is volatilized as SnL. This behavior can be used to test
the purity of SnOj.** The oxides of arsenic and antimony likewise form
volatile iodides.
16. Carbon
Carbon, if present as hard coal, brown coal, charcoal, graphite, or in
heavy metal carbides, is not attacked at all if its mixtures with inorganic
materials are treated with hydrochloric acid. Nitric acid and aqua regia
produce only a slight effect. Consequently, carbon may be present in an
insoluble residue, provided the latter is not white or yellow. Materials of
these colors can be assumed to contain no free carbon. The presence of
carbon in coals can be detected by the glowing when the sample is heated
with access to air. The test can be made easily by slowly heating a few
milligrams of the insoluble residue on platinum foil.
A more sensitive test for carbon (in coals) is to drop small portions oi
the insoluble residue into molten potassium chlorate (m.p. 370C.), con-
tained in a porcelain crucible. The carbon oxidizes with decrepitation.
No higher oxides (especially MnOj), should be present, since they cause a
violent evolution of oxygen from the chlorate. If the test 9 (page 305)
has given a positive response for higher oxides, they must "be destroyed
beforehand by warming with cone, hydrochloric acid and hydrogen perox-
ide. The residue is washed, dried, and then tested with the melted chlorate.
The carbon of resistant graphite and resistant heavy> metal carbides cannot
be detected by this procedure.
< E. R. Caley and M. G. Burford, Ind. Eng. Chem., Anal. Ed., 8, 114'(1936);
see also L. Moser, Monatth., 63, 39 (1929).
VI. THE USE OF SPOT REACTIONS
IN QUALITATIVE ORGANIC ANALYSIS
The extensive study of the use of spot reactions in quaUtative organic
analysis is of fairly recent date.' The results have shown that a further
development of this field is both desirable and promising. Because of the
great number and variety of organic compounds, the primary and also the
easier task of organic spot'analysis is first of all to identify with reasonable
certainty particular groups of atoms in organic compounds. This detec-
tion is fully adequate for many purposes. The experience gained often
gives valuable hints leading to the development of spot tests for single
chemical materials.
The detection and characterization of organic compounds through
spot reactions are based on the utilization and adaptation of the most
varied reactions of organic compounds to the special technique of spot
testing. In the first place, there is a direct connection between inorganic
and organic spot analysis, when the problem is to detect certain metals in
organic compounds. In such cases, the procedures of inorganic spot test-
ing can be applied either immediately, or after destruction of the organic
portion of the sample. Furthermore, the selective or specific actions of
some radicals of organic compounds, which form the basis of the tests for
certain metals by means of organic reagents, may be use'd reciprocally
for the detection of these particular groups of atoms themselves^ An
example of this is the formation of the green copper salt of benzoin oxime:
COHBCH (OH)C (=NOH)CeHj

This constitutes a sensitive and selective test for copper (see page 65)
that is not limited to benzoin oxime because all acyloin oximes containing
the group CH(OH)C(=NOH) produce green insoluble copper salts
with Cu++ ions. The same holds for the anh"-dioximes with the group
C(=NOH)C(=NOH). All these dioximes form red or orange-
yellow inner complex salts with Ni++ ions. Accordingly, they react like
the familiar dimethylglyoxime (see page 114) because of their nickel-
binding group.
Organic compounds are so varied that it is seldom possible-to count
on the immediate presence of salt-forming groups, whose reactions with
metal ions are both characteristic and aipplicable in analysis. For the most
As far as can be ascertained from the literature, an organic spot test, that for
the detection of CSj (see page 417), was first described by F. Feigl and E. Chargaff
[Z. anal. Chem., 74, 376 (1928)]. Late' I. M. Korenman, Chem. Zentr., 1931, II,
601, tested a number of well known color reactions of organic compounds with regard
to their suitability as spot tests, and gave, in some cases, the sensitivities obtained.
E. Eegriwe described interesting examples of the detection of organic compounds
which for the most part can be accomplished with one drop of test solution.
' See F. Feigl, op. cit. (this text, page 2), particularly Chapter V,
309
310 VI. ORGANIC SPOT TESTS
part, the reactions of organic compounds tha;t have value in spot tests are
due to the presence of groups that can react in other ways. Such groups,
either by themselves or through the influence of other groups, make possible
chemical attacks that lead to reaction products which can be detected
easily. The vulnerability of organic compounds to oxidation, reduction,
fission, condensation, etc., offer possibilities in this direction. Conse-
quently, the detection of organic compounds by spot tests often necessi-
tates a preliminary treatment of the sample. It must be subjected to such
degradations, rearrangements, and synthetic reactibns as can be carried
out on a semimicro- or microscale without significant losses of material, or
without much expenditure of time. Obviously, this involves both a limi-
tation and an advantage. Among the advantages is the fact that only
simple methods are used in organic spot analysis and the apparatus of
inorganic spot testing suffices for these operations.
The following sections contain descriptions of only such quaUtative
organic tests as can be carried out as spot reactions. These tests comprise
merely a part of the methods that may be called on when solving the
numerous problems presented by quaUtative organic analysis.. Physical
methods (distillation, determination of mefting and boiUng points, solu-
bility tests, etc.) which are often indispensable for the identification of
certain products, are not included here. These methods and procedures,
which lie without the province of spot test analyses, are discussed at length
in texts devoted to qualitative organic analysis. Among these are:
Clarke, B. L., Handbook of Organic Analysis, 4th ed.. New York, 1926.
Kamm, 0., Qualitative Organic Analysis, 2nd ed., Wiley, New York, 1940.
Meyer, H., Analyse und Konstitutionsermittlung organischer Verbindunên
I, 5th ed., Springer, Berlin, 1931.
Rosenthaler, L., Nachweis organischer Verbindungen, 2nd ed., Leipzig,
1932.
Staudinger, R., Introduction to Qualitative Organic Analysis,^ttansl&ted by
W. T. K. Braunholtz, Van Nostrand, New York, 1925. The 2nd
German edition was pubHshed at Leipzig, 1938.
Mann, F. G., and Saunders, B. C , Practical Organic Chemistry, 2nd ed.,
Longmans, Green, London, 1938.
Hickinbottom, W. J., Reactions of Organic Compounds; Longmans, Green,
London, 1940.
A. DETECTION OF ELEMENTS IN ORGANIC COMPOUNDS

Testing for the presence of particular elements mjjrganic compounds
is one of the simpler tasks of qualitative organic analysis. Its purpose is
usually to provide the advance information which is essential when examin-
ing unknown products, because it gives important hints as to what the
nature of the more extended tests should be. ^ o r instance, if a simple
HALOGENS 311
preliminary test has established the absence of nitrogen there is no point

in testing for NO2 or NHs groups. Likewise, if sulfur is found not to be
present, SH, SOaH groups, etc. are certainly absent. The same is true of
other groups of atoms which contain nonmetals or metals, whose presence
or absence can be established by preliminary tests.
The presence of carbon and hydrogen can be assumed as a matter of
course in all organic conapounds, and no special tests are required for these
elements. The same is also usually true for oxygen, whose presence is
established along with that of oxygen-containing groups. Of the other
nonmetals that are important constituents of organic compounds, nitrogen
and sulfur merit particular attention. Tests for the halogens must often
be made, and sometimes for arsenic and phosphorus. Among the light
metals, the alkalis are especially likely to be encountered; less often, the
alkali earth metals. These are likely to occur as salts of organic acids.
As a rule, it is not necessary to test for the heavy metals, except mercury.
This element may be found in organic compounds, either in salts, or directly
bound to carbon.
The fundamental basis of all the tests -for nonmetallic and metallic
elements is the destruction of the organic skeleton by some convenient
means and thus arrival at a pure inorganic compound, which can be de-
tected by the methods of qualitative inorganic spot testing^ The disinte-
gration of the organic material is always accomplished by an oxidative
process carried out either on the dry material, by heating it with alkaline
oxidizing mixtures, or in the wet way, by digestion with concentrated nitric
acid (Carius procedure), or by digestion with concentrated sulfuric acid
(Kjeldahl method). Direct ignition of an organic product is permissible
when testing the sample for ash, and accordingly, when searching for non-
volatile inorganic constituents.
HALOGENS
1. Test by conversion into copper halide (Beilstein test).' Organic com-
pounds, which contain halogens (chlorine, bromine, iodine, and also CN
and CNS groups) form a volatile copper halide on heating with copper oxide.
The copper halide gives a characteristic green or blue-green color to a non-
luminous gas flame. This reaction is given by all classes of organic com-
pounds, but it must be noted that certain substances containing nitrogen,*
but no halogen, will give a positive test in the Beilstein reaction. Oxy-
quinoline, urea, thiourea, and substituted pyridines are pertinent examples.
The colored flame is due to the formation of copper cyanide.
UProcedureA piece of copper wire, about 1 mm. thick, is fused into
a glass rod, and the end of the copper wire beaten out to form a spatula 2
F. Beilstein, Ber., 5, 620 (1872).
See H. Meyer, op. eit. (tMs text, page 310), page 132.
to 3 mm. wide. The spatula is heated in the oxidizinglflame and is thus

coated with copper oxide. Such spatulas may be kept on hand. In order
to test for halogen, a little of the powdered sample is placed on the spatula,
or a drop of a solution (which should contain no inorganic halogen com-
pound) is gently evaporated to dryness. The charged copper wire is then
heated fairly strongly in the nonluminous flame of a Bunsen burner (first
in the inner zone and then in the lower part of the outer zone). A blue or
green color appears in the flame, and lasts for a time varying with the halo-
gen content. The yellowflamedue to sodium is seen almost always, partic-
ularly at the start. It may hide the green. Tliis interference can be
obviated by viewing the flame through a cobalt glass.
It is better still to use a platinum spatula.^ A little copper oxide is
mixed with the sample and then heated on the tip of the spatula.
Halogen was detectedîn the following amounts:
0.5 7 chloronitrobenzene C6H4CINO2
0.25 -i eosin CaoHgOeBri
0.25 7 iodoeosin C20H8O6I4
2. Test for fluorine by conversion into alkali fluoride.^ The Beilstein test
for halogens (I) in organic compounds is not suitable for the detection of
fluorine, as copper fluoride, in contrast to the other copper haUdes, is not
volatile.
On heating organic compounds with metaUic potassium, any fluorine
present is converted into potassium fluoride. This can be decisively
detected by the reaction tvith zirconium alizarinate described on page 202.
^ProcedureA few mg. of the sample are taken, or a drop of the
solution is evaporated to dryness in a small ignition tube. The evaporation
is accomplished best by heating while the tube is attached to a suction
pump. A piece of potassium the size of a millet seed is added. The tube
is heated, gently at first, and. then strongly for 1 minute. The-molten
metal thus comes into intimate contact with the sample. After cooling,
0.5 ml. water is placed in the tube and a few drops of a strongly acid (hydro-
chloric) solution of zirconium-alizarin. It is not necessary to filter off
particles of carbon. In the presence of fluorine, the red color of the zir-
conium "solution fades, and the yellow color of the free alizarin, appears.
Instead of melting with potassium, the sample can be ignited with
calcium oxide. The calcium fluoride in the residual can be tested with
zirconium alizarinate (see page 202). The ignition with CaO is/however,
more cumbersome than the conversion into KF.
Reagents: 1) Metallic potassium
A. Gawalowski, Z. anal. Chem., 64, 471 (1924).
F. Feigl and L. Badian, unpublished studies.
SULFUR 313
2) Zirconium-alizarin solution (for preparation, see page

202)
By means of this reaction fluorine was detected in:
200 y acetofluoroglucose C14H19O9F
200 T lactosyl fluoride C12H21OWF
100 7 /3-fluoronaphthaIene C10H7F
100 7 o-fluorobenzoic acid C7H6O2F
SULFUR
1. Test by fusion with alkali metals (Lassaigne's test). Alkali sulfide
is formed on heating organic sulfur compounds with metallic sodium
or potassium.' Very small amounts of sulfide can be detected by the
evolution of nitrogen in the iodine-azide reaction (see page 227). This
affords a sensitive and specific means of testing for organically combined
sulfur. The iodine-azide reaction is carried out in acetic acid solution;
any evolution of hydrogen sulfide from the acid solution can be prevented
by the addition of cadmium acetate.
IfProcedure'A very little of the powdered sample is placed in a
small hard glass tube with the end blown out to a bulb. If a solution is
used, a microdrop is evaporated to dryness in the tube. (This is best done
under slightly reduced pressure by connecting the tube to a suction pump.)
A small piece of potassium (size of a pin head) is introduced on a small
glass rod, and any sample on the walls of the tube can be stroked down
with the potassium. The tube is then carefully heated, starting from the
open end, until the potassium is melted and has mixed with the sample.
Finally, the tube is heated for a short time to redness, and plunged at
once into a micro test tube containing 5 drops of water. Without troubling
to filter off the particles of glass and carbon, 1 drop of cadmium acetate,
then 1 or 2 drops of acetic acid are added, and when cold, 1 or 2 drops of
iodine-azide solution. When a sulfur compound is present, bubbles of
nitrogen can be seen.
Reagents: 1) Metallic potassium
2) 20% cadmium acetate solution
3) 20% acetic acid
4) Iodine-azide solution (for preparation, see page 228)
Using this procedure sulfur was detected in:
0.3 y thiourea, CSCNHj),
1.2 7 sulfanilic acid, C6H<<^
'SOiH
.CO..
1.2 7 isatin potassium sulfonate, K08S-CjHj<^ P'CO
NH
1.27 H-acid, C,oH4(OH)(NH,)(S03H),
' F. Feigl and L. Badian, unpublished studies.
2. Test by reduction to sulfide in an alcohol flame.' Sulfurin difficultly

volatile organic compounds can also be converted into alkali sulfide by
fusing with KOH in the reducing portion of an alcohol fiame. The resulting
potassium sulfide is conveniently detected by the iodine-azide reaction.
The following procedure is about ten times as sensitive as the Lassaigne
test. It may also be used to identify insoluble sulfates (compare page 238).
IfProcedureThe end of a thin copper wire is dipped into saturated
potassium hydroxide solution and then drawn through an alcohol flame.
If necessary, this is repeated until a small KOH bead is formed. If the
bead is not at the end of the wire, the protruding portion is cut off. The
bead is touched to the sample so that a little adheres. If necessary, the
operator may breathe on the bead beforehand. The charged bead is put
into the flame, at first in the outer and then in the inner cone. It is allowed
to cool slowly by holding it close to the flame. The end of the wire carrying
the bead is cut off and placed on a slide. A drop of iodine-azide solution
is added and the result observed under the microscope. Alternatively,
the end of the wire is placed in a narrow centrifuge tube, a drop of reagent
is added, and the result is observed after ,centrifuging.
Detection of sulfur in insoluble sulfides and in difficultly soluble organic
compounds.^
^ProcedureThe end of a very thin copper wire is cleaned by rub"
bing with emery cloth, or by dipping into nitric acid. The cleaned end i^
plunged into saturated KOH solution and heated in a low flame (sulfur"
free gas or alcohol) so that a small bead of fused KOH collects near the end-
After breathing on this Ughtly, it is touched to the sample so that a little of
the latter adheres to the alkali. The bead is then heated, first in the upper,
i.e., the hottest part of the flame, then in the reducing zone. It is allowed
to cool near the flame. The end of the wire is cut off, placed on a slide,
treated with a drop of iodine-azide solution and observed under the micro-
scope. If less than 0.03 y sulfur is present, the evolution of gas is general
and quite vigorous, so that the positive result can be plainly distinguished
from that given by the blank. The latter sometimes gives small gas bub-
bles at single scattered places on the wire. These obviously are due to
sulfide inclusions in the copper. A general uniform evolution of gas is
never observed when the KOH bead in the blank dissolves.
Sulfur in easily volatile organic compounds.^
^ProcedureThe sample is reduced with metallic silver in a capil-
lary tube. Ordinary glass tubing is drawn down int^ 0.5-1 mm. capillaries.
These are filled with AgNOj-NHs-tartrate-NaOH solution and allowed
to stand overnight. After rinsing with water, the tubes are dried by
F. L. Hahn, Ind. Eng. Chem., Anal. Ed., 17,199 (1946).
F. L. Hahn,toe.cil. ^
priTROGBN 315
wanning and drawing air through them. The tubes are then drawn out to
6 to 8 cm^so that the ends are as thin as paper. The closed tubes can be
kept on hand indefinitely. A tube is prepared for use by breaking off the
very fine point and allowing a droplet of the sample to enter. Solid sam-
ples are fused, or dissolved in the smallest possible volume of a solvent that
has been tested to insure the absence of sulfur. The capillary is closed by
touching the tip momentarily to the flame. A zone about 2 cm. from the
end is heated. When it becomes hot, the capillary bends so that the sam-
ple approaches the flame, volatilizes, and is reduced in the superheated
zone. At this instant, a light snap is heard. After cooling, the tip is
broken off and a drop of iodine-azide solution is allowed to enter. The
reaction is observed under the microscope. As little as 0.05 7 sulfur gives
a vigorous reaction.
NITROGEN
1. Test by heating with calcium oxide (lime test). When organic com-
pounds containing nitrogen are heated with lime, ammonia is formed.
This can be identified by the black color or precipitate formed by its action
on a mixture of silver and manganese-salts (see page 184). If the sample
is heated with lime in a hard glass tube and a piece of filter paper impreg-
nated with the reagent solution is laid over the open end, it often happens
that substances which contain no nitrogen also cause a darkening of the
paper. This is due to the formation of pyro-compounds during the incom-
plete combustion of the organic compound. This interference mth the test
can be avoided if a little manganese dioxide is mixed with the lime; the
evolution of oxygen on heating to redness ensures complete combustion.
A little of the ammonia may be oxidized in this case, but since the test for
ammonia is very sensitive this loss is of no importance.
IfProcedure*'A trace of the sample is mixed in a small hard glass
tube with a mixture of lime and manganese dioxide. Alternatively, a drop
of the test solution is evaporated to dryness in the tube (this is best done
under reduced pressure using the suction pump). The residue is then
mixed with the lime and manganese dioxide. The open end of the tube is
covered with a piece of filter paper moistened in the reagent solution, the
glass stopper is put in place, and the tube is slowly heated to redness. A
black or gray stain appears on the reagent paper, according to the amount
of nitrogen present. The stain immediately turns blue on spotting with
benzidine (MnOj-benzidine reaction, see page 135).
Reagents: 1) Amixtureof ignited lime and manganese dioxide (10:1)
2) Silver-manganese sulfate reagent (for preparation, see
page 185)
> F. Feigl and L. Badian, unpublished studies.
3) Benzidine acetate solution (for ppparation.see page 135)

Nitrogen was revealed in:
2y sulfanilic acid, CH <C<3Q li 1
17 p-nitrosophenol, CjHj <^r^TT
27 o-mtroso-/3-naphthol, CioHj =C^T^fv

37 H-acid, C,oH4(OH)(NHj)(S03H),
37 codeine hydrochloride, CisHjiOjN-HCl
2. Test by fusion with alkali metals (Lassaigne's test). Almost all
organic compounds containing nitrogen form alkali cyanide on heating
with metalHc potassium or sodium. (Potassium reacts more quickly.)
The cyanide can then be identified, after acidifying, by the blue color
formed with copper and benzidine acetates (see page 67).
^Procedure"A small amount of the solid sample, or a drop of the
test solution, is placed in a glass capillary with one end enlarged to a bulb.
Liquid samples are taken to dryness in the tube. A, clean, dry piece of
metalUc potassium is added with the aid of a small glass rod. The tube is
heated, starting at the open end, until finally the potassium in the bulb
melts and mixes intimately with the sample. The bulb is then briefly
heated to redness, and placed while still hot in the bulb of the apparatus
described on page 31 (Fig. 30) which contains 5 drops of distilled water.
The tube breaks on touching the water. Two drops of acetic acid are
added without filtering off the particles of glass and carbon. The funnel
stopper is replaced and covered mth a piece of filter paper impregnated with
copper acetate-benzidine acetate. When large amounts of nitrogen are
present, and consequently a large amount of hydrocyanic acid, a blue color
forms at once. For small amounts, the contents of the apparatus must be
heated to boiling with a microbumer before the color appears. The re-
agent paper must be kept moist all the time, by adding a-drop of water
when necessary.
Reagents: 1) Metallic potassium ,
2) 30% acetic acid
S) Copper acetate-benzidine acetate solution (for prepa-
ration see page 208)
Nitrogen was detected in:
67 p-nitrophenol, CH4(OH)N08
67 p-nitrosophenol, C6H4(OH)NO *
67 o-nitrobenzaldehyde, C,H4(H0)N0,
12 7 a-nitroso-/3-naphthol, CIOH;(C)H)NO
4 7 azobenzene, CH5N=NCeHs
12 7 codeine hydrochloride, CuH,iOjN-HCl
PHOSPHORtrs 317
Test for nitrogen and sulfur in the same sample^^

Organic compounds containing both nitrogen and sulfur produce
cyanide and sulfide when fused with metalUc potassium (see pages 316 and
313). Since these products are easily identified by spot reactions, it is
possible to test for both of these elements in much less than 1 mg. of the
sample.
IfProcedureA httle of the solid sample, or a drop of the solution
which is then evaporated to dryness, is placed in a small hard glass tube
with a bulb at one end. A piece of potassium the size of a pinhead is
added on a small glass rod, and the tube is carefully heated, beginning at
the open end, until the potassium is completely melted and mixed with the
sample. The bulb is then heated briefly to redness, and while still hot,
placed in the bulb of the apparatus described on page 31 (Fig. 30), which
contains 5 drops of distilled water. The hot tube breaks, and a drop
of cadmiima acetate and 2 drops acetic acid are added, and the apparatus
closed with the funnel stopper, on top of which is placed a piece of paper
impregnated with copper acetate-benzidine acetate (for preparation, see
page*208). On heating gently, the liberated hydrocyanic acid causes a
blue fleck on the filter paper,, thus indicating that the original sample
contained nitrogen.
After liberating the prussic acid, the funnel is removed and the
contents of the tube are allowed to cool. Then 1 or 2 drops of iodine-
azide solution (for preparation, see page 228) are added. Evolution of
bubbles of nitrogen, indicates that sulfur was present in the sample.
An appraisal of the sensitivity of this test is given by the weight of
material that sufficed to give definite reactions for both nitrogen and
sulfur:
1.2 y thiourea, CS(NH,),
6 7 sulfanilic acid, CtH4(NHj)S08H
9 7 potassium isatin sulfonate, KOjSC6H8<^^CO
12 7 H-acid, C,oH,(OH)(NHj)(SO,H)s
PHOSPHORUS
Test by ignition with lime (conversion to phosphate).'^ Organic com-
pounds containing phosphorus form heat-resistant tertiary calcium
phosphate on heating with lime. The phosphate can be converted to
ammonium phosphomplybdate by the action of a nitric solution of am-
monium molybdate, and can then be identified by the very sensitive benzi-
dine reaction (see page 250).
tProcedureA few grains of the powdered substance are placed in a

hard glass micro test tube, or alternatively a drop of the test solution is
evaporated to dryness there (best done by gentle wanning while the tube is
attached to the suction piunp.) A few mg. lime (tip of knife blade) is
added and mixed in. The tube is heated, at first gently, and finally kept
for a few minutes at red heat. It is placed, while still hot, in 2 drops distilled
water in a depression of spot plate. The tube breaks on touching the
water. The mixture on the spot plate is treated with 2 drops cone, nitric
acid, which dissolves the calcium salts. A drop of ammonium molybdate
is then added. The spot plate is gently heated on an asbestos mat. After
cooling, a drop of benzidine and then 1 or 2 drops sodium acetate solution
are added. The mixture is observed for any blue color, which indicates
phosphorus (in the absence of arsenic).
Reagents: 1) Quick lime
2) Cone, nitric acid
8) Ammonium molybdate solution (for preparation, see
page 251)
4) Benzidine solution (for preparation, see page 26i)
6) Saturated solution of sodium acetate
As an example of the sensitivity of the test, phosphorus was detected
in as little as one ganmia of l-phenyl-l-choroethylene-2-phosphinic acid,
CeHs-CCnCHPOsH,.
ARSENIC
Test by heating with lime (conTersion to wsenate).'' AH nonvolatile
organic compounds containing arsenic form heat-resistant tertiary calcium
arsenate on heating with lime. The arsenate can be reduced to the
element by a solution of stannous chloride containing cone, hydrochloric
acid, and this produces a black precipitate or color (see page 79).
UProcedureÂ few grains of the powdered substanceare placed in a
micro test tiibe of hard glass, or alternatively a drop of the test solution
is evaporated to dryness there (preferably by warming and using the suc-
tion pump). A few mg. lime are placed in the tube, mixed in, and the tube
heated gently at first, and finally to redness for a few minutes. After
being allowed to cool completely, the contents of the tube are dissolved
in a few drops cone, hydrochloric acid (no particles of carbon should remain
if combustion has been complete). Two drops stannous chloride are added
and the mixture warmed. In the presence of arsenic, a black precipitate
or brown turbidity is seen. The turbidity can be made more visible by
shaking the mixture with ether. The dark particles can then be seen at
the interface between the ether and water.
oxTaEN 319
Reagents: 1) Calcium oxide (ignited)

5) Freshly prepared solution of stannous chloride in 35%
hydrochloric acid
Arsenic waS^revealed in
12 y chloroarsanilic acid, CjHiCKNHjXAsOsHj)
12 y dinitroaraanilic acid, C6Hs(N08)2(NHs)(AsO,Hj)
10 T sodium acetylarsenilate, ^^(NHCOCHa) (AsOaHNa)
8 y sodium p-hydroxyphenylarsenilate, CeH4(OH)(As03HNa)
OXYGEN
Test through solvate formation with ferric thiocyanate.^' Red ferric
thiocyanate, like green-blue cobalt thiocyanate (see page 112), can be
extracted from its water solution by shaking with ether, amyl alcohol, and
other oxygen-containing organic solvents. In contrast, solvents that are
free of oxygen, such as benzene, toluene, carbon tetrachloride, etc., are
inactive. Since solid ferric thiocyanate shows this same solubility distinc-
tion toward these two classes of liquids, a test for oxygen in organic com-
pounds can be based on this differential behavior. Obviously, this action
is due to the fact that the molecules of oxygen-containing Uquid or dis-
solved organic compounds are capable of forming stable solvates with
ferric thiocyanate molecules through the auxiliary valences of their oxygen
atoms. The molecules of liquid hydrocarbons and their halogenated
derivatives lack these coordination-active atoms, and accordingly, form
no solvates with this ferric salt. This assumption is supported by the
fact that hquid hydrocarbons and their halogenated derivatives acquire
the ability to dissolve ferric thiocyanate when either solid or liquid oxygen-
containing materials are dissolved in or mixed with them. In principle,
this effect is analogous to the solvate formation that occurs when iodine
dissolves in organic solvents, producing a brown color. The violet iodine
solutions, which probably contain no solvate, change toward brown when
coordination-active organic compounds are introduced, and thereby cause
the formation of iodine addition compounds which dissolve with a brown
color."
It should be noted that sulfur- and nitrogen-containing compounds
act like the oxygenated materials, relative to the solubility of ferric thio-
cyanate. Consequently, the test is characteristic for oxygen only if the
absence of sulfur and nitrogen has been proved. Furthermore, acids and
oxidizing compounds interfere with the test.
" D. Davidson, Ind. Eng. Chem., Anal. Ed., 12, 40 (1940).
" Compare F. Feigl, op. cit. (this text, page 2), page 64.
IfProcedureFilter paper is impregnated by plunging it once into a

methyl alcohol solution of ferric thiocyanate and then drying it in the air.
The reagent paper must be freshly prepared each time! Several drops
of the solution to be tested is placed on the paper. A positive reaction is
indicated if a wine-red color appears. Solids should be dissolved before-
hand in hydrocarbons or their halogenated derivatives
Reagent: Separate solutions containing 1 g. FeCls and 1 g. KCNS
dissolved in 10 ml. methyl alcohol are prepared. The
solutions are united and allowed to stand for several hours
before filtering off the precipitate of potassium chloride
B. DETECTION OF CHARACTERISTIC GROUPS

IN ORGANIC COMPOUNDS
The tremendous number of organic compounds would present a vast
chaos of materials if there were no possibility of arranging them into classes
(alcohols, carboxyl compounds, amines, etc.) whose members can be char-
acterized because they contain certain like groups of atoms. Accordingly,
the most important task of qualitative organic analysis is to recognize,
as well as possible, such typical groups. These are not only indispensable
for a classification, but often they also confer certain chemical and physical
properties on organic compounds.
Comparatively few characteristic groups can be detected directly,
that is, by immediate reaction with suitable reagents that produce com-
pounds having distinctive colors or that can be recognized easily by spot
reactions. Usually it is necessary to treat the sample by condensation,
oxidation, etc., to give products which, in their turn, can be detected easily
by appropriate reagents.
It is not good practice to test unknown materials directly for the
presence of typical groups of atoms. Rather, as in qualitative inorganic
analysis, a series of preliminary tests should be made, that will often afford
valuable clues as to which atomic groups are likely to be present. The
following exploratory tests are recommended:
Microscopic examination for uniformity
Test for particular elements (see page 310)
Test for basic groups (see page 478)
Behavior on heating
Solubility in water (if necessary after addition of acid or alkali)
Solubility in organic solvents (if necessary after addition of ^cid or
alkali)
Recrystallization atod determination of melting point
NTTROSO COMPOUNDS 321
NITROSO COMPOUNDS (NO-GROUP)

1. Test with ênol and solforic acid. Either aliphatic or aromatic ni-
troso compounds when warmed with cone, sulfuric acid and phenol
produce a red color, which turns blue with alkalis. The mechanism of this
reaction is not yet established .^^
^Procedure'*A little of the powdered substance is melted in a
microcrucible along with a particle of phenol. After cooling, a few drops
of pure cone, sulfuric acid are added. The sample turns dark cherry-red.
After diluting with a little water, the solution is made alkaline with a few
drops of sodium hydroxide. It then turns deep blue. A solution of the
sample in ether, which evaporates readily, may be used instead of the solid.
Reagents: 1) Phenol
S) 4: N sodiuih hydroxide
2. Test with sodium pentacyanoammine ferroate.'' Nitroso compounds
form brightly colored complex compounds with the prussic salts, sodiimi
pentacyanoaquo ferroate Na3Fe(CN)6H20 and sodium pentacyanoam-
mine ferroate Na3re(CN)6NH3. This color reaction'* depends on the
exchange of the water or ammonia molecule of the prussic salt for a molecule
of the nitroso compound, e.g.:
Na,[Fe(CN)6NH3] + RNO = NH3 + Na3[Fe(CN)6RNO]
It is noteworthy that the entrance of the RNO molecule into the
inner sphere of the prussic salt, with expulsion of the NH3 or HjO molecule,
occurs only in the light. In the dark, the exchange proceeds at an im-
measurably slow rate.'' This is the only known instance of the direct
analytical application of a photo reaction.
Aromatic thioaldehydes and a few thioketones" also react with
prussic salts to give a blue color; certain aromatic hydrazines give red or
violet colors (see page 385). Interference due to hydrazines may be
prevented by the addition of a few drops of form aldehyde; formhydrazone
is formed at once; it does not react with prussic salts.
IfProcedureA drop of the test solution is mixed on the spot plate
with several drops of a freshly prepared solution of sodium pentacyano-
ammine ferroate. After a little while, an intense green color, or more
rarely, a violet color, is formed.
C. Liebermann, Ber., 7, 247, 287, 806, 1098 (1874).
" F. Feigl, V. Anger, and 0. Frehden, Mikrochemie, 16, 181 (1934).
" F. Feigl, V. Anger, and O. Frehden, Mikrochemie, 16,181,183 (1934).
" Compare O. Baudisch, Ber., 64, 413 (1921).
'H. W. Schwechten, Ber., 66, 1734 (1932).
Reagent: 1% solution of sodium pentacyanoammirie ferroate."

The various limits of identification attainable by means of tests 1
and 2 on different nitroso compounds are given in Table 6.
NITRO COMPOUNDS (NO2-GROUP)
1. Test by reaction with sodium pentacyanoammine ferroate after re-
duction to nitroso compounds.'' The color reaction of nitroso compounds
with sodium pentacyanoammine ferroate just described can also be applied
TABLE 6. NITROSO COMPOUNDS
Test with
aHtOH+HiSOt Na.Fe(CN).NH,
Nunc Fonnula
Limit Limit
of iden- Color of iden- Color
ti6ck- tifica-
tion tion
p-Nitrosodi- (CH,),N-C,H4N0 0.57 Pink-yel- 0.15 7 Emerald

methyl- low-green green
aniline
p-Nitroso- H0C,H4N0 0.47 Red-blue 0.15 7 Dark green
phenol
a-Nitroso- C,i,H,(NO)(OH) 0.57 Red-blue I7 Olive green
0-naphthol
^-NitFoso-a- CioH,(NO)(OH) 0.6 y Red-green I 7 Olive green
naphthol
Tetrahydro- CioH,o(NO)(OH) 0.57 Red-green No reaction
/S-nitroso-
a-naphthol
Isonitroso CHjCO CH, CO CH: NOH Dark red to 2 . 5 7 Brown lilac
acetylace- green-
tone yellow
Isonitroso C.H,-COCH:NOH I7 Brick-red Green
aceto- to yellow
phenone
to the detection of nitro compounds, if the nitro group is reduced to the

nitroso group. This reduction can be carried out electrolytically in a
drop of the test solution. The electrolysis is accomplished in neutral or
alkaline solution, in the presence of the reagent, and between a nickel and a
lead electrode.**
UProcedureA drop of the alcoholic or aqueous test solution is mixed
in a microcrucible with a drop of a freshly prepared, solution of sodium
For preparation, see K. A. Hofmann, Ann., 312, 21 (1900).
i F. Feigl, V. Anger, and O. Fr'ehden, Mikrochemie, IS, 181, 183 (1934).
" O. Dieffenbach, D. R. P., 192. 519; Chem. Abstracts, 2, 1765 (1908).
NITRO COMPOUNDS 323
pentacyanoammine ferroate and a drop of alkali. If the addition of

alkali causes a coloration, then a drop of sodium sulfate solution should
be used instead as the electrolyte.
The current is then allowed to pass through the solution in the micro-
crucible, using a nickel wire as cathode and lead wire as anode. The
source of current can be either a flashlight battery or a 4-volt storage bat-
tery. The electrolysis should continue for at least 10 minutes, and for
small amounts of test substance, up to half an hour. The liquid becomes
colored during the electrolysis, and the color, which deepens on standing,
is usually green, more seldom violet.
A blank test with sodium sulfate shows no alteration in the pale
yellow color, but with alkali there is a slight deepening in the yellow
shade.
Reagents: 1) 1% solution of sodiimi pentacyanoanomine ferroate
(for preparation see page 322)
S) 4 N sodium hydroxide
3) 4% sodium sulfate solution
The limits of identification for different m'tro compounds attained
with this test are ^ven in Table 7.
2. Test for m-dinitro compounds by reaction with potessiom cyanide.'*
If m-dinitro compounds are warmed with a solution of alkali cyanide, a
red-brown to violet color or precipitate is formed. The color is permanent
in the presence of dilute acids. This behavior is in contrast to that of
nitrophenols, whose color change is reversed when acids are added. The
constitution of these products of the cyanide reaction is only partly known.
Presumably they are substituted phenylhydroxyl amines.**-" For exam-
ple, 2,4-dinitrophenol (I) forms 2-hydtoxyIamino-3-hydroxy-6-nitroben-
zonitrile (II) (m-purpuric acid)
OH
NHOH
+ 2KCN -I- H,0 -> I -I- KHCO, + NH,
1,8-Dinitronaphtbaline is different from the other jjm-naphthalene

derivatives and behaves h'ke a m-dinitronaphthalene with potassium
" V. Anger, Mikrochim. Acta, 8, 6 (1937).
" L. Pfaundler and A. Oppenheim, Z. Chem., [2], 1, 470 (1865).
" W. Borsche and E. BScker, Ber., 37, 1844 (1904).
cyanide. Mononitrobenzene and o-dinitrobenzene deriyatives, and also

1,5-dinitronaphthalene do not react, so that m-dinitro compounds may
be detected even in the presence of other nitro compounds.
IfProcedureA drop of a solution or a few grains of the solid sample
are mixed with a drop of a potassium cyanide solution in a microcrucible
and heated gently over a microburner. In the presence of m-dinitro com-
pounds, a violet or red color appears. It remains unchanged even on the
addition of a few drops of hydrochloric acid.
The limits of identification attained with this test are shown in Table 8.
ALCOHOLS
1. Test for primary and secondary alcohols by conversion into alkali
xanthates.^^ Primary and secondary alcohols react with carbon disulfide,
in the presence of alkali hydroxides, to give alkali xanthates:
ROH + CSa + NaOH = CS(OR)(SNa) + HjO

All alkali xanthates form violet compounds with molybdates in solutions
containing mineral acids (see page 93). The colored products are soluble
in chloroform. Primary and secondary alcohols, after conversion to
xanthate, can be detected by the molybdate reaction.
Esters react similarly to alcohols owing to the fact that, under the
conditions of the test, they are partially saponified to alcohols. Com-
pounds containing the CH2 CO CH2 group also react with carbon disulfide
and alkali. These form orange-red compounds^ which on treatment with
molybdates give chocolate-brown precipitates insoluble in chloroform.
They therefore interfere with the detection of small amounts of alcohols
by the xanthate test.
T A B L E 7. N I T R O COMPOTINDS ^'
Limit of
Name FormuU ideiitific&- Color
tioa
Nitrobenzene CHjNOj l.'Sr Dark violet
0,TO,p-Chloronitro- ClCHi-NO, 2y Green

benzene
15 7 f
m-Dinitrobenzene CjH4(N0,), ^ 7 Brown-violet
" G. Dragendorff, Die, gerichUiche chemische Ermittlung von GifUn, 1895, p . 111.
" H . Apitzach, Ber., 38, 2895 (1905). ^
ALCOHOLS 325
TABLE 7. Continued
Limit of
Name Fonnula identifica- Color
tion
0-, p-Nitrotoluene CH3CaH4-NO. 77 Violet-red

8T
0-, p-Nitrophenol HOC,H,NO, 0.4 7 Dark green

0.4 7
Picric acid CeH,-OH-(NOj)j 87 Dark olive

green
0-, m-, p-Nitrobenzal- N08C,H4CHO 47 Olive green

dehyde
m-, p-Nitrobenzoio NOj-CHiCOOH 87 Lilac dark

acid 2.57 green
0-,TO-,p-Nitrocinnamic NOr C H . - C H = C H COOH 37 Green

acid 47
37
o-f m-, p-Nitraniline NHj-C,H4-N0j 47 Green

47
0.25 7
1,5-Nitronaphthyl- NHjCioH.-NOj 0.37 Dark brown

amine,
o-,m-, p-Nitrophenyl- N0s-C,H4-NH-NHj 0.57 Green

hydrazine 1.57
0.5 7
6-NitroquinoHne CHeN-NO, 57 Light green
IfProcedure^Âdrop of the test solution (in ether, if possible) is

placed in a small test tube along with a drop of carbon disulfide and a few
centigrams of solid sodium hydroxide. The mixture is shaken for about 5
minutes. One or 2 drops of molybdate solution are then added, and as
soon as the alkali has ,di^lved, the solution is carefully acidified and
shaken with 2 drops of^(?nlOToform. When primary or secondary alcohols
are present in the test solution, the chloroform layer is violet.
Reagents: 1) Carbon bisulfide
2) Finely powdered alkali hydroxide
S) 1% ammonium molybdate solution
4) 2 A^ sulfuric acid
5) Chloroform
" Studies with R. Zappert.
326 VI. OBOANIC SPOT TESTS
T A B L E 8. m-DiNiTBO COMPOUNDS
llimit
Name Formttla of iden- Colot
tifica-
tion
m-Dinitrobenzene C J H * ( N O 0 J ( 1 , 3) 10 7 Violet
Chlorodinitro- C.H,Cl(N02)s(l, 2, 4) l 7 Red

benzene
Picryl chloride CaisCl(NOj).(l, 2, 4, 6) 27 Red-brown
Dinitrophenol C.H,{OH)(N05)2a,2,4) l 7 Red
Picric acid Cai,(OH)(NO,),(l, 2, 4, 6) 27 Red-brown
Dinitraniline CJI,(NH,)(NO,).(l,2,4) l 7 Red ,
Picramine C.H2(NH,)(NO,),(l,2,4,6) 27 Ped-brown
Dinitrochlorobenioic C,HsCUC00H)(N0,),{l,'4, 2, 6) 27 Red-brown

acid
Dinitroaminobenzoic C.H,(NH2)(C00H)(N0,),{1, 4, 2, 6) l 7 Red-brown

acid
1,8-Dinitronaph- CuH,(NOj),(l, 8) 10 7 Brown

thaline
Dinitro-a-naphthol CH5{0H)(N0,),{1,2, 4) 27 Dark brown
The following amounts of alcohols were detected:

1 mg. ethyl alcohol
1 mg. methyl alcohol
1 mg. propyl alcohol
1 mg. butyl alcohol
1 mg. isobutyl alcohol
0.5 mg. isoamyl alcohol
1.0 mg. allyl alcohol
0.5 mg. cyclohexanol
0.1 mg. phenyl ethyl alcohol
2. Test for polyhydric alcohols by oxidation with periodic acid. Polyhy-

droxy alcohols such as glycol, glycerol, erythritol, mannitol, etc., can be
broken down to formaldehyde and formic acid by excess periodic acid in
ALCOHOLS 327
the cold; the periodic acid is reduced to iodic acid."-'" The reaction can
be expressed:
CH,OH-(CHOH)_, -CHjOH + n HIO4
- 2CH,0 + (n + 1) HCOOH + n HIO, + H,0
Sensitive tests are available for the organic products of this oxidation.
Accordingly, the presence of polyhydroxy compounds can be established by
treating the sample with periodate and then testing for (o) formaldehyde or
(6) formic acid. The test described under (b), which is based on the detec-
tion of the formic acid, is more sensitive than that for formaldehyde (o),
since, as the reaction shows, 1 molecule of a polyvalent alcohol furnishes
only 2 molecules of CH2O as against (n + 1) molecules of HCOOH.
The reaction is given by almost all glycols and also by many carbo-
hydrates that do not normally react with fuchsin-sulfurous acid; mono-
saccharides also give a positive reaction. Cane sugar gives the reaction
only after boiling, when the acid probably breaks up the disaccharide into
the two monosaccharides, which in turn give the glycol reaction.
The oxidation with periodic acid also serves to differentiate between
tartaric and citric acids. Tartaric acid, which has two adjacent hydroxyl
groups is probably oxidized to to glyoxylic acid, and reacts with fuchsin-
sulfurous acid, while citric acid shows no visible change.
(a) Oxidation with periodate and detection of formaldehyde.^^
The reaction with fuchsin-sulfurous acid (see page 339) can be used to
detect the formaldehyde after destroying the excess periodate and iodate.
Most polyhydroxy alcohols can then be detected, provided aldehydes are
absent.
^ProcedureA drop of the aqueous or alcoholic solution of the poly-
hydroxy alcohol is mixed in a microcrucible with a drop of periodate solu-
tion and a drop of dilute sulfuric acid and allowed to stand for 5 minutes.
The excess periodic acid is then reduced with a few drops of sulfurous
acid, and the sample treated with a drop of fuchsin-sulfurous acid. After
a short time, at longest half an hour, a red to blue color appears. When
testing for polysaccharides the procedure is similar except that the contents
of the covered crucible are heated to boiling, and then likewise left to stand
for about 5 minutes.
Reagents: 1) 5% potassium periodate solution
2) Fuchsin-sulfurous acid
" L. Malaprade, Compt. rend., 18C, 1132 (1927).
" L. Malaprade, Bull. soc. ehim. [4], 43, 683 (1928).
1 F. Feigl and R. Zappert, unpublished studies.
S) 1 iV sulfuric acid
4) Saturated solution of suifurous acid
The following amounts were detected:
57 ethylene glycol 25 7 arabinose
2.5 7 glycerol 25 7 saccharose (with boiling)
57 mannitol 12.5 7 dextrose (with boiling)
25 7 glucose 50 7 starch (with boiling)
12.5 7 levulose 100 7 tartaric acid
25 7 lactose 100 7 mucic acid (dissolved in dioxane)
The following gave a positive reaction: erythritol, cherry gum, gum
arabic.
The following did not react: citric acid, 1,10-decanediol, inositol,
pentaerythritol, pentaacetylglucose, and acetylcellulose.
(6) Oxidation with periodate and detection of formic acid.^^
The detection of the formic acid produced when polyhydric alcohols
are oxidized with periodic acid is based on the oxidation of formic acid with
free bromine:
HCOOH + Br2 -^ 2HBr + CO2
The formaldehyde formed is thus also oxidized to formic acid and then to
CO2 so that eventually practically all of the carbon of the polyhydroxy
compound is converted into carbon dioxide. This can be detected by,
passing the gas into baryta water (formation of BaCOa).
[[ProcedureThe microdistillation apparatus (Fig. 33, page 32)
is used. A little of the sample is treated with 2 drops 5% potassium
periodate and 2 drops 1 N sulfuric acid and then warmed slightly. Bro-
mine water is then added, drop by drop, until a distinct yellow is obtained.
A glass bead is introduced and the stopper put in place. The distillaiion
tube is inserted into a small test tube containing baryta water. (The re-
agent is protected against the carbon dioxide of the air by coverrng it with a
little paraffin oil.) The distillation apparatus is gently warmed."' If the
liquid in the receiver becomes turbid, polyhydroxy compounds'are indi-
cated.
The following quantities were detected by this procedure:
2.5 7 glycerol 2.5 7 maltose , '
37 mannitol 77 saccharose
57 glucose 67 lactose
57 levulose 67 dextrin ,
57 arabinose 37 mufiic acid
2.5 7 mannose 20 7 sfarch
" O. Frehden and K. Fiirst, Mikroehem. ver. Mikrochim. Ada, 26, 36 (1939).
PHENOIA 329
3. Other tests for alcohols. 1. The conversion of Ce(N03)7" into

Ce(OR)(NO)r~ is accompanied by a color change (yellow to red), that
can be used for the detection of primary, secondary, and tertiary alcohols.**
One ml. of a solution containing 40 g. (NH4)jCe(N0j) in 100 ml. 2 A'^
nitric acid is diluted with 2 ml. water or dioxane. To this is added 1 drop
of a solution prepared by dissolving the material to be tested in as little
water or dioxane as possible (7d". Limit: about 400 y). Aliphatic bases
interfere by forming precipitates, oxidizable compounds (phenols and
aromatic amines) by giving colored products.
PHENOLS
1. Test with nitroos acid**. Many phenols form p-nitroso derivatives (I
or II) with nitrous acid, and these give indophenols (III) by condraisation
with the expe^ phenol in the presence of cone, sulfuric acid:'**
HO< >NO 0=< >=NOH

(I) (II)
' H0-<(3-N=<^>=0
(III)
p-Substituted phenols and nitrophenols do not react, but phenol

ethers and thiophene give an intense phenol reaction.
1[Procediire**A drop of the test solution (in ether) is allowed to
evaporate to dryness in a microcrucible, then treated with a drop of cone,
sulfuric acid containing a little nitrous acid, swirled, and then left for a few
minutes. The sample is then cautiously diluted with a drop of water.
Sometimes the color deepens. After cooling, the mixture is made alkaline,
when a further color change often results
Reagents: 1) Cone, sulfuric acid containing 1% HNO2
2. Test with 5-iutroso-8-hydroxyqiiinoIine.*' The Liebermann reaction,
described under 1, consists in the conversion of phenols to p-nitrdso com-
poimds by the action of nitrous acid, and these react further with the
phenols to form indophenols. An alternative method is to use a p-nitroso
compound directly as the reagent. A solution of 5-nitroso-8-hydroxy-
" F. R. Duke and G. F. Smith, Ind. Eng. Chtm., A-nal. Ed., 12, 201 (1940).
" C. Liebermanii, Ber., 7,-248, 806, 1098 (1874).
* H. Decker and B. Solonina, Ber., 86, 3217 (1902).
'F. Feigl and R. Zappert, unpublished studies.
Studies with Th. 0sterhud.
22
330 YI. ORGANIC SPOT TESTS
quinoline which in cone, sulfuric acid condenses with phenols (with a free
para position) to form indophenols, has proved suitable:
HO- -NO -H,0
- ^ -
= N - < ^ - O H
< >"
IfProcedureA drop of the alkaline test solution is evaporated to
dryness in a microcrucible and after cooling a drop of the reagent is added.
A dark color appears on gentle warming.
Reagent: 1% solution of 5-nitroso-8-hydroxyquinoline in cone, sul-
furic acid.
This procedure revealed:
1 y phenol (dark brown) 5 y o-nitrophenol (green-yellow)
2 y resoreinol (red-violet) 5 y o-cresol (dark brown)
7 y pyrogallol (black) 5 y xylenol (violet)
4 y pyrocatechol (greenish black) 10 y a-naphthol (dark brown)
3. Test with nitrous acid and mercuric nitrate,*' Nitrous acid solutions
containing mercuric nitrate react with phenols, either in the cold or on
slight warming, and produce red colors, or yellow precipitates that dissolve
in nitric acid to form red solutions. The reaction,probably depends on the
formation of a nitro compound, which then reacts with the phenol. Both
aniline and phenol ethers also show this reaction, as they produce phenol
on boiling with nitrous acid.
Di-o- and di-m-substituted phenols,'* such as picric acid, do not react;
neither do hydroxyanthraquinones. This Millon test is especially recom-
mended for p-substituted phenols, which do not respond to Tests 1 and 2.
UProcedure"A drop of the aqueous, alcoholic or ether solution is
mixed in a microcrucible with a drop of the reagent solution and left for a
few minutes. If no change occurs, the mixture is briefly heated to boiling
over a microbumer. A red color forms in the presence of phenols.
Reagent: One part mercury is dissolved in one part fuming nitric
acid and diluted with 2 parts water
The limits of identification and the colors for the different phenols
are given in Table 9. _ -
" E . Millon, Compl. rend., 28, 40 (1849); A. Alm^n, Z. anal. Chem., 17, 107
(1878); P. C. Plugge, Arch. Pharm., 228, 9 (1890).
W. Vaubel, Z. angew. Chem., 13, 1127 (1900).
" F. Feigl and R. Zappert, unpublished studies.
TABLE 9. PHENOI,S
Test with
Name Formula
Liebermann's reagent UiUon's reagent
Phenol CHsOH IT Blue red l7

green
Pyrocatechol 57 Green-red- 57
blood-red
CJl4(OH)2
Resorcinol 57 Red-blue 0.5 T^
Hydroquinone 10 7 Green-red 10 7 Heating
Orcinol G,H,(0H)2CH, 57 Yellow-red- 57

purple
Phloroglucinol C,H,(OH), 10 7 Blood-red 57

*
Pyrogallol C,H,(OH), 10 7 Violet-brown 5 7
Thymol CJI,(CH,)(C,H,)OH 57 Green-red-

blue
p-Nitrophenol C.H,(OH)NOt' No reaction 27 Heating
o-Hydroxyben- 27 Red-light 57
zaldehyde green
m-Hydroxy- 10 7
benzalde-
C,H4(CH0)(0H)
hyde
p-Hydroxy- No reaction l7 Heating

benzalde-
hyde
Protocateohuic C.H,(CHO)(OH), No reaction 47

aldehyde
Vanillin CJI,(CHO)(0CH,)OH No reaction 47
Methyl C,H4(0H)C00CH, l7
salicylate
Salol C,H4(0H)C00C,Ht 47 Green-red-

blue
p-Hydroxy ben- C6H4(OH)COOH No reaction 27 Heating

zoic acid
Methyl p-hy- C,H4(0H)C00CH, No reaction l7 Heating

droxy benzo-
ate
331
TABLE 9. Contitvued
Test with
Nme Formula 1
Liebennaiui'i reageot Millon's reagent
1
o-Naphthol Green IT
CHTOH
fl-Naphthol Dark green l 7
o-Hydroxy- C,H,(OH)N No reaction 0.5 7

quinoline
m-Hydroxy- C,H4(0H)CH:CHC0,H 57 Do" not

cinnamic heat
acid
ENOLS
Test with bromine and potassium iodide. All ends take up bromine
instantaneously with intermediate formation of dibromoenols, whicli form
labile a-bromoketones on elimination of hydrogen bromide. These
a-bromoketones oxidize hydrogen iodide and liberate iodine, the enols being
regenerated.*" Enols can therefore be detected by treating' the sample
with excess bromine, removing the unused bromine and adding potassium
iodide to the acid solution. A liberation of iodine indicates the presence of
enols.
The equations in the case of the enol form of ethyl acetoacetate are:
CH,C(OH)=CHCOOCJI + Br,-> CH,C(OH)BrCHBrCOOCH
CH,C(OH)BrCHBrCOOCjH, - CH,COGHBrCOOCJI. + HBr
CHiCOCHBrCOOCOij + 2 H I - C H , C 0 C H , C 0 0 C a i +HBr + I
IfProcedm-e*'Bromine water-is added to a drop of the test solution
until a permanent yellow color forms, and then sulfurous acid until the
solution is decolorized. The excess sulfur dioxide is driven off by^boiling.
The solution is then treated with a few drops of potassium iodide solution
and starch solution. A blue color indicates the presence of enols.
Reagents: 1) Bromine water (saturated) '
8) Sulfurous acid
S) 5% potassium iodide solution
4) Starch solution; ^
A poative reaction was given by the following: 8D 7 acetoacetic ester,
70 7 malonic ester, 120 7 benzoylacetic ester.
" K . H. Meyer,.5r., 47, 835 (1918).
Studies with O. Frehden;
CABBONTL COMPOUNDS 333
CARBONYL COMPOUNDS OCO-GROUP)

Test for aldehydes and aliphatic methyl ketones by interaction with
Msolflte. Approxiinately neutral solutions of aldehydes and aliphatic
methyl ketones form well ciystalliaed compounds** with sodium bisulfite.
These products are possibly the alkali salts of a-hydroxysulfonic acids:*'
R R OH
^C==0 + NaHSO, -* yC^^
H H SO,Na
R . R OH
^C==0 + NaHSO, - ^C(^
H.C H.C SOJâ
The bisulfite is rapidly consumed and converted into a compound

which differs from free bisulfite in that it no longer reacts with iodine.
Therefore, when a solution of aldehyde or methyl ketone is mixed with a
dilute solution of bisulfite and then a blue starch-iodine solution is added,
and the color is not discharged, it indicates the presence of aldehydes or
ketones. Of course, no other substance which will consume iodine must be
present.
^[Procedure**A drop of the alcoholic or aqueous test solution is
mixed with a drop of an approximately 0.001 N bisulfite solution. If
the original solution is alcohoUc it is advisable to dilute with 4 or 5 drops
of water. After about 5 minutes, a drop of a 0.001 N iodine solution is
added, and a drop of a starch solution made very faintly blue with iodine.
If the blue color remains, the test is positive, indicating the presence of
aldehyde or ketone. A blank test is advisable for the detection of very
small amounts.
Reagents: 1) 0.001 N sodium bisulfite solution
) Approximately 0.001 N solution of iodine in potassium
iodide
S) 1% starch solution faintly colored with iodine
The dilutions of i ) and ) should" be so adjusted that 10 dropa of the
bisulfite solution require 11 of 12 drops of the iodine solution to give a
permanent blue.
" C. Bertagnini, Compl. rend., 36, 800 (1852); Jahresher. Fortachr. Chem. vr-
wandter Theile andtr^ Wiaaentehaflen, 1863, 615.
F. Raschig and L. Prahl, Ann., 448, 266 (1926); see also G. Schroeter, Ber.,
69, 2341 (1926); 61. 1616 (1928).
The following were revealed:

0.05 7 formaldehyde l7 m-nitrobenzaldehyde
0.5 7 acetaldehyde l7 p-aminobenzaldehyde
57 oenanthal 20-y vanillin
57 furfural 15 r anisaldehyde
27 benzaldehyde 500 7 glucose
47 benzaldehyde-o-sulfonic acid 500 7 levulose
47 o-hydroxybenzaldehyde 500 7 lactose
17 m-hydroxybenzaldehyde 50 7 acetone
10 7 p-hydroxybenzaldehyde 2 0 7 methyl ethyl ketone
47 o-nitrobenzaldehyde 20 7 acetophenone
No reaction was given by: cane sugar, benzophenone, benzil, ethyl
alcohol, purified dioxane (boiling with hydrochloric acid and distillation
over sodium).
o-DIOXO AND OXOMETHYLENE COMPOUNDS
(COCO AND CHjCO GROUPS)
1. Test for aliphatic 1,2-dioxo compounds by conversion into nickel
dioxime salts.*' Aliphatic and monocyclic hydroaromatic o-dioxo com-
pounds react with hydroxylamine and produce 1,2-dioximes that can form
red 'or yellow inner-complex nickel salts.*'
O
c=o -C=N
\
+ 2 NHjOH + I Ni+ > i / 2 + 2 H , 0 + H+
-C=0 C==N
OH
It is possible to distinguish, through this reaction, aliphatic (or mono-
cyclic hydroaromatic) dioxo compounds from aromatic dioxo compounds,
such as benzil, phenanthraquinone, camphor quinone, etc. The latter
are orthoquinoidal in character and hence are not oximated, but instead
are reduced by hydroxylamine.
^ProcedureA drop of the test solution is treated in a centrifuge
tube with 1 drop hydroxylamine solution and warmed briefly on the water
bath. A drop of the clear solution is then placed onfilterpaper and spotted
with 1 drop nickel acetate solution. A more or less intense yellow or red
appears, either at once or after fuming over ammonia. '
M . Ishidate, MifcrocAm. ^ d a , 3, 283 (1938). "
< See F. Feigl, op. cil. (this text, page 2), page 96.
0-DIOXO AND OXOMETHTLENE COMPOUNDS 335
Reagents: 1) Hydroxylamine solution: 1 g. hydroxylamine hydro-

chloride, 1 g. sodium acetate, 2 ml. water
2) 5% nickel acetate solution
The identification limits for the detection of aliphatic 1,2-dioxo
compounds are given in Table 10.
2. Test for oxomethylene compounds by conTersion into 1,2-diketones/'
The conversion of aliphatic 1,2-diketones into 1,2-dioxime nickel
salts as described in 1 can also be used for the detection of oxomethylene
compounds, if the CHj group adjacent to the CO group can likewise be
oxidized to a CO group. Selenium dioxide is a suitable oxidant, and it is
specific for the CHsCO group.**
The reaction is not completely decisive for theCHjCO group,
in so far as the o-dioxo compounds, which finally enter the test reaction,
may sometimes originate in other groupings which produce them when
oxidized by selenious acid. Instances are:
o) Compounds of the acyloin type, RiCOCH(OH)Rj, can be
oxidized, just as the oxomethylene groups, to the corresponding dioxo
compounds. This grouping, in distinction to the oxomethylene grouping,
is easily oxidized to o-diketones by otljer oxidizing agents also (chromic
acid, potassium ferricyanide, etc'^).
b) Selenious acid is also capable of oxidizing unsaturated hydrocar-
bons to the corresponding a, jS-unsaturated ketones*' which then, in turn,
may be further oxidized, as in a), to diketones.
c) The groupingCHOHCH2 also can be oxidized to diketone.
llProcedureOne drop of the alcoholic test solution is placed in a
capillary tube along with several grains of selenious acid. The capillary
is fused shut and heated for 20 minutes at 150 to 170 C. When cool,
the capillary is opened, its contents transferred to a centrifuge tube, and
warmed briefly with 2 drops of the hydroxylamine solution just described.
The oxime is formed and the excess selenious acid is reduced to selenium.
A little animal charcoal is added and the selenium is separated by cen-
trifuging. One drop of the clear supernatant solution is placed on paper
and spotted with 1 drop 5% nickel acetate solution. A yellow or red fleck
appears if the oxomethylene group is present
The identification limits for the detection of oxomethylene compounds
are given in Table 10.
" M . Ishidate, Mikrochim. Acta, 3, 283 (1938).
" H. L. Riley, J. F. Morley, andN. A. C. Friend,/. Chem. Soc, 135,1875 (1932)
" E. Schwenk and E. Borgwardt, Ber., 66, 1609 (1932). C.Dupont, J. Allard,
and R. Dulon, Bxdl. soc. chim. [i], 53, 599 (1933). W. Zacharewicz, Chem, Abstracts
30, 8191 (1936).
ll
il o
s
?-
^
US
i t
n
p
o
o
O
s
h
E
o
a
o
6o
w
o
6o
6
o
o
u wo
oo
ow
I I
5
w
o w
M
o oo oo
z<O o
n
o
H
O
m
<
H
o
6 si I \ I B-A o
a
o
a
o o
o6 ow 3-W'O OW
3 9 9 %
sa 8W
<!0 | g o W -o So
s
^
0-DIOXO ANP OXOMETHTLENE COUPOTTNSS 337
uI I 10 p
I to
a
o I
w
o
o
.1
o
w AJ \ II K
o uo
OW
6o / \ -
I o
c 5
w w
I 2. OO
So
i
\ /
39 ow ow
JS *^
ft. O / \
3. Test for aromatic o-dioxo compounds by conyersion into oxazine dyes."*

The action of 2-ainino-5-dimethylaminophenol (I) on aromatic o-diketones,
such as phenanthraquinone (II), involves first a mutual reduction and
oxidation to the tautomeric system of the forms (III) and (IV). The
reaction continues and a deep blue oxazine dye (V) is formed:
NH, O
(CH,)sN OH
(I)
/ \
NH HO
+ X
(CH,),N
A/\ OH HO
AA (CH,),N
X
(III) I
v/
(IV)
The formation of this dye occurs only with aromatic dioxo compounds
which aire not oximated when subjected to the procedure described in 1.
Accordingly, aliphatic 1,2- and aromatic o-dioxo compounds can be dis-
tinguished from each other by the dioxime formation on the one hand,
and through the oxazine formation on the other. - -
Care must be taken that the sample contains no oxidizing agent,
since the latter will react with the reagent and form colored quinoidal
compounds.
IfProcedureOne drop of the test solution is placed in a micro, test
tube and treated with 2 drops freshly prepared reagent solution. A
more or less intense blue appears either immediately or after gentle warm^
ing, depending on the quantity of dioxo compound presenl. When dealing
with small quantities it is well to run a blank and to view the cdlor against
a white background. . - -'
Reagent: 0.05 g. 2-nitroso-5-dimethylaminophenol" is suspended
" M. Ishidate, Mikrochim. Acta, 3, 283 (1938).
" For preparation, see R. Mohlau, Ber., 26, 1059 (1892).
ALDEHYDES 339
in 5 ml. glacial acetic acid. It is shaken with zinc dust (with

cooling) until decolorized, filtered, and the filtrate diluted
to 10 ml. with glacial acetic acid. The reagent must
always be freshly prâred because it turns light blue on
standing in contact with the air
The reaction as described revealed: 2.5 y benzil; 1 y camphorquinone;
0.25 y phenanthraquinone.
ALDEHYDES (CHO-GROUP)
1. iTest with triphenylmethane dyes.'' Triphenylmethane dyes are
decolorized by sulfurous acid (page 234) and fo^n N-sulfinic acids of the
dye leucosulfonjc acid. The resulting colorless solutions turn red to blue
on the addition of aldehydes. The comphcated mechanism of the de-
colorization of fuchsin and the restoration of the color by aldehydes, is
due to the conversion of fuchsin (I) into a quinoid dye (II) :*'
HjN
H,N-
>=<Z =NH
(I)
RCH(OH)SO,-
KI>. "^
/0=^ y=NH
RCH(OH)-SOj-
(II)
An analogous change occurs with other triphenylmethane dyes.
The reaction between aldehydes and solutions of fuchsin or malachite
green, which have been decolorized by sulfite, can be carried out as a spot
reaction â) on a spot plate, or (b) on filter paper.
"[[Procedure'^(a) A drop of the alcoholic or aqueous solution is
treated on a spot plate with a drop of sulfurous acid and a drop of fuchsin
sulfurous acid and allowed to stand. The red to blue color appears in 2
minutes to half an hour according to the amount of aldehyde present.
Reagents: 1) Fuchsin sulfurous acid (SO2 is passed through a 0.1%
solution of fuchsin until the color is discharged)
* 2) 1% solution of sulfurous acid
H. Sohiff, Ann., 140, 93 (1866); B. v. Bitto, Z. anal. Chem., 36, 373 (1897);
E. Votocek, Ber., 40, 414 (1907).
w H. Wieland and G. Scheuing, Ber., 64, 2527 (1921).
** F. Feigl and R. Zappert, unpubliahed studies.
340 TI. OKOANIC SPOT TSSTB
The following were detected:

1 1 formaldehyde 50 7 m-hydroxybenzalde-
4 7 acetaldehyde (freshly distilled) hyde
20 r furfural (freshly distilled) 1000 7 p-hydroxybenzalde-
30 7 benzaldehyde (freshly distilled) hyde
40 7 o-nitrobenzaldehyde 1000 7 anisaldehyde (freshly
40 7 m-nitrobenzaldehyde distilled)
40 7 p-nitrobenzjddehyde 8 7 ciimamaldehyde
100 7 o-hydroxybenzaldehyde (freshly distilled)
Oenanthal gives a slight reaction; vanillin, p-aminobenzaldehyde, and
p-dimethylaminobenzaldehyde give none.
UProcednre"*(b) A drop of a neutral aldehyde solution is placed
on filter paper impregnated with a solution of malachite green decolorized
with much alkali sulfite. A green spot develops.
Reagent paper: 0.8 g. malachite green is suspended in a little water
and brought into solution by adding 3 g. sodium
sulfite, and warming. Two grams more of the sulfite
is added, and the solution filtered. Thin filter paper
is bathed in the cooled yellowish liquid and dried in
the air
This color reaction will reveal 20 to 300 7 aldehyde.
2. T8t with o-dianiddine.'' Primary aromatic amines combine with
aliphatic and aromatic aldehydes in acetic acid solution with loss of water.
The condei^tion products, which are sometimes colored, are known as
Schiff's bases. For example:
/NHCH,
CH,- CHO + 2 CHjNH, - CH,- CH< + H.O
^NHCH,
CHjCHO + CjajJH, - C,H,CH==NC,H, + Hrf)
0-Dianisidine is especially suitable for the formation of colored Schiff's
bases:
H,CO OCH,
H,N NH,
Ketones do not generally interfere, as they are rather inactive, but

large amounts of certain ketones may give yeUow, green or br^wn colora-
tions, especially on heating. This may interfere with the detection of very
small amounts of aldehydes, or the ketone may be m i s ^ e n for an aldehyde.
" O. Frehden and K. Ffirst, Mikrochem. ver. Mikrochim. Acta, 26, 39 (1939).
* R. Wasicky and O. Frehden, Mikrochim. Acta, 1, 56 (1937).
ALDEHTDEB 341
Formation of traces of ketimides is probably the cause of these extraneous

colors.
Alicyclic compounds such as pinenes, camphenes and others, espe-
cially when present in high concentrations, form brown colors with the
reagent They can interfere with the test when the sample is a mixture,
such as ethereal oils. The brown reaction products are probably addition
compounds.
^ProcedureA drop of the sample is mixed with 3 or 4 drops of reagent
solution in a microcrucible. A bright color usually appears even in the
cold; the color is intensified by heating, either on an asbestos plate or over a
microbumer. The reaction may also be carried out on filter paper, by
treating a drop of the sample solution with the reagent solution. The
color may be deepened by warming over a microbumer.
Reagent: Saturated solution of o-dianisidine in glacial acetic acid.
This is purified, when necessary, by heating with absorbent
charcoal and filtering, 2,7-diaminofluorene may be used
in place of o-dianisidine,. as it forms even brighter colors
with some aldehydes
The colors formed and the limits of identification obtained with this
test are listed in Table 11. \
3;. Test widi azobenzenephenylhydrazine sulfonic 8cid.*' The aqueous
solution of azobenzenephenylhydrazine sulfonic acid (I) reacts with alder
hydes giving deep red or blue solutions. Apparently hydrazones of
aeobenzenephenylhydrazine (II) are formed:
~N=N< >NHNHSO.H
(F
/ \_N=N(^ \NHN=CCHR
(II)
This color reaction may be applied to the detection of aldehydes.

It is carried out in strongly acid solution, with heating, and the product
of the reaction is extracted with chloroform in the presence of alcohol.
It should be noted that the color of the product differs for aromatic and
aliphatic aldehydes; the former are red, the latter blue. Aromatic and
aliphatic aldehydes may be differentiated by this color difference.
Ketones react similarly to aldehydes, but much less readily. The
following do not react: esters, alcohols, phenols, naphthols, amines, amides,
quinones, and also chloral.
*' F. Feigl and G. Frank, unpublished studies.
TABLE 11. ALDEHYDES

Color 1 Limit of
Formula
In the cold On heating tion, T
Formaldehyde HCHO Pale yellow Orange- 40

brown
Acetaldehyde CHjCHO Orange Dark brown 30
Paraldehyde (CH,-CHO), Dark olive Dark red- 4

green brown
Bromal CBrjCHO No reaction Darlf green 40
Acrolein CHjiCHCHO Red-brown Violet- 0.1

brown
Crotonaldehyde CH,.CH:CH-CHO Dark red Dark brown- 2

red
Propionalde- CHaCHs-CHO Dtfrk olive Red 20

hyde green
Oenanthol CH3(CH!)5CHO Red-brown Red 9
Decylaldehyde CH3-(CHj),-CH0 Pale olive Dark brown 200

green
Glyoxal OHCCHO Brown- Yellow- Polymer-

green brown ization
a-Oxy-n-buty- CHjCHjCHOHCHO No reaction Slight

ric aldehyde brown
Citral C(CH,):CH-CHO Dark red Red-blabt , ^ 0.1

1
CHj-CHrCH:C:(CHs)j
Citronellal CH(CH,)-CH,-CHO Deep dark" Carmine 10

1 green
CHj-CHtC(:CHj)-CH,
Anisaldehyde /0CH,(4) Dark Red 2

orange
^CHO (1) /
AXDEHYDE8 343
T A B L E . 11. Continued
Color Limit of
Name Formula
In the cold On heating tion, 7
p-Amino ben- / N H s (4) Orange- Red-brown 0.4

zaldehyde CSHZ brown
\ C H O (1)
Benzaldehyde CeHsCHO Orange Red-orange 3
Benzaldehyde /SO3H (4) Brown-red Dark red 3

o-sulfonic acid CSHZ
^CHO (1)
yCE(CB.,h (4) Dark Olive 3

Cumic aldehyde CeH/ carmine yellow
^CHO (1)
p-Dimethyl- /N(CH3)2 (4) Orange-red Dark 0.2

aminobenzal- carmine
dehyde ^CHO (1)
Piperonal Bright red Dark red 4

(heliotropin) CHs<^\c,H3CH0
Opianio acid C,H,(OCH,)!- COOH CHO Olive green Brown 70
Salicylaldehyde / O H (2)
(o-Oxy benz- CH/ Orange Orange 5
aldehyde) ^CHO (1)
m-Oxybenzalde- / O H (3) Dark Dark 4

hyde CeR/ brown- cherry
^CHO (1) red red
t
p-Oxybenzalde-'> ^ " ^ \ / O H (4) Dark Cherry red 5
hyde orange-
I ^CHO (1) red
o-Nitrobenzal- / N O , (2) Green- Red-brown 5

dehyde brown
X;HO (1)
p-Nitrobenz al- / N O , (4) Orange- Red-brown 1

dehyde cji4<r brown
^CHO (1)
344 V I . OHQANIC SPOT TESTS
TABLE 11. Continued

Color Limit of
Name Fonnula identifica-
tion, r '
/ In the cold On heating
Phenylacetalde- COIsCH.CHO Dark Dark brown Always

hyde brown-red polymer-
ization
o-Phthalalde- /CHO (2) Bright Bright

hyde C,H/ yellow yellow
^CHO (1) precipi- precipi-
tate tate
Protooatechuic / O H (4) Brown-red Dark red 7

aldehyde C H ^ O H (3)
\CHO (1)
Tolyl aldehyde CHjCHiCHO Dark Cherry red 5

orange-
red
/ O H (4) Bright Cherry red 3

Vanillin C ^ i ^ C H , (3) orange-
\CHO (1) red
Cinnamalde- CaisCH:CHCHO Dark Cherry red 0.05

hyde cherry
red
2-Oxy-l-naphth- / O H (2) Orange Brick red 10

aldehyde
^CHO (1)
Furfural C4H,0(CH0) Dark red- Deep blue- 0.02

violet violeT"
IfProcedureA drop of the test solution is mixed with about 7 drops

reagent solution and 4 drops cone, sulfuric acid in a test tube. The tube is
then dipped in a boiling water bath for 30 seconds and allowed to cooH
A few drops alcohol are added and enough chloroform to form a layer.
About 5 drops hydrochloric acid are added and the mixture shaken vigor-
ously. In the presence of aldehydes (ketones) the chloroform layer is
colored. /
Reagents: 1) Cone, hydrochloric acid ^
2) 0.018 g. azobenzenephenylhydrazine sulfonic acid'*
in 100 ml. water
S) Chloroform
" For preparationêe J. Trogerand O. MOlle/, / . pro**, Chem'. [2], 78, 371
(1908). , '
ALDEHTDES 345
The following were detected by this test:

0.25 7 acetaldehyde 0.57 m-oxybenzaldehyde
0.25 7 formaldehyde 0.27 p-nitrobenzaldehyde
0.36 7 paraldehyde 0.16 7 vanillin
0.16 7 oenanthol I7 piperonal
4.5 7 glyceraldehyde 0.57 2-oxy-l-naphthaldehyde
27 phenylacetaldehyde 1.27 dimethylaminobenzalde-
0.2 7 benzaldehyde hyde
0.35 7 anisaldehyde 0.27 acrolein
0.35 7 salicylaldehyde 0.1 7 crotonaldehyde
0.11 7 cinnamaldehyde 0.357 furfural
0.867 o-benzaldehyde sulfonic acid 40 7 acetone
0.57 o-nitrobenzaldehyde 130 7 acetophenone
4.87 o-phthalaldehyde 25 7 cyclohexanone
0J25 7 3-nitrosalicylaldehyde 127 benzoin
6.87 5-mtro8alicylaldehyde 557 epichlorhydrin ,
Ir protocatechuic aldehyde
4. Test by catalytic acceleration of the oxidation of p-phenylenedianune by
hydrogen peroxide.*" p-Phenylenediamine (I) is oxidized by hydrogen
peroxide in acid or neutral solution to a black compound (II). The
product is known as Bandrowski's baae.
NH, NH, NH,
+ 3 H,0, + 6H,0
NH. NH,
(II)
It has been found that the velocity of the oxidation is appreciably
increased by aldehydes.*' This peroxidase reaction may be applied to the
detection of aldehydes, if the test is carried out in certain definite concen-
trations of reagent and acid, at which the oxidation rate of the uncatalyzed
reaction is lowered, while the action of the aldehydes is not appreciably
affected.
In neutral solution all aldehydes form a black color or precipitate,
with other preceding transitory colorations, which last a little longer when
annnatic aldehydes are involved. In acid solution, the aliphatic aldehydes
behave in the same way as in neutral solution, but most aromatic aldehydes
' F. Feigl and G. Frank, unpubliBhed studies.
M G. Woker, Ber., 47,1024 (1914). See also G. Woker, Die KaUilyae (Vols. 27/28
of Die Chemische Analyse), Enke, Stuttgart, 1931, p. 232.
346 VI. OEGANIC SPOT TESTS
form a yellow precipitate or color that persists for some time. This differ-
ence in behavior is useful in distinguishing between aliphatic and aromatic
aldehydes.
Nitriles, aldehyde ammonia, and aldehyde bisulfite compounds behave
similarly to aldehydes. Oximes are less reactive, and' ketones.have no
catalytic effect.
^ProcedureA drop of the reagent solution, 2 drops acetic acid, and
2 drops hydrogen peroxide are mixed with a drop of the test solution
on a spot plate. A color appears in the presence of aldehydes; this appears
at once when large amounts are present, or after a short time when small
amounts of aldehyde are involved. It is advisable always to carry out
a blank test on a drop of water, and further to carry out a parallel test
omitting the acetic acid, as some aldehydes react more rapidly in acid and
others more rapidly in neutral solution. A yellow color in acid*eolution
indicates the presence of aromatic aldehydes.
Reagents: 1) 2 N acetic acid
2) 2% solution of p-phenylenediamine
3) 3% hydrogen peroxide^
The limits of idenlification obtained with this color reaction are listed
in Table 12.
5. Other tests for aldehydes. 1. The formation of alkyl hydroxamic acids
from benzene sulfohydroxamic acid, alkali, and aldehyde" can be used as
the basis of a spot reaction for aldehyde.'* One drop of the test solution is
mixed with 1 or 2 drops of an alcohol solution of benzene sulfohydroxamic
acid and 1 drop 1 N sodium hydroxide. After 5 minutes the mixture is
acidified with 1 drop 0.5 N HCl. The addition of 1 drop 1% ferric chloride
solution produces a red color {Id". Limit: 2 to 100 7 aliphatic or aromatic
aldehyde).
2. The test for sugars described on page 410, by reducing silver oxide,
is a special application of a general aldehyde test." This reaction may be
used to differentiate aldehydes from ketones. Among the aliphatic alde-
hydes, the reactivity decreases as the number of carbon atoms increases.
Benzaldehyde and aromatic aldehydes react quite slowly.'^ Organic
compounds that form silver sulfide interfere.
3. One drop test solution is shaken with 1 ml. ammoniacal fuchsin
solution. If a Adolet color appears within 1 minute, aldehyde is present.*'
Aldehydes, such as vanillin and salicylaldehyde, which are insoluble in
1 A. Angeli, Chem.-Ztg., 20,176 (1896);E. Rimini, Gazz.chim.itdl.,81,84(1901).
" F. Feigl and R. Zappert, unpublished studies. ^
" E. ToUens, Ber., 16,1635 (1882).
M W. Ponndorf, Ber., 64,1913 (1931).
" A. B. Wang, Chem. Abstracts, 26, 1920 (1932).
ALDEHYDES 347
T A B L E 12. ALDEHYDES AND ALDEHYDE DERIVATIVES
Color Limit
Formula
In neutral tifica-
In acid solution tion, r
solution
Formaldehyde HCHO Green Black 0.02

Black Black
icetaldehyde CH,CHO Green Black 0.01

Black Black
Propionaldehyde CaHsCHO Brown Brown 35

Black Black 10
Oenanthpl C.H,,CHO Green Violet 0.3

Black Black
Phenylacetalde- CJIsCHj-CHO Green Violet- 10

hyde Black black 5
Glyceraldehyde CHjOHCHOHCHO Violet Greenish 12

Black Black 8
Acrolein CHi=CHCHO Green Red 0.25

Black Black
Crotonaldehyde CHr-CH=CHCHO Light Brown 0.12

brown Black
Black
Benzaldehyde C.HsCHO Yellow Brown 3.5

Black
o-Benzaldehyde Gai4(S0,H)CH0 (1, 2) Green - Red-violet 1.6

sulfonic acid Black
Phthalic acid C,H4(CH0), (1, 2) Yellow Black 4

dialdehyde 1
o-Oxybenz alde- Orange- Yellow 0.7

hyde yellow Black
Cai(0H)CH0
m-Oxybenzalde- Yellow Violet 0.6
hyde Black
o-Nitrobenzalde- Violet Violet 0.6

hyde Black
CJl4(N0,)CH0
p-Nitrobenz alde- Orange- Red- 0.8
hyde red brown
Black
348 VI. OBGAmC SPOT TESTS
TABLE 12. Continued-

1.
Color Limit
Name Formula
1 of iden-
tifica-
In acid solution t1 In neutral
solution tion, 7
Anlsaldehyde CH,O-C.H<-CH0 Light Darker 5

yellow
Protooatechuio CJEI,(OH),CHO (1, 2, 4) Orange . Greenish- 1.2

aldehyde , brown
Vanillin C.H,(OH){OCH,)CHO (1, 2, 4) Yellow Brown 2

Black
Cinnamaldehyde C.H.CHCHCHO Orange Violet 0.2

Black
6-Nitrososalicyl- /OH Orange Brown 0.15

aldehyde bisul- CJI,(OH)(NO.)CH<( (2,6,1) Black
fite ^SOJâ
Salicylaldehyde /OH Orange YeUow 0.78

bisulfite CJI.(OH)CH(( (2,1) Black
\S0,N
Anisaldehyde /OH Light Brown * 6.6

bisulfite CH.O~C(Jic-CH< (1,4) yellow
\S0Jfa
Cinnamaldehyde /OH Yellow- 31ack 0.8

bisulfite G.H.CH=CHCH<
^0,Na
Furfural bisulfite /OH YeUow Brown 0.66

C4H.0-CH<; Darker Black
\SO,Na
Acetaldehyde /OH Green Green 0.06

ammonia CHr-CH<r Black Black
\NH,
Hexamethylene (CH.)J>f4 Violet Violet 50
tetramine Black Black
Mandelonitrile COI.CHOHCN Yellow Dark- 4

Brown brown
Propionaldehyde C,Hr-CHONON Violet' " - Dark- 34

eyanhydrin brown 10
METHTli KETONES 3^Q
water, also react. (The fuchsin solution contains 0.05 g. rosaniline ba^^
dissolved in 100 ml. water, treated with 2 ml. cone, ammonia, boiled for 5
seconds, cooled, and made up to 200 ml. with COj-free water.)
a,/3-UNSATURATED AND AROMATIC ALDEHYDES
OC===CCHO-GROUP)
Test vith hydrogen sulfide and sodinm pentacyanoanunine feiToate.s
An aqueous solution of sodium pentacyanoammine ferroate NasFe(CN)j,
NHj gives a deep blue color with thioketones, and aromatic, and a.g,
imsaturated aldehydes in the presence of hydrogen sulfide. The reactiojj
with aldehydes, probably involves formation of thioalddiiydes, whiclj
normally polymerize readily. However, in the presence of pentacyano^
ammine ferroate, they react in the initially produced monomolecular fon^^
(equation 1), with the ferroate, with replacement of ammonia (equation 2).
E C H O + H2S = R C H S + H,0 (i)
Na,Fe(CN)6NH, + R-CHS = NaFe(CN)s(R-CHS) + NH, (2)
^[ProcedureA drop of the reagent solution and a drop of ammoniunj
sulfide solution (free from polysulfides) are mixed in a microcrucible
A drop of the aqueous or alcoholic test solution is added, and the mixture
neutralized with dilute acetic acid. In the presence of the reactive aide,
hydes, a blue to green color forms according to the amoimt of aldehyde
present. *
An excess of acetic acid is to be avoided, as a bluish turbidity can
appear even in a blank test. The strength of the acetic acid should there,
fore correspond to the sulfide solution used.
Reagents: 1) 1% solution of sodium pentacyanoammine ferroate
(preparation, see ptê 322 footnote 20)
2) Ammonium sulfide solution
S) Dilute acetic acid
The limits of identifimtion to be obtained with this reagent are give^
in Table 13.
METHYL KETONES (CH.CO-GROUF)

1. Test with sodium nitropnisside.*^ Acetone gives an intense red-
yellow color with sodium nitroprusside and alkali; this changes to pink-
violet on acidifying with acetic acid. Under these conditions an alkaline
H. W. Schwechten, Ber., 66, 1734 (1932). Compftre also F. Feigl, V. Anger,
and R. Zappert, Mikrochemie, 16, 192 (1934).
" JabirMher. Fortschr. Chem. verwmdter Theile anderer WisaenschaSten, 1888,
p. 1648; B. V. Bitto, Ann., 287, 372 (1883).
solution of sodium nitroprusside is decolorized, i The mechanism of this

color reaction is not known. Other methyl ketones react similarly to
acetone, whereas other ketones give no reaction. '
TABLE 13. a ,/3-UNSATUBATED AND ABOMATIC ALDEHYDES

Limit of
Name Foimub Identifica*
tion, y
Benzaldehyde CHjCHO 1
Anisaldehyde Caii(OCH,)CHO (1, 4) 2
Salicylaldehyde 2
m-Hydroxybenzaldehyde Cai4(0H)CH0 1
p-Hydroxybenzaldehyde 2
o-Benzaldehyde sulfonic acid CJI(SO,H)CHO (1, 2) 3
o-Nitrobenzaldehyde * 4
m-Nitrobenzaldehyde CJH4(N0.)CH0 1
p-Nitrobenz aldehyde 2
o
Protocatechuic aldehyde CJI,(OH),CHO (3, 4, 1) 1
Vanillin C,H,(OH)(OCH,)CHO (4, 3,1) 1
Heliotropin 1
H . C ! < ( 2 J > C J H I C H 0 (3, 4,1)
o-Phthal aldehyde C,H4(CH0), ( l / a r - _ 1
Cinnamaldehyde Cja,CH:CHCHO 2
Furfural HC- CH 1
II II
HC CCHO
\y
0
fProcedure''A drop of the aqueous OE, alcoholic test solution is
mixed in a microcrucible with a drop of sodium nitroprusside solution and a
METHYL KETONES 351
drop of sodium hydroxide solution. After a short time, when a slight color
usually develops, 1 or 2 drops glacial acetic acid is added. A red or blue
color indicates the presence of a methyl ketone.
Reagents: 1) 5% solution of sodium nitroprusside
5) Glacial acetic acid
2 y acetophenone (blue) 2 y acetyl acetone (purple)
10 y acetone (pink) 4 y acetoacetic ester (orange)
10 y methyl ketone (pink) 10 y diacetyl (pale pink)
10 y methylheptanone (brown- 15 y pyruvic acid (alkaline:
violet) red; acid: dirty brown)
10 y methyl stearyl ketone (red) 15 7 acetone dicarboxyhc acid
(violet)
2. Test by conversion into indigo.*' The dye indigo is formed by the action
of o-nitrobenzaldehyde (I) on acetone in alkaline solution. o-Nitrophenyl
lactyl ketone (II) is first formed, which loses a molecule of acetic acid and
probably forms o-nitrostyrol (III) as intermediate, which by intramolecular
condensation is converted into indolone (IV), and this polymerizes to
indigo (V):
CHs-COCH,
0-Nitrobenzaldehyde reacts similarly, to form indigo, with all sub-

stances that contain the CHj-CO grouping, so that the formation of the
dye may be applied as a test for this grouping.
" A. V. Baeyer and V. Drewsen, Ber., IB, 2856 (1882); F. Penzoldt, Arch. klin.
Med., 48,132 (1883). Compare also R. J. Le Ffevre and J. Pearson, / . Chem. Soc, 136,
2807 (1932).
352 . VI. OKQANIC SPOT TESTS
IfProcedure'*'A drop of the test solution, whicH, if passible, should

not be alcoholic, is treated in a micro test tube with aidrop of an alkaline
solution of o-nitrobenzaldehyde, and gently wanned in a water bath. The
cooled mixture is extracted with chloroform. A blue color in the chloro-
form layer indicates the presence of a methyl ketone. AlcohoUc solutions
sometimes produce a red instead of a blue color in the chloroform layer.
Reagents: 1) Saturated solution of o-nitrobenzaldehyde in 2 iV
sodium hydroxide
2) Chloroform
The following amounts were detected;
100 7 acetone 200 7 acetyl acetone
150 7 methyl ethyl ketone 40 7 diacetyl
150 7 methylheptanone 300 y acetoacetic ester
50 7 acetophenone 100 7 acetaldehyde
OXIMES AND HYDROXAMIC ACIDS 0 0 = N O H GROUP)
Test by flitting nlS hydroxyuunine and ondation to nitrous add." The
test for hydroxylamine, described on page 189, which is based on oxidation
to nitrous acid with iodine, diazotization of sulfanilic acid, and coupling
with a-naphthylamine, may also be applied to the detection of aldoximes
and ketoximes. As a preUminary it is necessary to heat the oxime with
cone, hydroehloric acid to split off hydroxylamine, the aldehyde or ketone
being regenerated. After the decomposition and cooling, the product of
the hydrolysis is treated as though only hydroxylamine hydrochloride were
present.
^[ProcedlireThe sample substance (solutions should be evaporated
to dryness) is heated in a microcrucible with 3 drops cone, hydrochloric
acid mitil the volume is reduced to one-fifth of the original. A few mg.
solid sodium acetate, 1 or 2 drops of a solution of sulfanilic acid, and a drop
of iodine in glacial acetic acid are added in succession. ThiB^mixtiire is left
standing for 2 or 3 minutes. Any excess free iodine is removed by sodium
thiosulfate, and then a drop of a-naphthylamine solution is added. A
more or less intense red color appears, according to the amount of oxime
present.
Reagents: 1) O.l N iodine in acetic acid: 1.3 g. iodine in 100 ml.
glacial acetic acid
S) Sulfanilic acid solution: 10 g. sulfanilic acid in 750
ml. water and 250 ml. glacial acetic acid ^
3) 0.1 N sodium thiosulfate _
4) a-Naphthylamme solution: 3 g." Base in 700 ml. water
plus 300 ml. glacial acetic add
" F. Feigl, R. Zappert, and J. V. Sanchez, Mikrochemie, IT, 169 (1936).
"F. Feigl and V. D^mant, Mikroehim. Ada, 1,^32 (1937).
THIOKETONEB AND MERCACTANB 353
The limits of identification for different oximes and hydroxamic

acids, using this test, are given in Table 14.
THIOKETONES AND IVÊRCAPTANS O C = S AND
> C S H GROUP)
Test by catalysis of the iodine-azide reaction." The reaction:
2NaN, + I, = 2NaI + 3N,
TABLE 14. OXIMES AND HTOHOXAMIC ACIDS
Limit of
Name FoRnula identifica-
tion, y
Acetone oxime H,C-C(NOH)-CH. 0.08

Diacetyl dioxime H,CC(NOH)C(NOH)CH, 0.03
Isonitrosoacetophenone CH^COCH(NOH) 7
Cyclohexanedione dioxime CJI,{NOH). (1, 2) 0.1
Camphorquinone oxime C,HCOC(NOH) 0.5
Benzil dioxime CJI,C(NOH)C(NOH)CJIs 0.05
Oxobenzalbutanone oxime CJI,CH=C(CH,)C(NOH)CH, 0.2
Desoxybenzoin oxime CJI,-C(NOH)CHr-COIs
Benzoin oxime CBtC(NOH)CH(OH)CJI,
Isomtrosomethyl ethyl ketone H,CCOC (NOH)CH,
Methyl ether of salicylaldoxime CJI,(OCH,)CH(NOH)
Benzhydroxamic acid C^Hr-C(NOH)OH
Benzenesulfydroxamic acid CO!,80,(NH0H)
Benzylbenzoin oxime C^,C(NOH)C(OH)CJI,
GHiCiHi
a-Nitroso-P-naphthol NO NOH 0.5
which alone pfoceeds extremely slowly, is catalyzed not only by inorganic

sulfides, thiosulfates and thiocyanates (see pages 227, 240, and 212) but
also by organic compounds containing the groups ^ C = S or ^CSH.
Other organic sulfur derivatives such as thioethers (RSR), disulfides
(RSSR) [with the exception of diacyldisulfides (RCOSS
COR)), sulfones (R-ÔjR), sulfinic acids (RSOjH), and sulfonic
acids (RSO3H) or the salts of these two acids, all exert, no, or at the
most, a very slight effect on the reaction.
" F. Peigl, Mikroehemie, 16,1 (1934). Compare also E. Chargaff, Diuertation,
Vienna, 1928:
354 VI. OHGANIC SPOT TESTS
The mechanism of the catalytic effect of mercaptans and thioketones

on the iodine-azide reaction has not yet been completely elucidated.
In all likelihood, the same explanation will not be valid for all compounds.
The action of mercaptans is probably analogous to the caialytic activity of
inorganic sulfides (see page 227). It probably involves the formation of a
reactive labile intermediate compound, RSI (1), which reacts with sodium
azide, as shown in (2). The summation of (l)and (2) gives the equation
of the uncatalyzed reaction, in which the regenerated catalyst no longer
appears:
RS Na + Ij - RSI + Nal rapid (1)
RSI + 2 NaNs -^ RSNa + Nal + 3 N, . . rapid (2)
2 NaNs + I2 -2 Nal + 3 Nj rapid (1 + 2)

Thioketones probably also form an analogous labile intermediate
SI
product containing iodine, ]>C<^, , that can react with sodium azide
with regeneration of the catalytically active thioketones:
QT
>C<j + 2 NaNa -> > C = S + 2 NaI4- 3 N2
It is also possible that another type of intermediate compound is formed,
as discussed in more detail (see page 417) in the test for carbon disulfide.
Hence the evolution of nitrogen in the iodine-azide reaction can be used
equally well for the detection of the > C = S and ^CSH groups as for
inorganic sulfides. Under certain conditions (see below), it may also be
used to differentiate between these two groups.
^ProcedureA drop of a solution of the test: substance in water or
an organic solvent" is mixed on a watch glass with a drop of iodine-azide
solution, and observed for any evolution of little bubbles of nitrogen.
Either a solid or liquid compound (after removal of the solvent)-may be
tested directly with the reagent. A positive reaction is then especially
easy to see, even with very small amounts of substance.
Reagent: A solution of 3 g. sodium azide in 100 ml. 0.1 N iodine
solution
Compounds containing the ^ C = S and ^CSH groups may be
differentiated by the fact that the latter are converted to disulfide:
2 (RSH) + I2 -RSSR + 2 HI
which does not react vnth the iodine-azide solution. Therefore, when a
sample gives a positive reaction with iodine-azide solution, a fresh sample
" Carbon disulfide should not be used as a solvent, since as a thio compound it
reacts with the iodine-azide solution (see page 417).
CABBOXYLIC ACIDS AND THEIB DERIVATIVES 355
should be wanned for a short time with iodine plus sodium acetate and then
tested again with the iodine-azide solution. When the reaction is again
positive, the > C S group is present.
The limits of identification are given in Table 15. As the drop size
for the organic solutions is not constant, the niunber of drops per ml. have
been determined in each instance, in order to obtain the volume requisite
for the calculation of the concentration limit.
The detection of sulfur dyes and the differentiation of animal and vege-
tablefibersby means of the iodine-azide reaction are discussed on pages
481 and 484.
CARBOXYLIC ACIDS AND THEIR DERIVATIVES
Test by Conversion into the Iron (III) Salts of Hydroxamic Acids
Carboxylic acids, esters, and anhydrides can be readily converted
into hydroxamic acids, R-CO(NHOH). The procedure is different and
characteristic for each type of compound.
All hydroxamic acids give a red or violet color with ferric chloride in
weak acid solution. This color reaction is due to the acid CO-NHOH
group, which is present in all hydroxamic acids. It reacts with the ferric
ion to form soluble inner complex salts:
H
I
NO
/
RC
\
OFe/3
The conversion into hydroxamic acid and the formation of iron (III)
hydroxamate is used as a test for carboxylic acids and their derivatives.
Test for Carboxylic Acids (COOH group)'^
Carboxylic acids cannot be converted into hydroxamic acids by direct
action with hydroxylamine. The tcid chloride must be formed first and
this readily gives the hydroxamic acid on treatment with hydroxylamine
and alkali. The underlying reactions of the test are:
R-COOH + SOCU -> R-COCl + SOj + HCl
R-COCl + NH2OH + NaOH- R-CO(NHOH) + NaCl + H,0
3 R-CO(NHOH) + FeCl, -^ 3 HCl + FeIR-C0(NH0)]3
'* F. Feigl, V. Anger, and O. Frehden, Mikrochemie, IB, 18 (1934). Compare
D. Davidson, J. Chem. Education, 17, 81 (1940).
356 VI. ORGANIC SPOT TBST8
T A B L E 15. THIOKETONES AND MERCAPTANS
Limit of identijScii- No. of

Name and {ormult tion and con-, 1 Solvent drops
centTfttion limit] per ml.
i
p, p '-Dimethoxy thiobenzophenone
0.1 y Acetone + 60
CH,0<(^~ y'C/ SoCH.
1:200,000 water
8
4-Thio-a-naphthoflavone
S
II
0.02 7 Acetone + 66
c 1:1,000,000 water
CO
0
Diphenyl thiocarbonate
Acetone + 60
CH,(>-C&-OC,H, 1:20,000 water
Di-p-tolyl trithiocarbonate 0.1 -y Acetone + 50

H,CC,H4-B-CSS-C,H4CH, 1:200,000 water
Methyl a-naphtbylcarbodithionate
CitHTCSSCHj 0.12 7 Methyl 80
1:100,000 alcohol
Thiourea
0.006 7 Water 20
SC(NH,), 1:10,000,000
sym. Diphenylsulfourea
CHJfHC8NHCiH. 0.67 Alcohol + 80
1:200,000 water
Diphenylthiocarbazone (dithizone)
C,H,N=NC8NHNHCH, 2.5 7 Acetone + 40
1:10,000 water
Rubeanic acid
HJ!T_CS-CS-NH, 0.037 Acetone + 30
1:1,000,000- water
Thioglycolic acid 0.057 Water 20

CHiSHCOOH 1:1,000,000
>%
CARBOXTLIC ACIDS ANP THEIR DBBIVATXVB8 367
TABLE 15. Continued
Limit of identifica- No. of

Name and formula tion and con- Solvent drops
centratioa limit per ml.
Thioacetic acid 0.0003 y Acetone + 30

CH.COSH 1:100,000,000 water
Methylxanthic methyl ester 0.03 7 Acetone + 30

CH,0-CS-SCH, 1:1,000,000 water ,
Potassium xanthate 0.04 7 Water 25

C,H.O-CSSK 1:1,000,000
Rhodanine
HN CO
0.003 7 Acetone + 35
SC
1 1CH, 1:10,000,000 water
s
3-Amino-4-phenyl-6-thiotriazole
NHi-C ^NCH,
0.03 7 Acetone + 30
n 1C S H
N 1:1,000,000 water
Allyl mustard oU 15 7 Acetone + 35

SC:N-CH,-CH=CH, 1:2,000 water
Phenyl mustard oil

S=C=NQHs 0.25 7 Acetone + 40
1:100,000 water
^[Procedure'A drop of the test solution is evaporated to dryness in a

microcrucible, or a minute sample of the solid is treated there with 2 drops
thionyl chloride and the mixture evaporated almost to dryness to convert
the carboxylic acid into its chloride. Two drops of an alcoholic solution of
hydroxylamine hydrochloride are then.added and drops of alcoholic caustic
soda until the liquid is alkaline to litmus paper. Reaction takes place on
reheating. The mixture is acidified with a few drops of dilute hydro-
chloric acid, and treated with a dilute solution of ferric chloride. The
color changes range from brown-red to dark violet (the acidity of the solu-
tion should again be tested with litmus).
Reagents: 1) Thionyl chloride <

2) A saturated alcoholic solution of hydroxylamine hydro-
chloride
S) Altoholic sodium hydroxide solutibn
4) 1% solution of ferric chloride
5) 0.5 N hydrochloric acid
The limits of identification obtained with several carboxylic acids are
given in Table 16.
TABLE 16. CARBOXTLIC ACIDS
Limit of
Name Fonnula identifica- Color
tion
Sodium acetate CH.COONa 100 7 Violet-red

Monochloroacetic ClCHjCOOH 12 7 Violet
acid
Dichloroacetic CHChCOOH 11 7 Red-violet
acid
GlycocoU NH.CH.COOH 15 7 Lilac
Stearic acid CI7HHC00H 20 7 Brown-violet
Crotonic acid CH^CH=CH-COOH 33 7 Violet
Oleic acid CHr (CH,)7-CH=CH- (CHj)7-C00H 11 Y . Red-violet
Succinic acid HOOC CHzCHj COOH 11 r Violet
Tricarballylic acid C H , CH CH, llr Violet
i I I
COOH COOH COOH
Citric acid CHj C(OH)CHj Violet-red
I I I
Phenylacetic acid COOH COOH COOH 11 7 Red-violet
Cinnamic acid C.H5-CH,C00H 33 7 Violet
Anthranilic acid CHsCH=CHCOOH 12 7 Dark violet
Thioacetic acid C,H4(NH,)C00H (1, 2) Violet-red
CH,COSH ^
Test for Esters of Carboxylic Acids (COOR group)"

Esters of carboxylicjjcids can be converted to hydroxamic acids on
treatment with hydroxylamine hydrochloride in the presence of alkali:
RCOORi + NHsOH = RCO(NHOH) + RjOH
These give colored inner complex iron (III) salts with ferric chloride (see
page365). Lactones r6act similarly to esters; they may be regarded as
inner esters. _ -
" F. Feigl, V. Anger, and 0 . Frehden, Mikrochemie, 16, 12 (1934).
CARBOXYLIC ACIDS AND THEIR DERIVATIVES 359
f ProcedureA drop of the ether solution of the ester is treated in a

porcelain microcruciBle Avith a drop of alcoholic hydroxylamine hydro-
chloride solution and one of alcoholic caustic potash. The mixture is
heated over a microflame until the reaction begins, which can be seen by a
slight bubbling. After cooling, the mixture is acidified with hydrochloric
acid, and a drop of ferric chloride solution is added. A more or less intense
violet color appears according to the amount of ester present.
Reagents: 1) Saturated alcoholic solution of hydroxylamine hydro-
chloride
^) Saturated alcoholic potash
S) 1% solution of ferric chloride
4) 0.5 N hydrochloric acid
The limits of identification for different esters are given in Table 17
(page 360).
0=0
Test for Carboxylic Acid Anhydrides Ô group
C=0
Carboxylic acid anhydrides react with hydroxylamine to give hy-

droxamic acids:
> 0 + NH5OH = RCO(NHOH) + RCOOH

K
o
These give soluble colored inner-complex iron (III) salts with ferric chloride
(see page 355).
^ProcedureA drop of the ether solution of the anhydride is mixed
in a porcelain microcrucible with 1 or 2 drops of the reagent solution and
evaporated to dryness over a microbumer. A few drops of water are added.
A violet or pink color is formed according to the amount of anhydride
present.
Reagent: A 0.5% alcoholic solution of ferric chloride acidified with a
few drops cone, hydrochloric acid and saturated, warm,
with hydroxylamine hydrochloride
The limits of identification for different anhydrides are given in
Table 18 (page 361).
" F. Feigl, V. Anger, and 0 . Frehden, Mikrochemie, 15, 12 (1934).
coo^
1,2-DICARBOXYLIC ACIDS
COOH
Test by Melting with ResorcinoF?
(I:
GROUP
)
Dicarboxylic acids with the carboxyl group in' the 1,2 position'*
(one COOH group may be substituted by a SOgH group) or their deriva-
T A B L B 17. EBTBRS O F C A B B O X T U C ACIDS
d Limit of
identifica-
Name Fonnula Coloi
tion
Ethyl formate HCOOCiH, .117 Violet-brown

lilac
Ethyl ortho- HC(OC,H,). 10 7 Violet-red
fonnate
Btbyluretban NHfCOOCtH, 10 y Gray-violet
Ethyl acetate CH,-COOC,H. 2y Violet
Vinyl acetate CH,COOCH=CH, 11 7 Violet
Phenyl acetate CHiCOOCOI. 2.5 7 Violet red-
/ ' brown red
GlycoooU thyl HClHiNCHiCOOCH, 13 7 Violet-light
ester hydro- brown
chloride
Ethyl stearate CH,(CH,)COOC.H, 12 7 Violet-red
Cetyl palmitate CH,.(CH,),COOC,JI 11 7 Violet
Glyceryl oleate lCH,(CH,),CH=CH(CH,),COO].Glyc. 10 7 Violet
Diethyl oxalate H.C,OOCCOOCsH, 37 Red violet-vio-
let gray
Diethyl malonate H.COOCCHr-COOCH, 2 . 6 7 Violet-red
Propyl benzoate C,H,COOC,HT 37 Violet
Methyl salicylate HOCJHiCOOCHi 2 . 5 7 Dark violet-
green violet
Phenyl salicylate H0-CJl4C00(C,H,) 67 Dark blue-
violet
Potassium CHjOCSSK 11 7 " "Dark red to
xanthate violet-red
a-Naphthyldithio- CIQHT CSS Cxxi 11 7 Deep violet-
carboxylio acid brown to
methyl ester dark brown
Coumarin , 6 7 Violet-red
CH. 1
-
CTSf '
/
tives, such as esters, anhydrides, or imides, fomr3yes of the fluorescein
type (sacchareins) when melted with resorcinol. These products give a
" F. Feigl, V. Anger, and O. Frehden, unpublished studies.
' Carboxyl groims in the peri position behav^like those in the ortho position.
1,2-piCABBOXTIiIC ACIDS 361
TABLE 18. CAHBOXTUC ACID ANHYDBIDES
Limit
Name of iden-
Formols tifica- Color
tlon
Acetic anhydride CH,.CO ST Violet

>0
CH,CO
Succinic anhydride CHiCO Red-brown

I >0
CH.CO
Thapsic anhydride 0C-(CH,),4-C0 10 7 Pink
Camphoric anhydride CH. 10 T Lilac
|H,CCCH, > 0
H.Cx CO
OH/
Benzoic anhydride
Phthalic anhydride
(r^ -CO
6y
By
Pink
Violet
-CO
m-Nitrophtbalic CO 10 r Pink
anhydride /V^' \
/vxy
NO,
^00
Hemipinio anhydride 6-r Lilac
.o/y^CO/
OCH,
24
362 VI. ORGANIC SPOT TBSTS
vivid green-yellow fluorescence in alkaline solution. The reaction

proceeds:
CH,CH,-COOH CH,CH,
i
COOH
HiSOt
HO OH HO HO HO OH
CH,CH,
CH,.CH,COONa
HO O OH O O OH
The 1,2-carboxylic acids with a free OH group adjacent to the
carboxyl group:
>CCOOH
C(OH)COOH
react m a different manner. They give off CO by the action of cone,
sulfuric acid on the resorcinol melt, to form semialdehydes of maJonic
acid or its homologs (equation 1), and these condense with resorcinol to
produce lunbelliferone or its homologs (equation 2 ) :
COOH COOH COOH
I
CH, CH. CH
HiSO<
1 (1)
CHOH CHO CHOH-
COOH
HOC H
\
/ \ CH /VCs CH
+ 1 + 2H,0 (2)
CO
^CO
HO
\ / \
HO
/ /Vô/
HO HO
The resulting lunbelliferones are ahnost colorl^s, but give an appre-
ciable fluorescence even in daylight, while under the mercury vapor lamp
the fluorescence is a brilliant blue.
SULFONIC ACIDS 363
1[ProcediireA few mg. of the test substance is placed in a micro-

crucible, or a drop of a solution is evaporated there to dryness. A little
freshly sublimed resorcinol and a few drops pure cone, sulfuric acid are added
and the mixture kept at 130 C. for 5 minutes, either on an asbestos plate
or, better still, on an aluminiun block provided with wells to hold 2 crucibles
and a thermometer. When the reaction is complete, the crucible plus
contents is dropped into water in a 50 ml. beaker to dissolve out the
products. The solution is made alkaline with sodium hydroxide. In the
presence of substances containing one of the pertinent groups, a fluorescence
occurs, which is especially bright in ultraviolet light.
A blank test should always be carried out, because when the tempera-
ture has exceeded 130 C, even a blank test shows afluorescence,which is
green by dayli^t, and green-blue in ultraviolet light, and this might lead
to false conclusions. Apparently, at the higher temperature, the resorcinol
partially decomposes and gives rise to dicarboxylic acids.
Reagents: 1) Sublimed resorcinol
J?) Gone- sulfuric acid
The limits of idemiiUcation and the colors of thefluorescenceare given
in Table 19.
SULFONIC ACIDS (SO,H GROUP)
1. Test by fusion with an alkali hydroxide.^* If aromatic and aliphatic
sulfonic acids are fused with caustic alkalis, the sulfonic group is replaced
by the hydroxyl group with the formation of alkali sulfite. For example,
benzene sulfonic acid reacts:
CH5SO3H + 3 NaOH = CHsONa + Na,SO, -}- 2 H2O
The SOj liberated on acidifying even extremely small amounts of
sulfite can be detected by the induced oxidation of the green nickel (II)
hydroxide to the black nickel (III) hydroxide (see page 233). Hence, the
test for sulfite in the alkaline melt affords a means of detecting sulfonic
groups in the original sample.
Sulfinic adds, and likewise swZ/oncs, give rise to sulfite on fusion with
alkalis. Consequently, the test is specific for SO3H, SOjH, and
^SOj,*" provided divalent S compounds, which give rise to alkali sulfides on
fusion with alkali, are not also present. When this is the case, there may
be an appreciable oxidation of the sulfide to sulfite, which can be confused
with any formed from the sulfonic acid group. Further, on acidifying
" F. Feigl and A. Lenzer, Mikrochim. Acta, i, 129 (1937).
'" It should be noted that aromatic sulfinic acids and their alkaline salts are
autoxidizable to sulfonic acids or sulfonates and are, therefore, never pure. A spe-
cific, though not very sensitive reaction, for sulfinate is the precipitation of red-brown
Fe(III) sulfinate from solutions containing mineral acid. See Feigl, op. cit. (this
text, page 2), page 119.
364 VI. OBGANIC SPOT TESTS
TABXJB 19. DicABBOXTuc A C I D S
1 Canstitutioii
Color of fluorescence 1 Limit of iden-
tification, T
Muae \ In
In dayli(fat \ In ultraviolet
light
ultra-
day- violet
light light
Tricarballylic CH, CH-CH, Yellow- Grass S 5

acid 1 1 1
COOB. COOH COOH
rose green
Citric acid CHt C(OH)CHt Yellow Sky blue 15 1

I
COOH COOH COOH
Tartaric acid CHOHCOOH Brown Dark 25

~
1
CHOHCOOH
red blue-
green
Fhthalic acid C,H4(C00H), (1, 2) Yellow- Light 5 5

brown green
3-Nitrophthalic C,H,(N0,)(C00H), Red Pale

acid violet
Hetnipinic acid C,H,(0CH,),(C00H), (1,2,3,4) Dark red Green
Trimellitic acid C!|H,(C0,CH,), (1,2,4) Yellow Light 2.5 2.5

trimethyl ester green
Dihydroxyma- C(0H)C00H Red Blue gray 40 15

leic acid il
C(0H)C00H
Succinic acid or CH.COOH Yellow Emerald 5 5

potassium suc-
cinate
t s green
CHj-COOH
Succinic CH.COv YeUow Emerald 5 6
anhydride green
CHfCcy
Succinimide CH.COv Yellow Emerald 6 5

green
CH.CO^
Malic acid CHjCOOH Yellow ,Light 1

\ blue
CHOHCOOH
SmiPONIC ACIDS 365
TABLE 19. Continued
Color of fiuorcKcnce Limit of iden-

tification, t
Name ConstitutioD In
In daylight In ttlUaviolet In altr&-
light li^t violet
light
SiMXihatin Yellow Greenish 10 s
00-=
yellow
ABparagine NH, Dark Dark 5 10

( wine- green
COOH red
13 H . C 0 N H i
Naphthalic acid Yellow- Dark 6 6

/ \COOH green
brown
<^ ^COOH
the melt, hydrogen sulfide is formed, which precipitates black nickel sulfide.
Any formation of alkali sulfide on fusion with caustic alkali may easily be
discovered from a preliminary test. In this, it is sufficient to take up the
mdt in water and add sodium nitroprusside; a violet color (see page 226)
indicates the presence of sulfide, or of bivalent sulfur in the origiaal sample.
In this case, this test cannot be applied directly for the detection of sul-
f<Kuc groups, etc.
Mercaptans and thioketones can be taken out if a water suspîsion
of the sample is warmed with lead carbonate and filtered. Insoluble lead
mercaptides or lead sulfide are formed; the filtrate contains the soluble
lead salts of the sulfonic acids.
IfProcednreÂ veiy little of the solid sample, or the evaporation
r^due from one drop of test solution, is heated with a grain of solid sodium
bydroxide over a small flame until the mixture just melts. A hard glass
tube, whose bulb has a capacity of about 3 ml. is used. After cooling, the
melt is dissolved in 2 drops water, 1 or 2 drops cone, hydrochloric acid are
added (the acid reaction to be tested with a small strip of litmus paper),
and the waUs of the tube washed with water. The rim of the tube is care-
fully wiped dry, and a strip of filter paper containing Ni(OH)j is laid over
the mouth. The bulb is tiien immersed in hot water for a few minutes to
hasten the volatilization of the sulfurous acid. Any sulfite is evidenced
366 VI. OBQANIC. SPOT TESTS ,
by the change of color of the nickel hydroxide from green to black or gray.
When very small amounts are to be detected, it is best to spot the nickel
hydroxide with an acetic acid solution of benzidine; a blue color is formed
in the jjresence of a trace of Ni(OH). *
Reagents: 1) Sodium hydroxide (solid) '
3) Nickel hydroxide washed alkali-free, prepared by
precipitation of NiClj with NaOH (see page 234)
4) Benzidine: 0.05 g. benzidine or its hydrochloride dis-
solved in 10 ml. 2 N acetic,acid, diluted to 100 ml. with
water, and filtered
The limits of identification attained by this test for sulfonic and
sulfinic acids are given in Table 20.
2. Test by conversion into the iron (HI) salt of acethydroxamic acid.^<
Sulfonic acids can be converted into sulfohydroxamic acids, which react
with acetaldehyde in the presence of alkaU:
RSO2NHOH + CH3CHO -> CH3CONHOH + RSOiH
giving acethydroxamic acid and sulfinic acids. Both of these compounds
react with ferric chloride in acid solution to give a red soluble iron (III)
salt of hydroxamic acid (see page 355), and an orange-red insoluble iron
(III) salt of the sulfinic acid, respectively.
The necessary conversion of the sulfonic acid to the sulfohydroxamic
acid, requires a preliminary preparation of the sulfone chloride, and this
can be converted to the sulfohydroxamic acid with hydroxylamine. Thi-
onyl chloride is used to prepare the sulfone chloride. The sulfohydroxamic
acid reacts with acetaldehyde to give acethydroxamic acid and sulfinic
acid, both of which, as stated, react with ferric chloride.
The equations showing the formation of the characteristic colored
iron salts, starting from the freeVulfonic acid, are:
R-SO,H + SOCU -* R-S0,C1 + SOj + HCI
R-SOsCl -1- NHsOH -> R-SO,(NHOH) + HCI
R-S02(NH0H) -1- CH3CHO -^ CHjCO(NHOH) + R-SOjH
3 CH3C0(NH0H) -1- FeCl, -^ Fe[CH,CO(NHO)la -|- 3 HCI
3 R-SOjH -I- FeCl, -^ Fe(R-SOj), + 3 HCI
In spite of the compUcated series of reactions, the procedure for carry-
ing out the test is relatively simple.
^ProcedureA httle of the solid test substance (if ne'cessary the
evaporation residue from a drop of solution) is fumedîn a microcrucible
with a few drops of thionyl chloride. The product is treated with 2 drops
' F. Feigl and V. Anger, Mikrochemie, 15, 23 (1934).
SULFONIC ACIDS 367
TABLE 20. SULFONIC AND SULFINIC ACIDS AND SITLFONES
Limit
Nuae FonnuU of idea-
tific&-
tion. If
Potaesium hydro- CJi(S0,H)80JC (1, 4) 5

gen benzene di-.
sulfonate
Sodium hydrogen C.,H4(S0.H)S0,Na (2, 7) 3

^-naphthalene di-
Bulfonate
Sodium hydrogen C,H4N(0H)(S0,H)S0.Na (8, 7, 6) 20

hydroxyquinoline
disulfonic acid
Sulfanilic acid CH4(NH,)S0,H (1, 4) 12
o-Benzaldehyde CH4(CH0)S0,H (1, 2) 12

sulfonic acid
Tartrazine HOOCC==Nv 12
1 >NC.H,SO,H
H 1 /
HO,SCHiNN==CCO
Potassium CH,(SO,K), 6
methionate
Camphorsulfonic CiHu(0)SO,H 5
acid
Benzenesulfinic C^SO^ 6
acid
a-Naphthalenesul- CigHrSOiH 12
finic acid
Sulfonal H,C\ /SOtCA 6
H.C^ \S0,C,H,
Trional HjCs, yfiOj C1H4 10
H,C/ ^SO,CH,
368 VI. OBGANIC SPOT TESTS , ' ,
of a saturated alcoholic solution of hydroxylamine hydrochloride and a drop

of acetaldehyde, then made alkaline with a little 6% sodium carbonate
solution. After a short time the mixture is a,cidified[ with dilute hydro-
chloric acid, A drop of a dilute aqueous solution of ferric chloride is added
and a brown to violet color or precipitate appears. A blank test remains
bright yellow. '
When the salt of a sulfonic acid is being tested, it should be evaporated
with hydrochloric acid before the treatment with thionyl chloride. Dye-
stuffs, whose color interfere with the recognition of the color change, can
easily be decomposed with a few drops of bromine water.
Reagents: 1) Thionyl chloride
Z) Alcohol-hydroxylamine hydrochloride solution (satu-
rated)
3) Acetaldehyde
4) 5% sodium carbonate
6) 0.5 N hydrochloric acid /
6) Dilute solution of ferric chloride
The following were identified: ;
12 y benzene sulfone chloride, CeHsSOjCl
20 y naphthalene-/3-sulfonic acid, CioHjSOjH
25 y sulfanilic acid, CeH4(NH2)S03H
10 y potassium hydrogen p-benzene sulfonate, CeH4(S02K)S08H
30 y heliaathin, (CH,)NaH4N = NC6H4SOsNa
15 y H-acid, doHiCOH) (NH,) (S0,H)2
AMINES
1. .Test for primary and secondary aliphatic, amines by conversion to

dithiocarbamate.^ The dithicârbamates*' of the corresponding bases are
formed almost instantly at room temperature by the action, of carbon
disulfide on fr^ primary and secondary aliphatic amines (dissolved in
inactive solvents, if necessary):
SNHiR ^ SNHjRiR,
C8, + 2NH,R - S c / CS, + 2NHR,R, - SC<^ /
NHR NR,R,
The dithiocarbamate may be detected, after the removal of the excess
carbon disulfide, which is readily volatilized at 46_C. The iodine-azide
test may be applied (as described aa page 353) because the dithiocarbamate
" F. Feigl and G. Frank, unpublished studiî.
" A. W. Hofmann, Ber., 1, 26,169 (1868).
AlONES 369
accelerates the reaction between sodium azide and iodine, since it contains
SH and CS groups. Alternatively, the dithiocarbamate is revealed by the
formation of silver sulfide, if a solution of silver nitrate is added to the
residue after evaporation to dryness.
When salts of the bases (such as the hydrochloride) are present, then
use may be made of the fact that triethylamine, which does not react with
carbon disulfide, is so strong a base tliat it can liberate primary and sec-
ondary amines from solutions of their salts. It is therefore sufficient to add
CSj and an excess of (CiH6)8N, or to add a mixture of (C2jl5)3N and
CS2 to the sample, and proceed as will be described.**
Tertiary aliphatic bases do not react. Aromatic amines, which can
also react with carbon disulfide with the formation of thiourea derivatives,**
do not do so under the mild conditions prescribed here. Accordingly, it is
possible to detect aliphatic amines in the presence of aromatic amines.
^ProcedureA drop of the alcoholic test solution, or of the free base,
is mixed with a few drops of an alcohol-carbon disulfide mixture in a
microcrucible, After about 5 minutes, t h e excess carbon disulfide is
volatilized. The apparatus described on page 37 may be used to advan-
tage. A few drops of an iodine-azide solution, or of a solution of silver
nitrate in nitric acid, are added. The mixture is observed for evolution
of nitrogen or for a blackening due to silver sulfide.
The detection of dithiocarbamates may also be carried out on filter
paper. The base and carbon disulfide (if necessary with addition of
N(C2H6)3) are mixed on filter paper and then spotted with an acid solution
of silver nitrate.
Reagents: 1) Mixture of carbon disulfide and alcohol (1:1)
2) Solution of 3 g. sodium azide in 100 ml. 0.1 N iodine
solution
S) Solution of silver nitrate in dilute nitric acid
For the limita 0/ identification see Table 21,
This dithiocarbamate reaction for primary ^.mines may also be applied
to deted. 1 ,Z-diketoms (in the absence of aldehydes). 1,2-Diketone8 read-
ily form condensation producl3 with ethylenediamine; the products are
known as dihydropyrazines. For example, benzil reacts:
N
CH.-C=0 H.N-CH. _ ^ ^ C . H . - c / ^ C H . (i,2.diphenyl-4.6-
C.H.-C=0 H.N-CH. " " C.H.-C^ y U ^^y^-^y^-'^^^
N
In the preBcnce of excess N(CiHOi and CSj, dithiocarbamates of triethyl-
amine are fonued e.g., RHNCSSHN (CiH,)i.
A. W. Hofmann, Ann., 67, 266 (1846); TO, 144 (1849).
TABI.B 21. PBIUABT ANP SECOKDABT ALIPHATIC Ainiras
Detection of dithio-
1 carbuiat*
Fomub
With /With
1 iodine- ' (itvcr
uide nitrtte
Ethylamine CHr-CHr-NH, ' 6.6 y 37
Propylamine CHaCHjrOHj^NHi 13 7 ID 7
Dipropyl- CHr-CHr-CHr-NHCHi-CHr-CHj 140 7 1267
amine
Isobutyl- CH,v 10 y 87
"mine )>CHCHi-^Hs
Di-iaoamyl- 102 7 114 7

amine ( %CHCHjCHiJNH
\CH/ /,
Heptyl- CHj(CH,)r-NH. 12 7 77
amine
Diethanol- (CHjOHCH2)2NH l7 0.67

amine
Benzylamine CJIr-CHr-NH, 16 7 8.67
Piperidine CHiCHi 4.67

H,c/ NNH
CHfCHf
Phenylhy- Cr-NHNH, 2507 2007

drazine
GlycocoU C,H,OOC-CHr-NH,HCl 100 7 - -70 7

eater hy-
drochloride
Leucylgly- HOOC-CHr-NH-COCHNH, 367 357

cine 1
(CH,).CHCH,
Leucylgly- HOOCCHr-NHCOCHr-NHCOCHNH. 3O7 357

cylglycine
(CH,),CHCH,^
1 /
Arginylgly- H,NCH-CONHCHr-COOH 26T 3O7

eine 1 NH
CHr-(CHi)r-NH-CNH,
-p S70
AMINEB 371
Accordingly, a drop of an approximately 0.02% alcoholic solution of

ethylenediamjne is mixed with a drop of the alcohol or ether solution of a
1,2-diketone, and allowed to stand for 10 minutes at room temperature.
An alcohol solution of carbon disulfide is then added and the mixture
evaporated on the water bath. A negative or very slight positive reaction,
compared with a blank test on pure ethylenediamine, indicates the presence
of 1,2-diketones. In this way, the following amounts were detected:
6 r diacetyl, CH| CO CO CH,
55 7 benzil, C.H&-CO CO C,Hs
6 y phenanthraquinone, CjH* CO CO CH4
'2. Test for secondary aliphatic amines with sodinm nitroprusside and
acetaldehyde.** Secondary aliphatic amines form blue-violet soluble
compoimds, of unknown constitution, with sodium nitroprusside and
certain aldehydes (the most suitable is acetaldehyde), in solutions rendered
alkaline with sodium carbonate. The reaction is analogous to that de-
scribed (page 408) in the test for glycerol, which depends on the blue-
violet color formed from sodimn nitroprusside, piperidine, and acrolein
developed from the glycerol. Primary and tertiary amines do not interfere
with the test, but the activity of the NH group appears to be affected by
other groups in the molecule (see Table 22).
fProcednreA drop of the test solution (neutral, acid, or alkaline) is
mixed, on a spot plate or in a microcrucible, with a drop of the reagent
solution, and a drop of a 2% solution of sodium carbonate is added. If
the test solution is acid, care must be taken to add sufiScient carbonate to
render the mixture alkaline. A blue to violet color is formed in the pres-
ence of secondary aliphatic amines. When small amounts are suspected,
a blank test is advisable.
Reagents: 1) 1% sodium nitroprusside solution to which 10% by
volume of acetaldehyde is added. The reagent must be
fresh
B) 2% sodium carbonate solution
The sensitivity of this reaction for a member of secondary amines
is listed in Table 22. The test may be applied to detect the presence of
secondary amines in ethylenediamine, and of mono- and diethylamine in
commercial triethanolamine.
3. Test for NH2, NH or N(CHa) groups by melting with fluorescein chlo-
ride." All compounds containing the NHj, NH or N(CH3) groups give
rise td rhodamine dyestuffs** when melted with fluorescein chloride and
F. Feigl and V. Anger, Mikrochim. Acta, 1, 138 (1937).
" F . Feigl, V. Anger, and R. Zappert, Mikrochemte, 16, 67 (1934).
" P . Friedl&nder, Fortschritte der Teerfarbenfabrikation, Vol. II (1891), pages
79, 81; ibid., I l l (1896), p. 174.
372 VI. ORGANIC SPOT TBST8
TABLE 22. SECONDARY ALIPHATIC AMINES^
i Limit of
identifir Concentra-
Name FonauU Color / tion limit
cation
Diethylamine (C,H,).NH Blue- 4T 1;12,500

violet
Diethanol- (C,H.OH),NH Blue 100 7 1:500

amine
Di-isoamyl- [(CH,),CHCH,CHj],NH Blue- 2T 1:25,000

amine violet
Adrenalone (HO),C,Hr-COCH,NH CH, Blue 10 7 1:5000
Spermidine H,N(CH,)4v Violet 70 7 1:700

>NH
H.N(CH,)/
Spermin H,N (CH,),NH CHr-CH, Violet 80.7 1:600

1 '
H,N- (CH,),NH.CHr-CH,
Pyrrolidine H,C CH, Blue 0.5 7 1:100,000

1 1
H,C CH,
NH
I-Proline HtC CH, Blue l7 1:50,000

1 1 !
H,C CHCOOH
NH ^,
Piperidine /CH,CHr< Blue- 5 7 " 1:10,000

H,C<r >NH violet
X!Hr-CH,/
2,2'-Dimethyl- / CH,CHCH,\ Blue 100 7 1:600

dicyclohexyl- 1 H,C< >CH )NH /
amine \ CH.CH, /,
l-Plienyl-2- H Blue 10 7 1:5000

methylamino C,Hr-CHr-CCH, /
propane J
1 HNCH,
AMINES 373
anhydrous zinc chloride. The properties of the dyestuffs vary characteris-

tically according to the different types of amine used. The formation is
shown in the following equation:
COOH
+ 2HC1
Detection of Primary Aliphatic Amines

On melting primary aliphatic amines or their salts with fluorescein
chloride, light red dyestuffs are formed that exhibit yellow-green fluores-
cence. The general formula of these products is:
COOH
They are symmetrical dialkyl rhodamines, and give an intense

fluorescence both in daylight and ultraviolet light. Rhodamines produced
from acid amides (see page 375) and also from ammonium salts show a
similar fluorescence.
^ProcedureA drop of the test solution, containinghydrochloric acid,

is evaporated to dryness in a test tube, and the residue mixed with a
little fluorescein chloride (from the tip of a spatula) and twice the bulk
of zinc chloride. The mixture is then heated in an air bath (iron crucible
or aluminum block) to 260 to 260 C. until all the zinc chloride has melted.
When cool, the melt is dissolved in alcohohc hydrochloric acid. In the
presence of primary aliphatic amines, the solution shows a yellow-green
fluorescence. For the detection of veiy small amounts of amines, the
solution should be examined for fluorescence in the light of a quartz
analytical lamp.
Limits of iderUification obtained by means of this test are given in
Table 23.
Reagents: 1) Fluorescein chloride**
2) Anhydrous zinc chloride
S) 10% alcohohc hydrochloric acid
Detection of Secondary Aliphatic Amines'"

Tetra-alkyl ihodamines are formed on melting secondary aUphatic
amines with fluorescein chloride:
L JCOOH
y^ o N"^'
R CI R
Acid solutions of these are red and exhibit an orange-redfluorescence.The

difference in the fluorescence color from that of primary amines, which is
yellow-green, gives a basis for the differentiation of these two classes of
compounds.
The test is carried out as described for primary amines.
Limits of identification iot a number of secondary amines are given
in Table 24.
Another test for secondary aliphatic amines is given on page 371.
For preparation, see A. v. Baeyer, Ann., 183, 18 (1876).
" F. Feigl, V. Anger, and R. Zappert, Uikrochemie, 16, 70 (1934).
AMINES 375
Detection of Aromatic Amines

Primary, secondary, and tertiary aromatic amines containing a
methyl group, when melted withfluoresceinchloride, give rise to dyestuffs
of the following types:
COOH
AiHN 0 NHAr
CI
r\
COOH
E
J>N O
l,j
N<
<R > ? <
R Ar ^j Ar
The alcoholic hydrochloric acid solutions of these dyestuffs are deep red-
violet, but imlike the rhodamines formed from the ahphatic amines, they
do not fluoresce. Hence the presence or absence offluorescenceaffords a
means of differentiation between aromatic and aliphatic amines. Benzal
derivatives of amines behave similarly to the parent compounds.
The test is carried out as already described for the aliphatic amines
(page 374 )s Limits of identification for a number of aromatic amines are
given in Table 25.
Detection of Acid Amides and Acid Nitriles'^
Acid amides behave similarly to primary aliphatic amines on melt-
ing withfluoresceinchloridei. Acid nitriles, after they have been saponified
to acid amides give the same products. The rhodamine dyestuffs formed
" F. Feigl, V. Anger, and R. Zappert, Mikroehemie, 16, 71 (1934).
have not yet been isolated; probably the products are ainalogpus to those
formed from primary amines. .
The test is carried out as described for primary iaUphatic amines
TABLE 23. PBIMABT AUPHATIC AMINES
Fluores- Ultralviolet Limit of

Name Formula Color cence fluorescence identifica-
tiOQ
Ammonium chlo- STHICI Pink Green Yellow- 30 T

ride green
Hydroxylamine NHjOHHCl Pink Green Yellow 207

hydrochloride
Hydrazine sulfate NH,.NH,-H,S04 Orange Green Yellow 207
Methylamine hy- CH,-NH,-HC1 Red Green Yellow 10 Y

drochloride
GlycocoU ester CH,COOC,H, Pink , Green Yellow 207

1
NH,
Benzylamine CHs-CHjNH, Red Green Yellow- 10 T

green
TABLE 24. SECONDABBT ALIPHATIC AMINES
Limit
Name Formula Color Fluores- Cltnviolet of iden-
cence fluorescence tifica-
tion
Diethylamine /CH| Red Orange- Orange- 4T

HN< red ^êd
X3,H,
Piper dine xCHjCH| Red Red Orange- 4T

HN<( >CH, r^d
X;Hr-CH,
Aceturic ethyl CHr-COOCH, Orange Orange Orange- 20->'

ester 1 yellow
NHCOCH,
(page 374) except that it is important that the sample'must be evaporated

from neutral solution; in acid solutions the acid amide may be saponified.
Dyestuffs with yeUovofluor^cenceare formed.
AUINES 377
TABLE 25. AROMATIC AMINES
Limit
Name Formula Color of iden-
tifica*
tion
Aniline Red-violet 5y
-NH,
a-Naphthylamine Dark violet 57
>NH,
^-Napbthylamine Red-violet 27
NH,
/J-Aminoanthra- C=0 NH, Red 47

quinone
C=0
Benzidine Red-violet
:N-<(3-
H, -NH, 47
o-Aminobenzalde- Red 27
CHO
hyde
NH,
p-Nitraniline Red-violet 57
H,N NO,
p-Phenylenedi- Purple l7
amine H IN/ \NH,
p-Chloraniline Purple 47
H,N -CI
H-acid CiJH4(0H)(NH,)(S0,H), Red-violet 10 7
Diphenylamine
o -NH-
Purple 87
378 VI. ORGANIC SPOT TESTS >
TABLE 25. Continued '
Limit
Name Formula Color of iden-
tifica- *
tiOQ
Hydrazobenzene Purple iy
<f \~NHNH<^ \
Acetanilide Scarlet 47
/ \NHCOCH,
Benzenesulfo-p-
nitranilide
<^ \SOjNH<^ V - N O , Blue-violet iy
p-Dimethylamino Cherry-red 4r
OHC--<(' \N(CH,),
benzaldebyde
Michler'8 ketone Red 2r

(CH,),N-<^|^ \-C0-<^ \N(CH,)I
Diethylaniline Pink 400-r

<^ ^N(C,EU),
Benzylidene-p-ni- Brown- 87
traniline
/ NCH=N<^^ \NO, violet
The limits of identification for various acid amides are given in

Table 26.
Detection of Pyrrole Derivatives**
Pyrrole derivatives form yellow-brown dyes when melted with
fluorescein chloride and zinc chloride. The products give a blue fluores-
cence in ultraviolet light. This reaction can be applied ajs a test for pyrrole
derivatives.
The procedure is the same as for the other compoimds (see page 374
et seq.). The test solution can be evaporated when either neutral or
alkaline.
The limits of identifixxiiion for a number of pyrrole derivatives are
given in Table 27.
4. Test for primary aromatic amines vith glutaconic aldehyde.*' Acid
solutions of primary aromatic amines give colored products** with/pyridine
irradiated with ultraviolet light. The reaction depends on the hydrolysis
F. Feigl, V. Anger, and R. Zappert, Mikrochemie, 16, 71 (1934).
F. Feigl, V. Anger, and R. Zappert, Mikrochemie, 16, 74 (1934).
H. Freytag and W. Neudert, J. prakt.Chem. 12], 13, 15 (1932).
TABLE 26. ACID AMIDES
DUrviolet Limit o
Nunc Formula Color Fluorescence fluorescence identifi-
cation
Acetamide CH.CONH, Orange Yellow 20-r
Benzamide C,HjCONHj Orange Green Yellow- 2O7

green
Semicarba- /N-HNH, Cherry-red Orange- Orange- 20 7

zide C0<' yellow yellow
PhthaUmide Yellow Yellow 40 r
Saccharin Red Yellow 50T
SO,
TABUB 27. PTHBOLE DEBIVATIVES
Ultraviolet Limit of
Name Formula Color fluores- identifi-
cence cation
Pyrrole HC CH (Charred) Blue 40-)'

II II
HC CH
^ \ /
NH
Indole
/N -CH
Brown-ried Blue 127
U NB[ ^
rCH
Carbazole '^, / \ Yellow-green Blue 30 7
( X) NH
u
Acetindoxyl / \ c(\ Brown-red Blue 2O7
NH
379
of pyridine in ultraviolet light to the ammonium salt of glutaconic alde-

hyde enol, as shown in (1). This gTves condensatfon products, of the type
of Schiff's base (2),"* with primary aromatic amines:
CH CH 1
^ \ /" \
HC CH + 2H,0 ^; HC CH
1 II 1 II (1)
HC CH IJC . CH
-- \ / ^ \
N 0 ONH
CH CH
/ \ ^ \
HC CH HC CH
1
=CH
11CH + 2ArNH, HX
1
-* ArN=CH
11CHNHArHX (2)
\ '
OH
Primary aromatic amines can therefore be identified by the colored
Schiff's bases formed with glutaconic aldehyde.
Free glutaconic aldehyde is very unstable, as it polymerizes readily,
and even its ammonium salt (formed by ultraviolet light on paper im-
pregnated with pyridine) decomposes in a few days. It is therefore best
to carry out the test with the aid of compounds that readily break up to
glutaconic aldehyde. Among such materials are sodium glutaconic alde-
hyde enolate (I) and 4-pyridylpyridinium dichloride (II):"
NaOCH=CHCH=CHCHO
(C ' (II)
Compound II breaks up with alkali to give the alkaliênolate. of
glutaconic aldehyde and 4-aminopyridine, and liberates the reagent thus:
A
CH NH, ,
\ /
NCI
1 + 3NaOH - ^ 1HC
/ \
CH
11 -f-
A ^ + 2NaCl + HjO
0=CH CHONa
/
N
N-HCl
F. Feigl and V. Anger, / . prakt. Chem. [2], 13, 180 (1934).
E. Koenigs and H. feeiner, Ber., M, 1049 (1931)/
AMINES 381
IfProcednreA drop of the test solution and a drop of the reagent

are placed in a microcrucible, made alkaline with 2 drops of sodium hy-
droxide, and at once 3 drops hydrochloric acid are added. In the presence
of a primary aromatic amine, a deep red to violet color or precipitate is
formed."
An alternative procedure is to impregnate spot paper with an alcoholic
solution of sodium glutaconic aldehyde enolate (prepared by adding so-
dium hydroxide to an alcohol-water solution of 4-pyridylpyridinium
dichloride). The warm test solution slightly acidified with mineral acid
is spotted on the dry paper. The pale brown paper is stained red, violet,
or dark brown. In the absence of amines, a white fleck is formed on the
paper, owing to the destruction of the sodium glutaconic aldehyde enolate.
Reagents: 1)1% solution of 4-pyridylpyridinium dichloride*'
S) 2 N hydrochloric acid
The limits of ideniification for a number of amines are given in
Table 28.
5. Test for primary aromatic amines with sodium pentacyanoaquoferriate.^'
A green or blue color results on mixing primary aromatic amines with a
sodium carbonate solution of sodium pentacyanoaquoferriate Naj-
[Fe(CN))HsO]. This color reaction also succeeds with solutions of so-
dium nitroprusside, that have been left for a long time in the light, or
treated with ultraviolet light for 15 minutes. Under these conditions the
following changes occur:
NajFe(CN)5N0 + HÔ - Na2Fe(CN8)H80 +N0 (1)
The aquoferriate formed according to (1) reacts with the primary aromatic
amines, with the liberation of one molecule of water. For instance.
Na,Fe(CN)sH20 + CHjNHj -* Na,Fe(CN)6(C,HtNH3 -|- HjO (2)
The resultant compounds (2) are green or blue.
^ProcedureA drop of the test solution is mixed with a drop of the
reagent solution either on a spot plate or in a microcrucible. If neces-
sary, a little dilute sodium carbonate solution is added. A more or less
intense green or blue color appears at once or after a few minutes.
Reagent: Sodiiun pentacyanoaquoferriate solution. A 1% solution
of sodiiim pentacyanoaquofeiToate (see page 323) is treated
with bromine water until the color is violet, and then suffi-
cient sodium nitroprusside is added to change the color to
' 4-Aminopyridine does not behave like an aromatic amine; therefore no
colored Schiff's base is formed when it breaks up.
' Fpr preparation, see E. Koenigs and H. Greiner, loc. cit,
V. Anger, Mikrochim. AOa, i, 3 (1937).

TABUS 28. FBIUABT ABOUATIC AMimss
test with
1
GlttUcosie aldehyde NMFt(CN)iH
FomnU
Umit of 1 Limit of
ideatifi- Color \ identifi- Color
cation OttlOB
Aniline
O-^' 0.1 y Red-
brown
0.6 7 Green
o-Nitraniline CH4(N0,)NH, l7 Rose-red Does not react
m-Nitraniline dH(NOi)NH, \y Bluish COT Green

red
p-Nitraniline C,H4(NO,)NH, 0.3 7 Rose-red 10 7 Green
m-Brom- 1-y Red 67 Green

Br-<^ \NH,
aniliae
p-Phenyl- 0.1 7- Violet 0.1 7 Blue

NHi<(^ \NH,
enedismine
p-Amino-
diphenyl 00-. IT Red IT Green
Benzidine 0.1 Y Red- IT Blue-

'"-<I>-0-- brown green
a-Naphthyl- 0.05 T Scarlet 27 Blue-

amine green
CIOHTNH,
/J-Naphthyl- 0.1 y Red 2T Green
amine
1,8-Naph- C,JI,(NH,), IT Red- 10 T Brown--

thylamine brown green
K-Acid Cfl4(0H)(NH,)(S0,H), 2T Orange 20T Brown
a-Amino- Does not react 10 T Green

pyridine
NH,
N
Amino- N ^N Does not react 100 V ' Violet-

tetrazole pink
11 1
N CNH,
\ /
NH
p
AMINES 383
yellow. 2% sodium carbonate solution is added. In-

stead, a solution of sodium nitroprusside in 1% sodium
carbonate which has been aged by keeping, or by 15 min-
utes irradiation in ultraviolet light"" may be used
The limits of identification for a number of amines are given in Table 28.
6. Other tests for primary aromatic amines. The fact that the hydrogen
atoms of the NHj group are readily replaceable forms the basis of the
following tests."* They may be carried out as spot reactions (in micro-
crucibles with heating):
1. Condensation with aromatic nitroso compounds with the formation
of azo dyes. Reagent: saturated solution of 5-nitroso-8-4iydroxyquinoline
or nitrosodimethylaniline in glacial acetic acid (7d". Limit: 1-100 y).
B. Condensation with furfural (or p-dimethylaminobenzaldehyde).
to Schiff's bases, which are violet or orange colored."' Reagent: solution of
10 drops furfural in 10 ml. glacial acetic acid or a saturated solution of
p-dimethylaminobenzaldehyde in glacial acetic acid {Id". Limit: 0.1-
200 7). Secondary aromatic amines, and also aliphatic amines and amino
acids react in the same way. Proteins react with p-dimethylamino-
benzaldehyde.
3. Condensation with chloranil to form compounds that are blue,
red, or brown. Reagent: saturated solution of chloranil in dioxane {Id'^.
Limit: 0.2-200 7). Secondary amines react similarly; amino acids do not
react. Phenols give red to violet colorations
4. Primary amines react with carbon disulfide forming sjToametrical
dialkylated thioureas and liberate hydrogen sulfide.^"* The latter can be
detected with lead" acetate paper in a suitable apparatus (Id". Limit:
1 to 6 7 amine).
6. The following procedure has been recommended."* One drop of
the ether or acetone solution of the sample is placed on filter paper. The
solvent is allowed to evaporate. The paper is then exposed, in turn, for
5 minutes each, to the vapors of cone, hydrochloric acid, and ethyl nitrite
(from alcohol, HCl, crystallized NaNOj). Then the paper is spotted with
an ether solution of resorcinol, held over ammonia, and finally steamed.
An orange, red, or violet color indicates the presence of diazotizable NH
groups.
! This is advisable when hydrazine or nitroso compounds are present, as
these react with excess of pnissic salts (see page 321).
"1 0 . Frehden and L. Goldschmidt, Mikrochim. Acta, 1, 338 (1937).
i< See also S. N. Chakravarti and M. B. Roy, Analyst, 62, 603 (1937).
>0. Frehden and K. FOrst, Mikrochim. Acta, 3, 197 (1938).
S. J. Bumistrov, Ckem. Abstracts, 34, 2287 (1940).
d-AMINO ACIDS (CH(NHs)COOH GROUP)

Test by conversion to aldehyde.*"* Amino acids are converted into the
next lower aldehyde by the action of alkali hypochlorites. For example,
glycocoU is converted to formaldehyde: |
H2NCH2COOH + NaOCl - HiCO + NH, + CO, + NaCl
The aldehyde may then be identified with fuchsin-sulfurous acid (see page
339) if a great excess of reagent is used, as this decomposes any imused
hypochlorite. Fuchsin-sulfurous acid itself gives no red color with hy-
pochlorite, but only a pale yellow decomposition product.
^ProcedureA httle of the test substance is treated with a few drops
of hypochlorite solution in a microcrucible and warmed gently. When
the reaction is complete, excess of fuchsin-sulfurous acid is added drop
by drop. A red color appears if amino acids are present.
Reagents: 1) Sodium hypochlorite (saturated solution)
2) Fuchsin-sulfurous acid (see page 339)
The following were detected by applying this test:
60 T glycocoll, CH,-NH-00011
100 y alanine, CH,-CH(NH,)COOH
CH(NH,)-COOH
100 y J-asparagine, I
CHtCONH,
CHiCOOH
100 y {asparaginic acid, 1
CH(NH,)-COOH ,
100 y tyrosine, CH,-OH(NH,).C/)OH
60 T di-iodotyroaine, HO<^ ^CH,-CH(NH,)-COOH
I , .
NH,
/
60 y d-arginine, C=NH
\
NH.(CH,),CH(UH,)COOH
" O. Frehden and L. Goldflchniidt, Mikroehim. Ada, 2, 186 (1937).
HTDRAZmES 385
HYDRAZINES
(o) Aliphatic and Aromatic Hydraanes (^N^NHj Group)
1. Test with sodium pentacyanoammineferroate.'"* Hydrazine reacts
similarly to nitroso compounds (see page 321) with sodiimi pentacyano-
ammineferroate, Na3Fe(CN)5NH8. Deeply colored soluble compounds
result, probably by the replacement of the NHa molecule in the prussiate
by a molecule of the hydrazine.
llProcedureSeveral drops of a solution of sodium pentacyanoam-
mine ferroate are added to a neutral, aqueous or alkaline solution of tht; test
substance, and left to stand for a little while. A deep red to violet color
, forms. A few substances turn yellow on making the solution alkaline.
.ReagerUs: 1) 1% solution of sodiimi pentacyanoammineferroate.
(For preparation see page 322.)
S) 2 N sodium hydroxide
The limits of identification attained for different hydrazines are given
in Table 29.
2. Test by the formation of hydrazones with azo dyestuffs.*"' Certain
water-soluble azo dyes, formed by coupling diazotized p-aminobenzalde-
hyde with naphthol or aminonaphthol sulfonic acids,*"* by virtue of their
free aldehyde group, can be condensed to hydrazones with acyl- and aryl-
hydrazines. The color is thus deepened or changed. For example, the
dye (I) formed by coupling p-aminobenzaldehyde and croceine acid (2-hy-
droxynaphthaIene-8-sulfonic acid) is yellow in aqueous solution and this
solution turns violet after adding acyl- or arylhydrazines due to the forma-
tion of the hydrazone (II). The following change takes place:
HO,S N - < 3 - CHO + H,NNH-<I>
OH
HO,S CH=.NNH
KI> + H,0
F. Feigl, V. Anger, and O. Frehden, Mikrochemie, 16,184 (1934).

>"F. Feigl, V. Anger, and R. Zappert, Mikrochmiie, 16, 190 (1934).
P. FriedlSnder, ForUchritte der Teetfarbenfabrikation, Vol. IV (1899), p. 706.
386 VI. OSQANIC SPOT TESTS
IfProcedureA drop of-a solution of the dyestuff in| dilute acetic acid
is mixed with a drop of 10% sodium acetate solution juid a drop of the
aqueous or alcoholic test solution is added. When large amounts of a hy-
drazine are present, the color change is almost instantaneous; smaller
amounts cause the change within 15 minutes. A blank test is advisable.
TABLE 29. HTSBAZINES
Lnait
Name FORDUb
of iden. Color CUar
tifica- (neutral) (aUutUiw)
tionUT
Phenylhy- CHcNHNH, 0.5 Red Red

drazine
Methylphcnyl- (C,H,)(CH,)N.NH, 3 Blood red Dark blood

hydrazine red
Diphenylhy- (C.H.),N-NH, 7 Violet Brick-red

drazine
o-Nitrophenyl- 1 Dark Light

hydrazine brown- yellow
red
w-Nitrophenyl- C^4(N0,)NHNH, 0.4 Cherry-red Brown-

hydrazine yellow
p-Nitrophenyl- 0.6 Blue-violet Brown-

hydrazine yellow
8-Hydroxy- C,B4(0H) (SO,H),NH -NH, 3 Dark Light red-

naphthylhy- violet yellow
drazine-^,6-
disulfonic acid
Semicarbazide NH.CONHNH. 0.3 Cherry-red Dark^

yellow
aaym. Diethyl- (CJI.)^-NH, 0.6 Dark Golden

hydrazine cherry
Benzoylhy- C,H,CONHNH, 0.12 Deep Straw

drazide violet yellow
Preparaiion of the reagent: p-Aminobenzaldehyde hydrochloride is

suspended in dilute hydrochloric acid and diazotized jadth this calculated
amount of sodimn nitrite (a mole NaNOj to 1 mole amine). The diazonium
solution is poured into the equivalent amount of croceine acid dissolved
in excess sodiimi carbonate, and the mixture finally acidified with acetic
acid. The solution of^he dyestufE will keep. ^
HTDBAZINBS 387
The various limits of identification for different hydrazines attained

with this reagent are given in Table 30.
(6) Arylhydradnes (ArNHNHj Groups)
Test with selenioos acid and a-naphthylamine."" Arylhydrazines are
oxidized by selenious acid to diazonium salts, which can be coupled with
aromatic amines, (a-naphthylamine is the most suitable) to form bright
red to red-violet azo dyestuffs."" Small amoimts of arylhydrazines (and
also arylhydrazones and osazones) may be detected by applying this reac-,
' TABLE 30. HTDBAZINES
Limit of
< Nuoe Foimula identifi- Color duuge
catioa
iny
Phenylhydrazine CH..NHNH, 1 Yellow-violet
^^ym. Methylphenylhy- C,H,.N(CH,)-NH, 2 Yellow-

drazine brown-red
asym. Diphenylhydrazine (C.H-,),NNH, 1 Yellow-red-

brown
o-Nitrophenylhydrazine 1 Yellow-
brown-red
C,H4(N0,).NH.NH,
m-Nitrophenylhydrazine 1 Yellow-violet
Semicarbazide H,N.CO.NH-NH, 1 Yellow-

brown-red
Benzoyl hydrazide C,H,CO-NH-NH, Yellow-orange

'
tion. The following equations show the reactions in the test for phenyl-
hydrazine; the other arylhydrazines react similarly:
/ \ N H N H , . H C l -f- SeO, N,CI -f Se + 2 H , 0 (1)
-N,CI NH,
-N - N- NH.-HCl (2)
"F. Feigl and V. Demant, Mikrochim. Acta, 1, 134 (1937).

"J. J. Postowsky and co-workers, Ber., 69, 1913 (1936).
IfProcedureA drop of the test solution is mixed with a drop of dilute

hydrochloric acid, either in a microcrucible or on a spotplate, and a small
amount of selenious acid is added. When large amounts of afylhydrazine
TABLE 31. HTDBAZINBS, HTDRAZONES, OSAZONES
Limit o{
Name \ Formula Color identifi-
cation
in-ir
Phenylhydrazine CJIiNH-NHj Red-violet 0.04
m- and p-Nitro- Cff.CNO,)NH-NH, Red-violet 0.06

phenylhydrazine
p-Bromophenylhy- C,HBiNH-NH, Violet 0.08

drazine
Tribromophenylhy - CHjBr.NH-NH, Red 1 hot

drazine 10 cold
Naphthylhydrazine C,oHr-NH-NH,, Violet 0.03
Levulinic acid HOOC(CH,)r-C (GH,)=N N H C H , Red-violet 0.1

phenylhydrazone
Propionaldehyde HC, CHj C H = N NHCOli Red-violet 0.09

phenylhydrazone
Glucuronic acid HOOC(CHOH)r-CH=N -NHCHj Red-violet 0.7

phenylhydrazone
CinnamoyI formic C , H r - C H = C H C = N -NHCJI.' Red-violet 2

acid phenylhy- 1
drazone COOH
o-Pyridylbenzoyl- C^4NC (C,H,)==NJ^HCai. Red-violet"^ .0.1

phenylbydrazone
Glucosazone OH HC=N-NHCH, Red-violet 0.4

1 1
HjC(CHOH).C=4^.NHC,H, 1
Dihydroxy-tartaric HOOCC==N - N H C H , Red-violet 0.7

acid osazone 1
HOOCC==N-NHC,H,
/
are involved, the mixture is allowed to stand 1 or 2 mmutes to permit the

red selenium to separate. A drop of an acetic acid solution of a-napthyl-
amine is added and a few crystals of sodium acetate. When primary aryl-
hydrazines are presentnred to violet dyes are fprmed. Tlie color can be
intensified by the addition of a drop of hydrochloric acid.
BEACnVE CHt AND NH:i GROUPS 389
Reagents: 1) Dilute hydrochloric acid

2) Selenioxis acid (soHd)
S) Sodium acetate
4) a-Naphthylamine solution: 0.3 g. a-naphthylamine is dis-
solved by boiling in 70 ml. water and 30 ml. glacial acetic
acid. After cooling, the solution is filtered from any
dark residue. The solution should be kept in the dark
The limits of identification for some of the arylhydrazines are given
in Table 31.
Test for arylhydrazones and osazones. The test for arylhydrazines,
just described, by oxidation with selenious acid to the diazonium salt and
coup^ng with a-naphthylamine, can also be applied to the detection of
arylhydrazones and osazones. These compounds are saponified by boiling
with cone, hydrochloric acid and spht off the arylhydrazine hydrochloride,
which is stable against boiling. The test is then carried out as described
for free arylhydrazines.
^[ProcedureA drop of the test solution, or, better, a crystal of the
solid, is evaporated nearly to dryness in a microcrucible with a few drops
of cone, hydrochloric acid. A small grain of selenious acid is added and
the mixture left to stand for 1 or 2 minutes. Then a drop of the a-naphthyl-
amine solution and^ few crystals sodium acetate are added. When the
color of the dye appears, it may be intensified by means of a few drops os
hydrochloric acid. A red to violet azo dye indicates that aryl-hydrazone
or osazones are present.
The limits of identifi4xUion for some hydrazones and osazones are
pvenjn Table 31.
REACTIVE CHj AND NH, GROUPS
Test with sodium l,2-iiaphtliaqiiiiione-4-siiIfoiiate."' 1,2-naphtliaqui.
none-4-sulfonic acid reacts in an alkaline solution with compoimds which
contain two removable hydrogen atoms attached to one carbon or nitrogen
atom, to form deeply colored paraquinonoid condensation products. If
aniline is taken as an example, the reaction can be represented:
O
OiNa + B,ff<f \ + 2NaOH
ONa
^ = N < ^ ~ \ + Na,SO, + 2H,0
" P. EhrUoh and C. A. Herter, Z^phyiiol. Chem., a, 329 (1904).

TABLE 32. REACTIVE CHJ AND N H J GBOUES
. 1 Limit
of iden-
tifica-
tion, 1 In alkaline
solution
Color
1
In acetic acid
oltttion
Mslonic CH,(CO,CH.), 1.2 Dark Yellow pre-

ester violet cipitate
Rhodanine HN CO 0.6 Dark blue- Red-yellow

1 1 violet precip-
SC CH, itate
s
Ethyl ace- CH.COCHrCOOCH, 1.2 Blood red- Yellow pre- Reaction
toacetate violet cipitate very slow;
enolic
form
Thiocyano- (CNS)CH,COOH 0.6 Red-brown Orange

acetic
acid
Dibenjoyl- C,H.COCH,COC,H, 12 Red-violet White-yel- Allow to

methane low pre- stand
cipitate some
time
m-Nitroan- C,H4(N0.)NH. 6 Yellow- Red pre- Allow to

iline brown cipitate stand
Benzyl- CH,CH,-NH, 0.6 Green Brownish

amine red
Semicar- H,N-CO-NH-NH, 0.6 Orange-red Light

4 yellow
bazide
Aniline C,H,NH, 0.12 Brick red Bright

orange-
' red
P-Naphtha- 1.2 Dark Yeliow-
0
/
quinoline violet brown
iodometh- precipi-
ylate
1 /CH, tate
/
BEACnVE CHi AND IIBt QBOTTPS 391
TABLB 32. Continued
Limit Color
ofiden-
Nime tificft- In allcaline In acetic acid Ronarks
tion.Y solution solution
iS-Naph- C,^,NH, 0.6 Yellow-red Red pre-

thylamine to red- cipitate
brown
Indole ^ 0.6 Emerald Violet at

green first,
then col-
CH -'
orless to
N gray
CH
CD HB
CH
Fiperidine CjHiJSrH 0.6 Scarlet Light red Reaction

precipi- without
tate addition
of alkali
Pyrrole HCCH HC=CH 0.6 Deep Dark olive Very in-

II II I I violet green tense
HC ce;HC CH, color
NH N
The test may only be applied for orientation purposes, as the reac-
tivity of the CHj and NHj groups is influenced by the other groups in the
molecule. For example, aniline derivatives with strongly negative groups,
e.g., trinitroaniline and tribromoaniline, will not condense in this way, in
contrast to aniline. Negative groups in the ortho and para position partic-
ularly cause much interference with the reaction; negative groups in the
meta position are less harmful.
IfProcedure"'A little of the solid or a drop of a solution is placed
in a microcrucible along with 2 drops naphthaquinone sulfonic acid solution,
and made alkaline with 2 drops sodium hydroxide. An intense color
appears. On acidifying with acetic acid, the color changes; sometimes a
precipitate forms.
Reagents: 1) Saturated solution of sodium l,2-naphthaquinone-4-
sulfonate in 50% alcohol
"> F. Feigl and O. Frehden, Mihrochemie, 16, 79 (1934).
S) 0.5 N sodium hydroxide i

S) 2 N acetic acid
The limits of identification attained with various compounds are given
in Table 32. '
TERTIARY RING BASES
Test with methyl iodide and sodium l,2-naphthaquinone-4-suIfonate."^
As stated on page 389, organic compounds which contain two replaceable
H atoms bound to one C or N atom, react with naphthaquinone sulfonic
acid, in alkaline solution to form colored quinoid compounds. The CH3
or CiHs groups, which in CHsI or CjHjI do not react with naphthaquinone
sulfonic acid, may be activated by attaching the alkyl iodide to a tertiary
N base or oxonium compound. The resulting quaternary compound reacts
at once with naphthaquinone sulfonic fl.cid to give colored (red, red-violet
or green) compounds. As the color reaction is very definite, the formation
of the quaternary compound and the reaction with naphthaquinone sulfonic
acid can be applied as a test for cyclic, tertiary ring bases, and for oxonium
compounds. It is, of course, essential that CH2 and NHj groups should
not be present, as they react with the naphthaquinone sulfonic acid (see
page 389).
The underlying reactions of the test can be expressed:"*
CH,
<^ ^ N + CH,I * <(^ ' JN (1)

\
I
CH, \
\
-so^^ + \N/K-
I (2)
Similar equations can be written for other alkylation agents, such as

dimethyl sulfate, ethyl bromide, ethyl iodide, and p-bronfotoluene sul-
" F. Feigl and O. Frehden, Mikrochemie, 16, 84 (1934)^.
"< The course of the reaction shown in (1) and (2) is very probable, but has not
yet been verified experimentally. The assumptions rest on the results of F. Krohnke's
work on the condensation of iodomethylatea of organic tertiary bases with alde-
hydes: Ber., 66, 604,13^ (1933).
^ TERTIABT ItmO BASES 393
fonic acid methyl ester. The formation of the quaternary compound

proceeds best with methyl iodide or dimethyl sulfate.
^[ProcedureA little of the test substance (either the solid or a drop
of solution) is mixed in a tall microcrucible with 5 or 6 drops of methyl
iodide or dimethyl sulfate, and heated to gentle boiling on an asbestos
plate. Substances hard to convert to quaternary compounds should be
heated for some hours with methyl iodide in a closed capillary tube in a
water bath at 100 C. The quaternary compound is treated with 2 or 3
drops of a saturated solution pt sodium naphthaquinone sulfonate, and
the mixture made alkaline with sodium hydroxide. The appearance of
color or change of color indicates that the test is positive. On acidifying
with acetic acid there is a change of color, as in the Ehrlich-Herter reaction
(see footnote 111, page 389).
Reagents: 1) ^Methyl iodide or dimethyl sulfate
2) A saturated aqueous solution of sodium, 1,2-naphtha-
quinone-4-sulfonate
S) 0.5 N sodiiun hydroxide
4) I N acetic acid
The limUs of identification attainable by this method are given in
Table 33.
C. IDENTIFICATION OF SPECIFIC ORGANIC COMPOUNDS

Comparatively few cases are known in which it is possible to make a
specific test for particular organic compounds through characteristic reac-
tions. Tlje principal reason is that the majority of all organic compounds
with typical groups of atoms also have homologous compounds. These
homologs are derived from a simply-constructed parent form by a more or
less extensive elaboration with analytically indifferent groups. For
instance, the aldehydes R CHO contain the typical group, CHO, while R
can represent an aliphatic or an aromatic radical. By virtue of the alde-
hyde group, all these compoimds are more or less active reducing agents and
are also characterized by the mobility of the 0 atom. These properties
are most pronounced in the parent compound, formaldehyde, HCHO.
This aldehyde occupies a unique position and accordingly specific -tests are
available for it. Aliphatic and aromatic aldehydes, in which the H atom
of formaldehyde has been replaced by aliphatic or aromatic radicals r^pec-
tively, exhibit differences that can be detected by analytical procedures.
This difference is due to the varied effect of the aliphatic or aromatic radical
on the chemical behavior of the CHO group. The individual members of
the great classes of aliphatic or aromatic aldehydes seldom show differences
that can be utilized analytically. A search for specific reactions under such
conditions is not promising. The same holds true for many other organic
compounds containing typical groups of atoms. As a rule, special reac-
394 VI. OKGANIC SPOT TESTS
tions are available only for the most simply constructed parent forms, bitt
not for the vast number of their homologs. Consequently, only such com-
TABLB 33. TEBTIAKT RING BABES
Color Limit
Name and fonnuU Metbylatint of iden-
agent tifica-
With NaOH With CHiCOOH tion
Pyridine CH,I Red to red- Orange- 12 Y

(CH,),SO. violet yellow
C,H,Br
a-Picoline CH.I Dark blue- Light yellow 12 T

C,H4NCH, (CH.),S04 violet
CHjBr
Quinoline CH,I Dark brown- Pink 25 7

C,H,N (CH,),S04 green to
CiHtBr black-
green
Quinsldine CH,I Dark blue- Pale greenish 12 T

CtHiNCH, (CH,),S04 violet to yellow
blue-green
2,6-Dihydroxypyridine-4-car- CH,I Black-green Pink stria- 25 T

boxylic acid tions then
CJl2N(OH),COOH^(2, 6, 4) green pre-
cipitate
Dimethylpyrone CH,I Brown-vio- Red color 25 Y

C,H,0,(CH,), (2, 6) (CH,)!SO let, after then dark
CHjBr short red pre-
standing cipitate
4 green-black
Chelidonic acid CH,I Dark olive Peach-red 25 Y

CiH,0,(OH),COOH (2, 6, 4) green to
green-black
Cinchonine CH,I Cherry-red Yellow 100 Y

CMHJSON, heated for
some hours
in a sealed
tube
pounds as have no homologs, or whose homologs react very sluggishly,

offer a possibility for specific tests. A decisive test by a special teactioa
for the original material is only possible whe^ these complicated organic
396 VI. OBQAinc SPOT TK8TS'
^ProcedureOne drop of the test solution, in a microcrucible, is

allowed to stand for several minutes, at room temperature, with 2 drops
20% sodium hydroxide and 1 drop cone, ammonia. A! particle of clay plate
is then added, and the mixture heated to boiling. After cooling, it is acidi-
fied with 20% sulfuric acid. The crucible is covered with a small watch
glass carrying a strip of moist reagent paper. The prusdc acid is expelled
by cautious heating. A blue cdor indicates the presence of chloroform.
TTie formation and liberation of the prussic acid can also be accomplished
in the apparatus described on page 31.
Limit of Identification: 16 y chloroform
Reagent: C!opper aceitate-diaminofluorene solution: 0.3% copper
acetate solution is mixed with an equal volume of saturated
solution of 2,7-diaminofluorene in 50% alcohol
METHYL ALCOHOL
Test by convemon to fonnalddJiyde."' Methyl alcohol may be oxidised
to formaldehyde by permanganate in dilute phosphoric acid solution.
The formaldehyde can then be detected by the selective chromotropic acid
reaction (see page 396). If the experimental conditions prescribed here
are maintain!, ethyl alcohol is oxidized only to acetaJdehyde (without
formation of detectable quantities of formaldehyde). The test may conse-.
quently be used for the detection of traces of methyl alcohol in the presence
of ethyl alcohol. For example, 5.3 y methyl alcohol may be detected
in a drop of 40% ethyl alcohol, which ccnresponds to a proportion limit of
1:1150. U n d ^ t h e conditions of the test, glycetol, arabinose, fructose,
lactose, and sucrose give yellow colors and furfural a brown color.
^[PlrocediireA drop of the test solution is mixed with a drop of dilute
phosphoric acid solution and a drop of potassium permanganate solution
in a test tube and left for i minute. A little solid sodium bisulfite is
added, with shaking, until the mixture is decolorized!" If-any brown
precipitate of the high^ oxides of manganese remans undissolved, a
further drop of phosphoric acid should be added and a very little sodium
bisulfite. When the solution is colorless, 4 ml. sulfuric acid and a little
finely powdered chromotropic acid are added; the, mixture is well shaken,
and then heated to 60" C. for 10 minutes. A violet color, tluit deepens
on cooling, indicates the presence of methyl alcohol.
Limit of Identification: 3.5 7 methyl alcohol
Concentration Limit: 1:13,600 /
Reagents: 1) Dilute phosphoric acid (10 ml.-^ per cent acid diluted
to 100 ml.
"' E. Eegriwe, Mikrochim. Acta, 2, 329 (1937).
Acsnc Acn> 397
8) 5% potassium pennanganate solution

3) Soditun bisulfite (solid)
4) 72% sulfuric acid (see page 395)
5) Chromotropic acid (solid)
FORMIC ACID
Test by oonrersioii to fonnaldehyde.*^* Formic acid is readily reduced
to formaldehyde by magnesiiun and hydrochl(ic acid. The formaldehyde
may then be identified by the chromotropic acid test (see page 395). Glu-
cose interferes with th^test owing to partial breakdown to formic acid;
no other sugars or acids interfere.
^[ProcedareA drop of the sample solution is mixed in a test tube
with a drop of dilute hydrochloric acid; magnesium powder is then added
imtil no further gas is liberated. Three ml. sulfuric acid and a little
chromotropic acid are then added; the tube is heated for 10 minutes at
60 C. A violet-pink appears if formic acid is present.
Limit of Identification: I Ay formic acid
Reagents: 1) 2 N hydrochloric acid
2) Magnesium powder
3) 72% sulfuric acid (see page 395)
ACETIC ACID
1. Test inSa. lanthannm nitrate and iodme."* When lanthanum salts
are mixed with iodine and ammonia in the presence of acetic acid or alkali
acetates, under suitable conditions, a dark blue precipitate or solution
results."' The effect probably is due to the adsorption of iodine on basic
lanthanum acetate; however, this occurs only on a suitable variety of tliis
substrate.
Nitrates, chlorides, bromides, and iodides do not interfere with the
detection of small amounts of acetate, even when present in 30 to 40 times
excess, but they weaken the intensity of the blue color. Sulfates, how-
ever, interfere in relatively small amounts, and similarly all anions that
form insoluble salts with lanthanum {e.g., phosphates), and all cations
that give precipitates with ammtHiia. Sulfates and phosphates may be
removed by precipitaticHi with barium nitrate and the test carried out on
the filtrate
Propionates react similarly to acetates.
^ ProeednreA drop of the test solution is mixed on a spot plate with
" E. Eegriwe, Z. antU. Chem., 110, 22 (1937).
I " D. Krflger and E. Tsehirek, Ber., 6S, 2776 (1929); S, 836 (1930).
> A. Dwnour, Comjtt. rend., iS, 976 (1867).
a drop of a solution of lanthanum nitrate and a drop of ibdine solution. A

drop of ammonia is added, and in a few minutes (in the presence of ace-
tates) a blue to blue-brown ring develops around the drop of ammonia."*
Limit of Identification: 50 7 acetic acid ,
Reagents: 1) 5% lanthammi nitrate solution
2) 0.01 N iodine solution in water
S) I N ammonia
2. Test by formation of indigo.'^ Acetone is formed by the dry distilla-
tion of calciimi acetate:
When acetone, in alkaline solution, is allowed to react with o-nitroben-

zaldehyde, indigo (see page 351) is formed, with intermediate production
of o-nitrophenyl lactic acid ketone. Starting with small amounts of cal-
civun acetate, indigo can be formed by the action of acetone vapor on
reagent paper impregnated with nitrobenzaldehyde. In this way, acetic
acid can be decisively detected in the presence of all the mineral acids.
Acetone vapor obtained by âporation of solutions only reacts slowly
and incompletely. The rapid formation of indigo in this test is due to the
fact that the acetone vapor formed in the distillation of calcium acetate
reaches the nitrobenzaldehyde at a higher temperature.
Propionic acid and other fatty acids cannot be detected by the indigo
reaction, for when their calcium salts are subjected to dry distillation,
higher ketones twithout the CH3CO group) are formed, but no acetone.
In the presence of other fatty acids, this test is less sensitive, because the
acetone is mixed with higher ketones as well as mixed ketones that are the
chief products in the distillatiof of the calcium, salts.
It must be noted that the acetic acid test is unsuccessful in the
presence of large amounts of copper salts. Chromates and manganese
dioxide are, however, without effect.
^ ProcedureThe solid sample is mixed with calcium carbonate, or
a drop of the acid solution is evaporated to dryness with calcium car-
bonate. The residue is transferred to the hard glass tube (Fig.>32) de-
scribed on page 31. The conversion into calcium acetate may also be
carried out in the ignition tube. The open end of the tube is covered
with a strip of filter paper moistened with a freshly prepared alkaline solu-
tion of o-nitrobenzaldehyde. The glass cap is put in place. The strip
of filter paper may alternatively be kept in position by running through it
"D. Krfiger and E. Tschirch, Mikroehemie, 8, 218 (1930).
"* F. Feigl, J. V. Sanchez, and R. Zappert, Mikroehemie, 17, 165 (1935).
GLTCOLIC ACTD 399
a thin thread of glass thickened to a knob at one end, which rests on the
paper and keeps it weighted down. The tube is then hung through the
asbestos plate and gradually heated. The acetone vaporizes and colors
the yellow paper blue or blue-green, according to the amount evolved.
When very small amounts of acetate are involved, it is advisable to remove
the glass cap together with the filter paper after the distillation, and to
spot the paper with a drop of hydrochloric acid. The original yellow
color of the paper is discharged by the acid so that the blue of the indigo
shows up more clearly against the white paper.
Limit of Idenlificaiion: 60 y acetic acid
Reagents: 1) Calcium carbonate (soM)
S) Saturated solution of o-nitrobenzaldehyde in 2 A^ so-
dium hydroxide
3) Dilute hydrochloric acid
3. Other tests for acetic acid. 1. The acetaldehyde formed by the dry
distillation of a mixture of acetate with Ca(0H)2 and calcimn formate may
be identified by the reaction with 5% sodium nitroprusside and 20%
piperidine (see page 408).*'* The procedure for this test is the same as
for test 2 above (7d". Limit: 10 to 15 7 acetic acid).
2. A drop of acetate solution that is exactly neutralized, may be
identified by the formation of the red-brown complex iron (III) acetate
with FeCU "* {Id". Limit: 10 7 acetic acid). It is best to neutralize acid
solutions by heating with CaCOj; and alkaline solutions by heating with
excess Zn(N03)2 and then filtering.
GLYCOLIC ACID
Test with 2,7-dihydroxynaphthalene and sulfuric acid.'^'^ On heating
glycolic acid (I) with a solution of 2,7-dihydroxynaphthalene (II) in cone,
sulfuric acid, a violet to violet-red color gradually appears. This color
reaction probably depends on the .condensation of the formaldehyde (spUt
HO-
CH,(OH)COOH
(I)
(II)
off from the glycolic acid) with dihydroxjmaphthalene, to form tfitrahy-

droxydinaphthybnethane. This colorless product gradually oxidizes in
the air to a deep red dyestuff.
"J. V. Sanchez, Chem. Abstracts, 30, 4432 (1936).
"* F. Feigl and R. Seboth, unpublished studies.
"E. Eegriwe, Z. anal. Chem., 89, 123 (1932).
400 VI. OBQANIC SPOT TiSSTS
Neither fonnic acid, acetic acid, oxalic acid, succinic acid, citric acid,
h&xzoic acid, nor salicylic acid interferes with the test. Both lactic acid**
and malic acid give a yellow color and greenfluorescencejwith the reagent,
while tartaric acid gives an olive to dark green color. Aldehydes such as
salicylaldehyde, anisaldehyde, or acetaldehyde react with 2,7-dihydroxy-
naphthalene similarly to formaldehyde, with formation of oxidizable con-
densation products.
IfProcedureA drop of the teat solution is mixed with 2 ml. of the
reagent solution and heated for 10 to J 5 minutes in a water bath. A red
to violet-red appears, according to the amount of glycolic acid present.
Ldmit of Identification: 0.2 y glycolic acid
Reagent: Solution of 0.01 g. 2,7-dihydroxynaphthalene in 100 ml.
cone, sulfxmc acid
A freshly prepared reagent sduti(i is yellow, with a green fluores-
cence, but both color andfluorescencedisappear on heating for a short time,
or after standing overnight in a stoppered bottle. The reagent is gradually
colored violet by the action of a number of" oxidizing ag^ts (peisulfates,
hydrogen peroxide, chlorates, and chroinates). On standing foi" a.number
of hours exposed to the air, a sKght red to violet-red forma. The reagent
remains colorless while being heated for ^ hour, but in the presence of the
slightest trace of formaldehyde liberated from glycolic acid, the charac-
teristic color develops at once.
This test is also applicable in the presence of citric acid. The glycolic
acid can be identified by the appearance of an orange to orange-red colora-
tion and a green fluorescence. In this way 1 y glycolic acid may be identi-
fied in the presence of 20,000 times the amoimt of citric acid.
LACTIC ACID
4
1. Test with p-hydrozydiidienyl and snlftiric acid (edm- test).Î,^Lactic
acid (I) evolves carbon dioxide on heating with cone, sulfuric acid, and is
converted to acetaldehyde, which can be identified by a color reacticm
with p-hydroxydiphenyl (II) and cone, sulfuric acid.
Cg,CH(OH)COOH
(I)
-OKI> (II)
Metaldehyde, paraldehyde, aldol, and propionaldehyde r e ^ t similarly

to acetaldehyde with p-hydroxydiphenyl and aulfuriS acid, forming deep
f ':
"* This reaction is also applicable aa a test for lactic acid according to a com-
munication from A. Bondi. Compare C. Weiimann, E. Bergmann, and Y. HinKh-
berg, / . Am. Chem. Soc^, 1676 (1936).
' E. Eegriwe, Zfanal. Cham., 96, 324 (1983). ^
GLTCBBIC ACID 401
violet compounds.' 'With formaldehyde the color is blue-green, with

butyraldehyde red, and with heptyl aldehyde orange. Accordingly,
a-hydroxybutyric acid and pyruvic acid give the same color reaction as
.laetic acid.
IfProcedureA drop of the test solution and 1 ml. cone, sulfuric add
are heated for 2 minutes in a diy test tube in a water bath at 85 C. After
cooling under the tap to 28" C., solid p-hydroxydiphenyl is added, the
mixture is swirled several times, and left to stand for 10 to 30 minutes.
The color appears gradually and intensifies after some time.
Limit of Identification: 0.5 y lactic acid
Reagents:.!) 96%.sulfuric acid
S) p-Hydroxydiphenyl (solid)
2, Test with o-hydroxydiphenyl and salfwic acid (flwêsceace test)."'
The acetaldehyde formed on heating lactic acid with cone, sulfuric acid
can also be identified by the blue fluorescence with o-hydroxydiphenyl.
Formaldehyde, metaldehyde, paraldehyde, aldol, and the next hiêr
homologs of the aldehyde series behave analogously to acetaldehyde.
Pyruvic acid does ndt interfere.
fProcedureA drop of the test solution is mixed with a crystal of
o-hydroxydiphenyl and 0.5 to 1 ml. cone, sulfuric acid in a dry test tube
and heated for 2 mmutes at 85" C. in a water bath. It is then examined
for a blue fluorescence while holding the test tube against black paper.
Limit of Identification: 1 y lactic acid
Reagents: 1) 96% sulfuric acid
^) o-Hydroxydiphenyl (solid)
GLYCERIC ACID
Test with Baphtlimreeordiiol and solftsric add."* On heating an aqueous
solution of i^yceric acid (I) with cone, sulfuric acid, in which a Uttle naph-
thoresorcinol (II)
CH,(OH)
w
/ Y Y - O H
I
CH(OH)
' ' '
COOH ijj
(I) (II)
is dissolved, an mtense blue forms. The chemistry of this color reaction
is not yet known.
"E. Eegriwe, Z. anal. Chem., M, 323 ff. (1933).
Most of the other hydroxy acids such as glycolic, lactic, a- and /3-hy-
droxybutyric, erythronic, gluconic, glyoxylic, pyruvic, levulinic, malic,
saccharic, citric, mesoxalic, and dihydroxjrtartaric acid, do not react under
the conditions of the test. Tartronic and quinic acids' give a greenish
color, glucuronic acid a yellow color with a greenish fluorescence, tartaric
acid a green to blue-green color, and malic acid a yellow color and a blue
fluorescence.
[[ProcedureA drop of the test solution is mixed with 0.75 ml. of the
reagent solution and heated for 30 to 60 minutes in a water bath at 90 C.
In the presence of glyceric acid a blue color appears, which is light or
dark according to the amount present.
Idmit of Identification: 10 y glyceric acid
Reagent: Solution of 0.01 g. naphthoresorcinol in 100 ml. 96%
sulfuric acid
PYRUVIC ACID
Test with o-hydroxydiphenyl and, sulfuric scid.'^' Pyruvic acid can
be reduced to lactic acid by the action of nascent hydrogen (from mag-
nesium and acid) :
CHsCOCOOH + 2 H -> CH3CH(0H)C00H
The lactic acid formed can be detected by conversion to acetaldehyde, and
the subsequent color reaction with hydroxydiphenyl and sulfuric acid
(page 400). The higher homologous a-ketonic acida behave similarly to
pyruvic acid.
f ProcedureA drop of the test solution is placed in a dry test tube.
A little magnesium powder is added and a small drop of sulfuric acid is
allowed to run down the sides of the tube. After the magnesium has
dissolved, a crystal of o-hydroxydiQhenyl and 0.5 to 1 ml. cone, sulfuric
acid is added. The mixture is heated to 85 C. in a water bath-for 2
minutes and observed for any color reaction.
Ldmit of Identification: 3 y pyruvic acid
Reagents: 1) Magnesiimi powder ,
S) o-Hydroxydiphenyl (solid)
OXALIC ACID ,
1. Test by conversion into glycolic Jicid.^'"' Oxalic acid is smoothly reduced
"E. Eegriwe, Z. anal. Chem., 96,;'325 (1934).
" E. Eegriwe, Z. anal. Chem., 89, 125 (1932).
OXAUC ACID 403
to glycolic acid by nascent hydrogen generated from magnesium powder

and dilute sulfuric acid. The glycolic acid can then be identified by the
delicate test with 2,7-dihydroxynaphthalene and cone, sulfuric acid,
described on page 399. Glyoxylic acid is also reduced by nascent hydrogen
to glycolic acid in the same way as oxalic acid. However, glyoxylic acid
is not precipitated by gypsum water from a neutral solution, and so oxalic
acid may be separated beforehand from the interfering acid. Tartaric
acid does not interfere with the test.
^ProcedureThe calcium salt is predpitated with gypsum water
from a neutral solution by the procedure used for the detection of oxalic
acid in the presence of tartaric acid and other anions."* The well-washed
precipitate is dissolved on the filter in warm 2 N sulfuric acid and a drop
of the filtrate is used for the test. The drop is placed in the bottom of a
dry test tube and a little magnesimn powder added. When the magnesium
is dissolved, 2 ml. of the reagent solution are added, and the test tube is
placed in boiling water for 15 to 25 minutes.
Limit of Identification: 1 y oxalic acid
ConcerUraiion Limit: 1:50,000
Reagents: 1) Solution of hydrated calciimi sulfate (gypsum)
2) N sulfuric acid
S) Solution of 0.01 g. 2,7-dihydroxynaphthalene in 100 ml.
cone, sulfuric acid ^
4) Magnesium powder
2. Test by formation of aniline blae.*** Oxalic acid when melted with
diphenylamine forms a triphenylmethane dye known as diphenylamine
blue or aniline blue. This dye is also formed when insoluble oxalates are
warmed with diphenylamine and syrupy phosphoric acid. The synthesis
of aniline blue from oxalic acid and diphenylamine can be represented:
I + <^ yNH.-^ y (1)

COff o
o--<o- II
-C + H,0
I
COH
"W. BSttger, op. cil. (tHs text, page 183), pages 485 and 488.
>F. Feigl and O. Frehden, Mikrochemie, 18, 272 (1935).
404 TI. OBOAMIC SPOT TESTS
O-^ UH <Z>-^-<Z>'
NH + HCOOH (3)
aniline blue
Formic, acetic, propionic, tartaric, citric, sucdnic, dihydroxymaleic,
benzoic, phthalic, tricarballylic, glycolic, and glyoxylic acid do not react
under the conditions of the experiment, so that the formation of aniline
blue in the reaction with diphenylamine is very selective for oxalic acid.
f ProcedureA tiny crystal of the sample (a solution must be evapo-
rated to dryness) is melted with a little diphenylamine in a micro test tube
over a free flame. On cooling, the melt is taken up in a drop of alcohol;
a blue color indicates the presence of oxalic add. Under ê same condi-
tions a blank test remains colorless.
Limit of IderUifieaiion: 5 y oxalic add
Reagent: Diphenylamiae (solid)
If oxalic add is to be detected in a mixture containing other anions
precipitbted 1^ CaCli (sulfate, sulfite, fluoride, tartrate, or racemate ions)
it is advisable to proceed as follows. Ilie acetic acid solution is treated
with CaClt; the precipitate is then collected on a filter or in a centiûge
tube, and freed from water, either by dlying or by washing with alcohol and
ether. A little of the precipitate^ mixed with diphenylamine in a dry test
tube, then syrupy phosphoric add is added, and the tube heated over a free
flame. This causes formation of caldum phosphate and liberation of oxalic
acid, which can condense to aniline blue with tiie diphenylamine. The
liquid turns blue, but the color fades on coolix^. - If the melt is taken up
in alcohol, a brilliant blue solution is obtained. If taken up in; water,
the excess diphenylamine is predpitated and colored light blue by absorp-
tion of the dye. A blank test that has been treated in the same way gives
a pure white predpitate of diphenylamine. The dye can be extracted
from the aqueous sdution with ether, which increases the sendtivity of the
reaction. After being left for a long time the trt tiiat has bben extracted
with ether again separates into two layers. The blue-violet product then
collects in the ethei>-water interface.
For the ^teîonof oxalic acid in leather, see page 486.
MALIC ACID 405
MALIC ACID
Test vith ^-naphthol and soUiuic add.^'* A bluish fluorescence is pro-
duced when maUc acid (I) is heated with cone, sulfuric acid containing
a Uttle j8-naphthol (II). The chemistry of this reaction is not yet ex-
plained. The following acids do not interfere: oxalic, tartaric, citric,
succinic, cinnamic, benzoic, salicylic, acetic, and formic. A few hydroxy
acids such as glycoUc and tartaric acid cause a more or less intense green
fluorescence.
HOCHCOOH / V V-OH
HtCCOOH
(D
(ID
IfProcednreTo detect malic acid in the mixed precipitate of the
calciiun salts that may contain citrate aiid succinate, either a little of the
precipitate or a drop of the solution of the precipitate in dilute sulfiuic acid
is used. This is treated with 1 ml. of a solution of /3-naphthol in cone,
sulfuric acid and heated for a short time on the water bath. In the presence
of malic acid a yellowish color with a bluish fluorescîce appears.
Limit of Identification: 10 7 malic acid
Reagent: 0.0025 g. /3-naphthol m 100 ml. M % sulfuric acid
TARTARIC ACID
1. Test with salftaric add and gallic acid.'** Jki heating caldum tartrate
with cone, sulfuric acid containing a little gaUic a d d a blue color results,
which is blue-green to yellow-greai when only veiy small amounts of tar-
trate are presrait. This reaction depends on the fact that cone, sulfuric
acid spUts tartaric acid (I) and produces glycol aldehyde ( I I ) :
COOH CHO
I I
CH(OH), -* H,0 + CO, -f CO + CH,OH
I
COOH
(D (II)
The aldehyde then forms a colored condensation product with galHc acid,
CdE,(OH),C(X)H.
Under these same conditions, colored products are produced also by
glycolic, tartronic, glyceric, and glyoxylic acids, and also formaldehyde, and
"E. Eegriwe, Z. anal. Chem., 89.121 (1982).
carbohydrates. No color is formed by oxalic, citric, succinic, lactic, malic,

cimiamic, salicylic acids and the fatty acids.
f ProcedureA very small sample of the calcium (precipitate is used
for this test. This should be filtered, washed, and dned on a hardened
filter paper (to avoid interference from fibers of cellulose which also react),
transferred to a test tube, treated with 1 ml. of the reagent solution, and
heated to 120 to 150 C. over a free flame. When only an extremely small
amount of the calcium precipitate is available, it is best to dissolve it on
the filter in sulfuric acid and to use a drop of the filtrate for the test. The
following colors are obtained with different amounts of tartaric acid:
100 7 tartaric acid, blue
10 7 tartaric acid, blue-green
5 7 tartaric acid, bluish green
2 7 tartaric acid, yellowish green
Reagents: 1) 2 JV sulfuric acid
2) 0.01 g. galhc acid in 100 ml. 96% sulfuric acid
2. Test with g,g'-dinaphthol and sulfuric acid."* A green fluorescence
appears on heating tartaric acid with cone, sulfuric acid in which /3,/3-
dinaphthol is dissolved.
/VA: -OH HO-
x/v \y\y
The following acids give no color reaction with this reagent: lactic,
malic, a-hydroxybutyric, j3-hydroxybutyric, erythronic, pyruvic, levu-
lim'c, oxalic, saccharic, citric, salicylic, m-hydroxybenzoic, p-hydroxy-
benzoic, protocatechuic, gallic, a-, fi- and 7-resorcylic, pyrogallolcarboxylic,
quinic, and cinnamic; formaldehyde and carbohydrates do not react.
Various colors are given by: glycolic and glyoxyUc acids (red-brown
to brown), glyceric and mesoxalic acids (gray), gluconic, glucuronic,
dihydroxytartaric, tartronic, and malic acids (green).
IfProcedureThe solid sample or a drop of a solution is treated with
a little solid /3,/3'-dinaphthol or a few ml. of a solution of dinaphthol in
cone, sulfuric acid, and heated for half an hour in a water bath at 85 C.
When tartaric acid is present, a more or less strongly luminous green
fluorescence gradually appears during the heating, and deepens on cooling.
At the same time the violetfluorescenceof the reagent itself ^disappears.
As little as 10 7 of tartaric acid can be detected >.if a drop of the test
solution is heated for 20 to 30 minutes with 1.2 ml", of the reagent solution.
0.05 mg. tartaric acid can be detected in the presence of any amount of
"E. Eegriwe, Z. anal. Chem.,W, 326 (1933).
CITRIC ACID 407
oxalic or succinic acids, and in the presence of 1000 times the amount of
citric acid, of 150 times the amount of cinnamic acid, or 10 times the
amount of malic acid.
Limit of Identification: 10 7 tartaric acid
Reagent: Solid /S^jS'-dinaphthol, or a solution of 0.05 g. /3,j8'-dinaph-
thol in 100 ml. 96% sulfuric acid
CITRIC ACID
Test by conTersion into citrazinlc acid."' The ammonium salt of 2,6-
dihydroxypyriduie-4-carboxyIic acid (V) (citrazinic acid) exhibits an in-
tense blue fluorescence in aqueous solution. Citric acid can easily be
converted to citrazinic acid, starting with a drop of the test solution. The
presence of citric acid can thus be detected by the blue fluorescence of the
ammonium salt of the citrazinic acid.
The stages in the conversion to citrazinic acid are: the treatment of
citric acid (I) with thionyl chloride to form aconitic acid chloride ( I I ) ;
this is converted into the triamide (III) by boiling with ammonia; this
compound in its tautomeric form (IV) gives ofE ammonia on heating with
80% sulfuric acid, the ring closes, and the acid amide group in the middle
is saponified. The product is citrazinic acid (V), and on the addition of
ammonia, forms the fluorescent ammonium salt (VI):
COCI CONH,
COOH
/OH snp, HiC^ ^CH NH. H.C^ ^CH
H.C^ \CHj OC CO OC CO
I I II II
HOOC COOH CI CI H.N NH, (III)
U) (ID it
COONH4 COOH CONH,
I I I
HC/ ^CH HG^ ^CH HC^ ^CH
II I *^^ II I *^^ II I
HO-Cv ^COH HOCv x,COH HOC COH
\N<i*^ \N-!^ I II
(VD (V) H,N NH (IV)
The test is specific for citric and aconitic acid; malic acid and tartaric
acid do not react.
^ProcedureA drop of the test solution is evaporated to dryness in a
>F. Feigl and V. Anger, Mikrochemie, 17, 36 (1936).
408 VI. OBOANIC SPOT TBSTS
microcrucible and the residue treated with 4 drops thionyl chloride and
taken to fumes. About 8 drops cone, aqueous ammonia are then added
and the mixture boUed over a microbumer imtil, about 2 drops liquid re-
main in the crucible. After cooling, 6 drops cone, sulfuric acid are added
and heating continued imtil sulfuric acid vapors are given off. The con-
tents of the crucible are washed into a test tube and made ammoniacal.
The solution is examined in ultraviolet light for an intense blue fluorescence.
Limit of Identification: 1 y citric acid
2) Cone, ammonia
S) C!onc. sulfuric acid
GLYCEROL
1. Test by conTeralontoacrokin.** Glycerol when heated with a dehydrat-
ing agent, such as potassium bisulfate, is converted into the unsaturated
aldehyde acrolein.'"
CH2(0H)CH(0H)CHs(0H) -> CHjiCHCHO -f 2 HjO
Acrolein gives a blue color, that turns violet-red"* with alkali, when
treated with an aqueous solution of sodium nitroprusside containing a little
piperidine. The chemistry of this reaction is not known. It has not been
possible to isolate a compound of definite formula from the components
necessary for the color reaction, although the acrolein may be substituted
by other aldehydes, and the piperidine by sec. aliphatic amines (page371).
The acrolein formed by removal of a molecule of water from glycerol
may alternatively be detected by reaction with dianisidine, in which case a
colored Schiff's base is formed, with elimination of a molecule of water.
Glycerides (animal and plant fats) also form acrolein on heating
with potassium bisulfate. The test may therefore be applied to the testing
of technical or natural products for fat or glycerol where~the-presence of
these is undesirable or not permitted.
f ProcedureA small amoimt of the test substance or a drop of the
test solution is placed in the hard glass tube described on page 31 (Fig. 32)
and mixed with finely powdered potassium bisulfate. A piece of filter
paper moistened with the reagent is placed over the open end of the tube
and covered with the glass cap. The acrolein produced by heating colors
the test paper a deep gentian blue. On treating the paper with dilute
sodium hydroxide, the blue aia changes to the color of a'i)each blossom.
" F. Feigl and O. Frehden, Mikrochim. Aela,-%^SJ (1937).
" ' C. A. Kohn, <^. W. FrMeniue, Z. antd. Chem., 80, 619 (1891).
" L . Simon, Compt. rend., 126, 1106 (1897); L. Lewin, Ber., 38, 3388 (1899);
E. Rimini, Gazz. chim. ittU., SO, I, 279 (1900).
CABBOHTPBATES 409
When using the alternative solution of o-dianisidine in glacial acetic

acid, a brown-red to yellow stain is formed on the paper.
Limit of Identification: 5 y glycerol
Reagents: 1) Freshly prepared mixture of 1 drop of 1% solution of
sodium nitroprusside and one drop of piperidine or satu-
rated solution of o-dianisidine in glacial acetic acid
2) Potassium bisulfate
S. Oflier tests for glyconl. The catalysis by glycerol of the decomposition
of oxalic acid at 100 to'llO" C , to form carbon dioxide and formic acid,
may be applied as a test."' The carbon dioxide formed may be identified
TABLE 34. BEDUCINO StiOASS
Identifiation limit
Reagent Color chiBge and concentration
limit
Nylander'8 solution (alkaline bismuth solu-

tion containing tartrate) Blackening IOT-;1 4000
Ammoniacal AgNOj solution Blackening 1
O.IT; 400,000
Magnesium hypoiodite [Mg(OH)i and KI|] Decolorization 6r; 1 8000
Alkaline 0.001% methylene blue solution Decolorization \y; 1 40,000
Alkaline dinitroaoetanilide (1, 3, 4) solution Violet h; 1 20,000
m-Phenylenediamine hydrochloride Yellow-green 0.67;! 80,000
(evaporated with 1 drop test solution) Fluorescence
by the decolorization of paper impregnated with sodium carbonate-

phenolphthalein solution (see page 254) {Id". Limit: 5 y glycerol). Al-
ternatively, the monofonnin (monoformic ester of glycerol) which is an
intermediate compound, may be detected by the test for esters given on
page 358 {Id". Limit: 40 y glycerol).
CARBOHYDRATES
1. Test for reducing sagsrs. Almost all the macrotests for reducing sugars
may be applied as spot tests. As yet only one test is available that is car-
ried out merely by mixing drops of test solution and reagent on paper.
Almost invariably it is essential to heat the reaction mixture (preferably in
a microcrucible). As all the tests depend on reducing properties, other
reducing substances must not be present.
The limits 0/ identification (drop size = 0.04 ml.) for a number of
reducing sugars are givrai in Table 34."
"O. Frehden and C.-H. Huang, Mikrochemie, 3, 20 (1937).
140 jp_ Feigi and G_ Frank, unpublished studies.
410 VI. ORGANIC SPOT TEfc^TS
The detection of reducing sugars through reduction of silver oxide

may also be carried out as a highly sensitive spot reaction on paper."'
Strips of filter paper are soaked in 0.2 N silver nitrate solution and dried.
Single drops of the alkaline test solution and of a sodium hydroxide solution
of approximately the same strength are placed next to each other on the
paper. Tw'o brown flecks of silver oxide develop. After about 1 minute,
the paper is placed in ammonia water. The unchanged silver oxide dis-
solves completely within several minutes, while a black fleck of finely
divided insoluble silver is left in thefleckproduced by the sample containing
reducing sugar.
Limit of Identification: 0.1 7 glucose
The test cannot be applied in the presence of organic compounds
containing CS or SH groups. Under the prescribed conditions, they form
black AgjjS, which likewise is not soluble in ammonia.
2. Test for ketohexoses with stannoas chloride, snlfurlc acid and iirea.'*^
A blue color is formed when ketohexoses are heated with a sulfuric acid
solution of urea containing stannous chloride. Aldohexoses give a red
color with this reagent, but only after prolonged heating. The chemistry
of this reaction is not known.
^fProcednre"'A drop of the sugar solution is treated with 6 to 20
drops of the reagent solution in a microcrucible, heated for a minute over
a microbumer, and allowed to cool. When ketohexoses are present a blue
color appears on cooling. The red color due to the aldohexoses only appears
after longer boiling and is less intense.
Reagent solution: 4 g. urea and 0.2 g. SnClj is dissolved by heating
with 10 ml. 40% sulfuric acid
The following were detected by means of this reaction:
8 y levulose (bljie) 20 y dextrin (red)
15 7 saccharose (blue) 30 y starch (red)
20 7 glucose (red)
3. Test for carbohydrates by hydrolysis to ftirfiiral."* Carbohydrates,
di- and polysaccharides are hydrolyzed by heating with strong mineral
acids. Monosaccharides are formed:
(CsHua). + X HiO -* a; C,HuO
" 1 F . Feigl, Chemistry <fe Industry, 57, 1161 (1938). See also page 346.
> J. H. Foulger, J. Biol. <!hem., 99, 307 (1932); Compt. rend., 196, 2984 (1933).
'* F. Feigl and R. Zappert, unpublished studiesh "^
"< O. Frehden and L, Goldschmidt, Mikroehim. Acta, S, 184 (1937).
TTROSINE 411
The monosaccharides on further heating are partly converted, by loss of
water, to furfural or its derivatives:
CH(OH)CH(OH) HC CH
I I II II
(HO)CH,CH(OH) CH(OH)CHO HOCH,C CCHO
\ /
O
These aldehydes are volatile in steam and react with o-dianisidine to
form colored Schiff's bases:
HC CH CH.O OCH,
2 HOCH,C CCHO + H,N NH,

\ /
O
HC- -CH CH.O OCH, HC- -CH
/
II II II
HOCHjC iC CCHjOH
O O
llProcedureA little of the sample is mixed with about 8 mg. oxalic
acid in a tall microcrucible and a few drops of dilute sulfuric acid are added.
The reaction is started by heating on an asbestos plate over a microbumer.
As soon as the contents of the crucil^le begin to brown, it is covered with a
small watch glass, carrying on its underside a piece of filter paper impreg-
nated with o-dianisidine in glacial acetic acid. The reagent paper turns
violet with the furfural vapor when sugars or carbohydrates are present.
After long exposure to the air the violet color of the paper gradually
changes to blue.
Reagents: 1) Dilute sulfuric acid (1:3)
) Oxalic acid (solid)
S) Saturated solution of o-dianisidine in glacial acetic acid
507 glucose 100 7 saccharose
50 7 levulose 100 7 lactose
10 7 sago starch 10 7 potato starch
10 7 arrowroot starch 10 7 cornstarch
507 agar-agar 6 7 gum arable
10 7 tragacanth 10 to 20 7 cellulose
TYROSINE
Test with a-nitroso-^-naphthoI.'** Tyrosine (I) and proteins give a
1" O. GerngroBS, K. Voss, and H. Herfeld, Ber., 66, 435 (1933).
412 VI. ORGANIC SPOT TB8TB
deep purple color on the addition of a-nitros6-/S-naphthol (II) and nitric

acid. The chemistry of the reaction is unknown. The nitric acid appar-
1 NO
V I
HO^\^ \CH,CHCOOH /\y\_,
(D
(II)
ently only oxidizes* the a-nitroso-j9-naphthol to a-nitro-/3-naphthol, as

it can be replaced by manganese dioxide or lead peroxide.
The reaction is specific for tyrosine in the presence of other amino-
acids, 3,4-dihydroxyphenylalanine, adrenaline, thyroxine, aldehydes,
sugars, or urea. Similar reactions are given by a number of p-substituted
phenols, such as tjrrosol, tyramine, p-cresol, p-ethylphenol, xylenol-1,2,4,
p-chlorophenol, p-bromo-m-cresol, hydroquinone monomethyl ether,
^-naphthol, and phenolphthalein.
fl^t>cediireA drop of the test solution is mixed in a microcrucible
with a drop of an alcoholic solution of a-nitroso-|3-naphthol and heated.
A drop of nitric acid ia added'to the hot solution. A purple color appears
in the presence of tyrosine. The color fades within a few minutes.***
Proteins, which almost without exception contain tyrosine, can be
readily detected by this reaction. Preferably they should be hydrolyzed
beforehand by heating with sodium hydroxide or sulfuric acid.
Limit of Identificaiion: 0.06 -y tyrosine
Conceniratim Limit: 1:1,000,000 , !
Reagents: 1) 0.2% alcoholic solution of a-nitroso-j3-naphthol
2) Nitric acid (sp. gr. = 1.4)
Tyrosine may be detected ii^pathological urine or serum as follows:"'
0.5 ml. of sample is diluted with 1 ml. water and 1 ml. 20%"trich]oroacetic
acid is added. The mixture is well stirred and either filtered or centri-
fuged from the precipitated albumio. As little as 0.05 y tyrosine can be
detected in a drop of the filtrate.
PROTEIN / /
1. Test with tetrabromophenolphthiEiIein ethyl ester.'*^ Tetrabromophenol-
phthalein ethyl ester is yellow
>" A. Maciag and R. Sch&ntal, Mikrochemie, 24, 250 (1938), state that the color
can be stabilized by adding ferric ammonium alum soluti^.
"' K. Nosaka, Mikrochim. Aeta',1, 79 (1937).
" F. Feigl and V. Anger, Mikrochim. Acta, 2, 107 (1937).
PBOTBIN 413
but ite alkali salts are blue. Tlieee salts are decompced by dilute acetic
acid with rêneration of the phenol. If the ester is brought into contact
with proteins, a blue color appears. Apparently this is due to the forma-
tion of a salt-like conipound,**"which, however, unlike the alkali salts, is
noit broken down by dilute acetic acid. The phenomîon known as "pro-
tein error" of indicators (displacement of the transformation range of pH
indicators) appears to be involved. This effect is shown very strongly by
tetrabromophenolphthalein ester. For practical purposes, the potassium
salt is used, as the ester is usually not available. The blue alcoholic solu-
tion of this salt is changed to yellow (color of the free ester) by dilute acetic
acid, but in, the presence of protein the color remains blue. It then only
changes to yellow on the addition of strong acetic acid or mineral acids.
The reaction is specific for native proteins.. Protein fission products
such as amino acids, di- and tripeptides, or peptones do not react. Alka-
loids of high molecular weight, when present in large concentration, may
give similar colors.
TfProcedoreA drop of the test solution is mixed on a spot plate or
in a microcruciblewith a drop of an alcoholic solution of the potassiiun
salt of tetrabromophenolphthalein ethyl ester and then acidified with 1 to 2
drops of dilute acetic acid. A blank test changes to yellow, while tiie color
remains deep blue in the presence of proteins. When only small amounts
of protein are present, the color is scntnewhat green.
Reagents: 1) 0.1% alcoholic solution of the potassiiun salt of tetra-
bromophenolphthalein ethyl ester**'
2) 0.2 N acetic acid
0.5 7 ^ g albumen' 57 edestin
0.51 hemoglobin 0.5 7 clupein
0.35 7 serum albumin 0.5 7 salmin
0.5 7 casein 17 gliadin
" R. Nietzki and E. Burckhardt, Ber., 30. 176 (1897).
For preparation, see R. Nietski and E. Burckhardt, loe. cU.
414 VI. OBGANIC SPOT TESTS .
A pathologically increased protein content in urine vaay be detected in

a drop of urine by means of this reaction.
2. Test after hydrolysis to amino adds. Proteins aire hydrolyzed by
strong mineral acids to simpler fission products (amino acids and poljrpep-
tides). These products may be identified either by melting with fluorescein
chloride (see page 371) or by condensation of the amino groups with p-di-
methylaminobenzaldehyde to produce colored Schifl's bases.'" When this
test is applied, it is of course essential that no other substance containing
amino groups should be present.
^ProcedureThe sample to be tested for proteins (solid or in solu-
tion) is mixed in a microcrucible with several drops of the reagent solution
and a drop of fuming hydrochloric acid. A violet color forms in the pres-
ence of proteins.
When the fluorescence reaction is applied, the sample is evaporated
to dryness with fuming hydrochloric acid and the residue treated as
described on page 374.
Reagents: 1) Saturated solution of p-dimethylaminobenzaldehyde in
glacial acetic acid
2) Fuming hydrochloric acid
S) Reagents given on page 374
Proteins, after hydrolysis, and identified by the formation of violet
Schiff's bases, gave identification limits:
l7 dried peptone 30 7 egg albumen
20')' blood albmnin 57 casein
100 7 hide powder 60 7 pancreatin
10 T edestin pepsin, very insensitive
PYRIDINE

Test by conversioii to ^taconic aMdiyde."* Pyridine can be converted
mto 4-pyridylpyridiniiun dichloride (I) on heating with thionyl chloride.
This product, on cleavage with alkali, gives rise to the alkali enolate of
glutaconic aldehyde (II) and 4-amrQopyridine' (III) (see page 378),
In acid solutions glutaconic aldehyde forms brightly colored Schiff's bases
(IV) with aromatic primary amines. The Schiff's base formed from glu-
taconic aldehyde and a-naphthylamine is an especiaUy brilliant red. The
following series of reactions are involved in this test for pyridine:
>" Compare 0 . Frehden and L. Goldachmidt, Mikrochim. Aeta,l, 351 (1937).
"' F. Feigl and V. Anger, unpublished studies. ' '
p-PHEMTLENEDIAMINE 415
0
/ \
N NCI HC^ CH
SOat I NOH I II
/ \ / \ OHG CHONa
(II)
N N-HCl
(I) ^
NHj-HCl
CHCHO
HC +2
\
CH==CHOH
2HC1
IfProcednreA drop of the solution to be tested for pjnridine is mixed

with a few drops thionyl chloride and wanned; any water present is re-
moved by the excess thionyl chloride. The mixture is evaporated almost
to dryness, a drop of water and a drop of sodium hydroxide are added, and
then acidified with a few drops hydrochloric acid containing a-naphthyl-
amine.
Limit of Identification: 5 y pyridine
2) ^ N sodium hydroxide
3) 2 N hydrochloric acid containing 1% a-naphthylamine
p-PHENYLENEDIAMINE
Test Iqr oxidatioB to indamine dye.*" When p-phenylenediamine is mixed
0. Heim, Ind. Eng. Chem., Anal. Ed., 7, 146 (1935).
416 VI. OBQANIC SPOT TESTS
with an oxidizing agent, in the presence of JEiniline, in ^slightly acid solu-

tion, a blue-green indamine dye is formed immediately:
-J-2H,0
NH, NH, NH NHj

Derivatives of p-phenylenediamine behave similariy. The reaction
may be applied to detect the presence of p-phenylenediamine, which is a
poison, in furs, hair dyes, etc.
f ProcedureA drop of the acetic acid test solution is mixed with a
drop of aniline water and several crystals of potassium persulfate are added.
A dark to light blue color develops at once, according to the amount of
p-phenylenediamine present.
Limit of Identification: 0.5 y p-phenylenediamine
Concentration lAmii: 1:100,000 ^
Reagents: 1) Aniline water. 1 drop aniline in 50 ml. water
2) Potassium persulfate
PHOSGENE
Test by conversioii to ^phenyk^bohydrazide.^'^ Phosgene reacts witii
alky] and arylhydrazines to form carbohydrazides.**' For example,
diphenylcarbohydrazide is formed from phosgene and phenylhydrazine
(in an inactive organic solvait):
C.HtNHNH, Civ C,HiNHNHv
+ >C0 - >CO + 2 HCl
C.H.NHNH, CK , C.H,NHNH-^
As extremely small amounts of diphenylcarbohydrazide^give a
bright violet salt with copper salts,"' the reaction is applied in-the test
for phosgene. As free hydrazine does not keep, it is advisable to use its
cinnamic acid salt, in a suitable organic solvent, for the reaction with
phosgene. /
^ProcedureA drop of the test soluticm is mixed in a microcrucible
with a small grain of phenylhydrazine cinnamate, and after 5 ininutes a
drop of copper sulfate solution added. In the presence of phosgene,
a red-violet to pink appears, according to the amount present.
Alternatively, spot paper (S & S 598g) Ss ini^regnated with 1%
"< V. Anger and S. Wang, Mikrochim. Acta, 8, 24 (1938),
i " G . Heller, Ann., 263, 277 (1891).
P. Caiieneuve, ^11. soc. chim., [3], 23, 701 (1900).
CABBON DISX7LFIDB 417
copper sulfate solution and dried. Just before the test a little solid phenyl-
hydrazine cinnamate is rubbed on it. A drop of the test solution is added,
followed, when the solvent has evaporated, by a drop of water. In the
presence of phosgene, a red-violet stain forms.
Limit 6j Idenlificxtiion: 0.5 y phosgene
Rmgents: 1) Phenylhydrazine cinnamate**'
S) 1% copper sulfate solution
The test may be applied to the detection of phosgraie in commercial
chloroform and carbon tetrachloride. Chloroform, for anesthesia, and
pure carbon tetrachloride contain only traces of C0C1 compared with the
technical products.
CARBON DISULFIDE
1. Test with sodiaiii a^dde and ioê."^ Aqueous solutions of sodium
azide (NaN) and iodine (as KI,) do not react together and the iodine titer
does not change on keeping the mixed solutions. When carbon disulfide
is added to a sodiimi azide-iodine solution a vigorous reaction begins at
once, with evolution of nitrcên and consumption of iodine;
2 NaN, + I = 2 Nal-H 3 N, (3)
The carbon disulfide appears to take no part in the reaction, but
acts as a typical catalyst. This catalysis is superficially similar to that
described on page 227 in the test for sulfides, thiosulfates, thiocyanates,
and for organic compounds containing the CS and CSH groups.
The catalytic effect of carbon disulfide on the iodine-azide reaction is a
typical intermediate reaction catalysis. The sodium azide and carbon
disulfide first form the sodium salt of azidodithiocarbonic acid, CS(SH)Ni.
This reaction is incomplete, but the azidodithiocarbonic acid can be recog-
nized by the formation of typical salts of the heavy metals (bismuth
or copper salts)."* The equiUbrium of reaction (1) is constantly disturbed
in the presence of iodine, as the dithiocarbonate formed is oxidized by
iodine, as shown in (2), so that the new formation of the azidodithiocar-
bonate and its oxidaticm proceed until all the sodiiun aside is consumed.
Summation of (1) and (2) gives (3), in which the catalytically active car-
bon disulfide is no longer shown as a participant in the reactions:
2 NaN, -I- 2 CS, = 2 CS(SNa)N, (1)
2 CS(SNa)N, -j-I, = 2 CS, -j- 2 Nal -H 3 N, (2)
2 NaN, -t- I, = 2 Nal + 3 N, (3)
>" For preparation, see C. Liebftrmann, Ber., 34, 1106 (1891).
F. Feigl and E. Chargaff, Z. anal. Chem., 74, 376 (1928).
" Compare F. Sommer, Ber., 48,1833 (1916).
418 VI. OHGANIC SPOT TESTS
Carbon disulfide can therefore be detected by the evolution of nitro-

gen, or by the utilization of iodine, in the iodine-azide reaction. It must
be noted that mercaptans and thioketones also catalyze the iodine-azide
reaction (see page 353). ,
UProcedureThe test for carbon disulfide in an organic liquid, e.g.,
alcohol, may be carried out by mixing a drop of the test solution and a
drop of the sodium azide-iodine solution on a watch glass and watching
for bubbles of nitrogen. When hydrogen sulfide or any other compound
is present, which utilizes iodine, the test solution must first be treated,
drop by drop, with an iodine solution in potassium iodide until the iodine
is no longer decolorized. The iodine-azide solution can be added then.
This test for carbon disulfide may alternatively be carried out simi-
larly to the sulfide,test (see page 228). In this, a drop of the test solution,
which, if necessary, has previously been treated with iodine, is removed
with a loop of platinimi wire and touched to a drop of the iodine-azide
solution hanging from a capillary tube. Any bubbles of nitrogen formed
may be seen rising in the capillary tube.
Limit of Idenlijlcation: 0.14 y carbon disulfide
Reagent: Sodium azide-iodine solution (see page 228)
2. Test with formaldehyde and plambite solution.^'<> Carbon disulfide
is converted into trithiocarbonate on treatment with alkali hydroxide:
2 CSj -f 6 KOH = 2 KjCSj + KjCO, + 3 HjO
The trithiocarbonate reacts with heavy metals to give insgluble salts,
which are usually colored, and can, as in the case of the lead salt, be readily
decomposed with formation of sulfide.
Appreciable amounts of carbon disulfide are rapidly converted into
lead sulfide on treatment with coqc. caustic alkali and a pliunbite solution.
Small amounts of carbon disulfide are only very slowly converted J o thio-
carbonate, even in the presence of large amounts of alkali. However, the
thiocarbonate formation, and consequently the production of lead sulfide,
may be remarkably accelerated by formaldehyde (in a manner not yet
understood). This effect affords means of detecting very small amounts
of carbon disulfide.
^ProcedureA drop of the test solution is placed on spot plate,
2 or 3 drops of formaldehyde solution is added, followed by a drop of a
strongly alkaline plumbite solution. The mixture is stirred. A black
precipitate, or a brown to black color is formed, depending on the amount of
carbon disulfide originally present.
Limit of Identification: 3.5 y carbon disulfide
" F. Feigl and K. Jfeisselberg, Z. anaJ.. Chem.,p, 101 (1931).
ASCOBBIC ACID 419
Concentration Limit: 1:14,^X)

Reagents: 1) Formalin (40%)
2) Alkaline plumbite solution
3. Test for carbon disulfide in the presence of hydrogen sulfide. The
test just described obviously cannot be used, without modification, for the
detection of carbon disulfide in the presence of hydrogen sulfide. The
characteristic formation of lead sulfide is then no longer specific. The
hydrogen sulfide is best removed by oxidation with bromine water:
HjS + 8 Br + 4 HjO = HjSO* + 8 HBr
and the excess bromine removed by sulfite:
Br, + SOr" + HjO = S07" + 2 Br" + 2 H+
The carbon disulfide can then be detected as described under 2.
An excess of sulfite does not interfere with the test as it is converted
into aldehyde bisulfite by the formaldehyde used in the reaction:
CHjO + NajSOa + HjO = CH2(OH)S03Na + NaOH
UProcedureA drop of the test solution suspected of containing CSs
and HjS is treated on a spot plate with concentrated bromine water,
added drop by drop, until the yellow color is permanent. The excess of
bromine is removed by adding a small crystal of sodium sulfite. Then
2 or 3 drops of a 40% solution of formaldehyde is added, followed by a drop
of a strongly alkaline solution of plumbite, and the mixture stirred. A
black precipitate, or a black to brown color, appears in the presence of
carbon disulfide.
The following limit of identification is independent of the amount
of hydrogen sulfide that may be present.
LimU of Identiijication: 10 y carbon disulfide
Reagents: As for test 2; also bromine watr and solid sodium sulfite
ASCORBIC ACID (VITAMIN C)
Ascorbic acid (I) is converted easily into dehydroascorbic acid (II)
I ^ 1 oxidation
0==CC(OH)=C(OH)CHCH(OH)<;H,(0H) reduction
(I)
0=CCOCOCHCH(OH)CHjOH
(II)
420 VI. OBOANIC SPOT TEBTS
Consequently, it is an active reducing agent which can be detected by

numerous color tests based on reducing reactionsi Insoluble inorganic
compounds precipitated in the capillaries of paper lind which consequently
are particularly reactive, can also be reduced by ascorbic acid. Two in-
stances of this behavior, that are accompanied by distinct color changes,
are given here.
1. Test by redaction of manganese dioxidi.'*> Ascorbic acid reduces
manganese dioxide to a manganous salt. Paper impregnated with highly
dispersed MnOj is prepared.easily by treating filter paper with potassium
permangana,te solution. Part of the cellulose is oxidized, and finely
divided MnOj is precipitated in the capillaties of the paper. The color of
the paper ranges from brown to almost white, according to the MnOt
content. Larger quantities of ascorbic acid are revealed directly by the
white fleck that results when a drop of the test solution is placed on the
brown paper. Practically colorless reagent paper should be used for minute
quantities of ascorbic acid. The removal of MnOj, in this case, is made
visible by bathing the spotted paper in benzidene solution which forms
"benzidene blue" with traces of MnOj (see page 134). Consequently, the
whole surface will turn blue, except those spots that had been reduced by
ascorbic acid.
P*rocediireA drop of the weakly acidified (acetic acid), neutral, or
alkaline test solution is placed on the reagent paper. After the liquid has
been absorbed, the paper is bathed in benzidine solution. A white fleck
on the blue paper indicates the presence of ascorbic acid.
lAmit o/ Identification: 0.03 7 ascorbic acid (in 0.004 ml.)
Concentration lAtnit: 1:130,000
Reagents: 1) MnO paper: 1 ml. 0.2 N EMnO* is diluted to KKK) ml.
The paper is soaked in this solution for 16 minutes.
After draiiting, it is dried in a current^f heated air
2) Benzidine solution: Saturated solution of ^benzidine
hydrochloride diluted with an equal volume of water,
just before using
It should be noted that other reducing ccanpouiuls in weakly acid
solution, exert the same effect on MnOi. Citric acid is an example. To
detect ascorbic acid in the presence of the latter (in fruit juices, for instance)
the test solution is shaken beforehand with an excess oS. calcium carbonate.
A drop of the suspension is t h ^ applied to the reagent paper. This pre-
liminary treatment produces insoluble calcium citrate and the reducticm
of MnOt by citric acid is thus prevented entirely. - The action of ascorbic
acid is not affected.
" F. Feigl and H. T. Cardoso, Reo. braail. biol., 2, 117 (1942).
TEST FOB BNZYUES 421
2. Test by redaction of ammoniaiii phosphomolybdate.''' Water-soluble

phosphomolybdic acid, HsP04-12 MoOj-aq, is reduced easily to molyb-
denum blue (see page 250). Ammoniimi phosphomolybdate, which is but
slightly soluble in water and mineral acids, reacts only with powerful
reducing agents to produce molybdenmn blue. Accordingly, compounds
with different redox potentials can be differentiated by this means. As-
corbic acid acts on ammonium phosphomolybdate and can therefore be
detected by spotting paper impregnated with (NH4)sPo4-12 MoO.
IfProcedoreA drop of the acid, neutral, or alkaline test solution is
placed on the reagent paper. According to the amount of ascorbic acid, a
blue or green fleck appears on the yellow paper immediately, or after sev-
eral minutes.
Limit of Identijication: 0.1 y ascorbic acid (in 0.01 ml.)
Reagent: Ammonium phosphomolybdate paper. Filter paper is
immersed in a saturated alcohol solution of phosphomolybdic
acid, allowed to drain, and dried in a current of cold air.
It is then bathed in a cone, ammonium nitrate solution that
has been acidified with several drops of nitric acid. After
washing with water, the paper is dried in a blast of heated
air. It can be kept for several days in the dark
Citric acid shows no reaction under the conditions just described.
Consequently, it is possible to detect ascorbic acid in the presence of aa
much as 1000 parts of citric acid.
Ascorbic acid can be detected in urine if the sample is treated before-
hand with several drops of cone. HCl. This prevents any reduction of
ammonium phosphomolybdate by thie uric acid.
Uric add and ureatea react quite readily with ammonium phos-
phomolybdate. These compounds may be detected through this reaction.
TEST FOR ENZYMES!"
A number of inorganic substances which can accelerate the velocity
of a particular chemical reaction may often be detected in extremely small
amounts by this catalytic action. The test is based either on tiie detec-
tion of a product of the catalysis or the disappearance of one of the partici-
pants in the reaction. Such tests for the catalytic substance are nearly
alwasTB specific. The following tests for certain enayme groups are based
on the same principle. These ^zymes are organic ^bstances that occur
in plant and animal material and, as catalysts, play an important role in
metabolic processes. Such îzymes (biocatalysts) are distinguished by
F. Feigl and H. T. Cardoso, Rev. brasil. biol, i, 117 (1942).
> N. B. Saatri and M. Sreenivasaya, Mikrochemie, l i , 160 (1038/34).
the deep-eeated changes they effect in definite substrate^, changes such as

oxidation, reduction, alteration of hydrogen ion concentration, formation of
chajracteristic compounds, etc. These changes may be recognized by the
use of spot tests and with very small amounts of substrate, and hence the
enssymes themselves identified by sensitive tests.
1[ProcedureA drop of the substrate solution and a drop of the solu-
tion to be tested for a particular enzyme are mixed on a strip of filter paper
or in a microcivicible. Both the sample and a blank test (a drop of vfater
and a drop of substrate) are kept for 40 to 60 minutes under a moist bell jar.
The product of the reaction is then treated with suitable reagents.
TABLB 35. ENZYMES
Eatjrme Substnte Rngeat Color
Diastase 0.5% Soluble starch Fehling's solution Brick-red or

orange
Inulase 0.5% Inulin Feliling's solution Brick-red or
orange
Invert ase 0.6% Cane sugar Fehling's solution Brick-red or
orange
înulsin 0.6% Salicin Fehling's solution Brick-red or
orange
Emulsin 0.5% Indican Treatment with alkali Blue
with access to air
Lipase 0.2% Emulsion of olive Methyl red Red
oil
Butyrase 0.2% Ethyl acetate- Methyl red Red
water emulsion
Urease 1% Urea Phenolphthalein Pink
Phenolase 1% Tincture of guaiac Phenolphthalein Blue
Tyrosinase Tyrosine Phenolphthalein Brown
pertinent details concerning the detection of several enz3Tnes are

given in Table 35.
Other reactions, described elsewhere in this book, may also be applied
as tests for enzjnnes. Some examples are given in the following sections."*
Urease
Urease causes urea to break up into ammonia and carbon dioxide.
It may therefore be detected by mixing a drop of the enzyme solution
and a drop of a 10% solution of urea in the apparatus described on page 31
(Fig. 30) and covering the fimnel stopper with a piece of filter paper im-
pregnated with a manganese-silver solution (for preparation see page 185).
" F. Feigl and O. Frehden, unpublished studies.
TBST FOR ENinrUES 423
In the presence of iirease, the paper turns black in about 10 minutee owing
to the action of the liberated ammonia.
Zymase
Zymase ferments sugar with the formation of alcohol and carbon
dioxide. The carbon dioxide produced may be identified by the reaction
described on page 254 (decolorization of sodium carbonate solution colored
red with phenolphthalein). The test may be carried out in the apparatus
describwi on page 31 (Fig. 27). A drop of the solution to be tested for
i^ymase is mixed with a drop of a 5% solution of glucose. In the presence
of zymase, the drop is decolorized in about 10 minutes.
g-GIncosidases (Emnlsin)
Emulsin causes the glucoside amygdalin to break down with libera-
tion of prussic acid, which can easUy be identified by the cyanide test
described on page 208 (blue color with benzidine-copper acetate).
A drop of the solution to be tested for emulsion is placed in the ap-
paratus described on page 30 (Fig. 31). A little amygdalin is added and
the funnel stopper is covered with a piece of filter paper impregnated with
the benzidine-copper acetate reagent (see page 208). A blue color after a
few minutes indicates prussic acid, and hence emulsin.
Lipases
Lipases are ester-splitting enzymes. They can easily be identified
by using the test for esters described on page 358.
A drop of a castor oil emulsion is placed in each of 2 microcrucibles..
A drop of the solution to be tested for lipase is placed in one of the crucibles.
After 1 to 2 hours, the contents of the crucibles are tested for esters. In
the presence of lipase, the reaction is negative, or decidedly weaker, while
the blank test gives the characteristic violet color due to esters.
Catalase
Catalases are ferments that catalyze the decomposition of hydrogen
peroxide with liberation of molecular oxygen. They can therefore be de-
tected by the disappearance of hydrogen peroxide from the substrate. The
titanium salt reaction described on page 150 is used for the peroxide test.
The test with PbS paper also serves well (page 268)."
A drop of the solution to be tested for catalase is mixed with a drop
fif a 3% solution of hydrogen peroxide and left for 1 hour. In the presence
" F. Feigl, Chemistry & Indutlry, 67, 1164 (1939).
424 VI. OHGAKIO SPOT TSStH
of catalase, the addition of a titanium salt will give |io color, or only a
slight yellow, while the blank test develops an orange-yellow.
A drop of the solution treated with hydrogen peroxide may also be
placed on PbS paper. The positive or negative response to the HjOj
reaction can be noted. '
Peroxidase (Blood)""
The hemoglobin of blood has the activity of a peroxidase and catalyzes
the oxidation by hydrogen peroxide of benzidine to benzidine blue (see
page 55).
A drop of the solution to be tested for blood {e.g., urine) is placed on
spot paper (S & S 698g) and treated first with a drop of 3% hydrogen
peroxide and then with a drop of 0.05% solution of benzidine in 10%
acetic acid. When blood is present, a blue stain appears after a time,
varying from a few seconds to 1 minute according to thcamount present.
The color lasts for about 1 hour.
The sensitivity and rapidity of the test may be increased, but at the
expense of the length of life of the color, by adding a drop of 2 N sodium
Jiydroxide to the spot paper before applying the specimen, and then pro
ceeding as just prescribed.
"K. Nosaka, Mikrochim. Acta, 1, 78 (1937).
VII. APPLICATION OF SPOT REACTIONS IN
TESTS OF PURITY, EXAMINATION OF
TECHNICAL MATERIALS, AND
STUDIES OF MINERALS
, Many of the spot tests described in the foregoing sections of this book
can be successfully applied either Unaltered, or with very little modifica-
tion, to the solution of problems presented to the practical and technical
analyst. In control tests, in tests of the purity of technical and pharma-
ceutical products, and in food analysis, it is sometimes very important to
be able to determine rapidly the presence or absence of a certain material
that affects the quality. Likewise, the rapid and certain detection of
definite elements or compounds in samples of minerals often has both scien-
tific and technical importance.
Without any claim to completeness (see also Chapter VIII), pertinent
examples are described in the following pages. The methods selected have
shown in repeated tests that they are especially suitable, and that they can
be successfully accomplished with even small amounts of the sample.
Detection of Silver in Alloys and Silver Plating'
The very sensitive silver test with p-dimethylaminobenzylidene rho-
danine (page 43), can be easily applied to the detection of silver in alloys,
metal coatings, jewelry, etc., without visible damage to the specimen.
^Procedure^The sample is drawn over a piece of unglazed porcelain
(streak plate). ' The hair-fine scratch on the porcelain is treated with dilute
HNO3, applied with a fine glass rod, and the plate is held over a flame until
the acid has evaporated. Filter paper (S & S 589g), moistened with dilute
nitric acid, is pressed against the plate, while still warm. After one
minutej the paper is spotted with the reagent solution. A red-violet
streak is formed.
This method of testing can be carried out so as to obviate any inter-
ference from mercury. The mercury salts can be volatilized by igniting
the streak, or the evaporation residue from a drop of the test solution.
Then in the subsequent treatment with dilute nitric acid only the silver
nitrate remains and is identified easily by the p-dimethylaminobenzylidene
rhodanine test.
"Studies with H. E. Ballaban. 28
425
426 VII. APPLICATIONS OF SPOT REACTIONS
Detection of Copper in ADoys^

The spot test for copper described on page 70 using rubeanic acid and
utilizing capillary separation in the paper, is useful in the qualitative analy-
sis of alloys, if minute quantities of copper are to be detected.
1[ProcedureA few grains of the sample are dissolved in 2 drops
dilute HNO3, using a Pavelka tube (Fig. 16, p. 25)'for gold alloys, 2 drops of
aqua regia are used. After solution, the liquid is evaporated to dryness and
the residue taken up by warming gently with a few drops dilute acetic acid.
By tilting the tube, a drop of the acetic acid solution is placed on spot paper
impregnated with a saturated alcoholic solution of rubeanic acid. In the
absence of other metals that react mth rubeanic acid, a black to olive
green circle or ring of copper rubeanate is formed.
When the solution also contains nickel, a violet ring of nickel ru-
beanate is formed around the copper stain, but separated from it by a
white circle (see page 71).
In the presence of silver or gold, a brown central circle is formed of
the silver or gold compounds with rubeanic acid, and this is surrounded
by a narrow band of copper rubeanate. The formation of these silver and
gold compounds, which can seriously interfere with the detection of small
amounts of copper, may, however, be prevented by warming the acetic
acid solution with a few crystals of potassium bromide or nitrite, or a little
hydrogen peroxide, before carrying out the spot test. The silver is thus
converted into AgBr or HAgBrj, and the gold compound is reduced to the
metal.
To detect traces of copper in metallic zinc or cadmium, the reaction
with ammonium mercury thiocyanate (violet precipitate) is suitable (see
^page 73). After solution of 1 g. metal in dilute nitric acid, evaporation
and solution of the residue in 2 ml. water, and the addition of excess am-
monium mercury thiocyanate, as little as 0.001% copper may be detected
in metallic cadmium and 0.002% copper in metallic zinc.^.
The use of l,2-diaminoanthraquinone-3-sulfonic acid (see page 68)
is recommended^ if copper is to be detected by a simple procedure and with-
out visible damage to the sample (alloys, plating, etc.). o
1l ProcedureThe sample is drawn forcibly across a streak plate,
or the unglazed edge of the bottom of an evaporating dish. Nitric acid or
aqua regia is applied to the streak with a thin glass rod. The solution is
evaporated by cautious fanning with a flame; overheating must definitely
be avoided. A strip of reagent paper moistened with 1 N NaOH is then
pressed against the still lukewarm streak plate (see page 69/. After about
*F. Feigl and H. J. Kapulitzas, Mikrochernie, B', 242 (1930).
F. Pavelka, Mikrochernie, 4, 200 (1926).
F. Feigl, Mikrochernie, 7, 11 (1929).
'H. E. Ballaban, Mikrochernie ver. Mikrochim. Acta, 27, 62 (1939).
DETECTION OF LEAD 427
half a minute, the paper is removed. A blue print (mirror image of the
streak) indicates the presence of copper. As little as hundredths of a
per cent of copper can be quickly detected in electroplatings, light met-
als, etc.
The test for copper, based on its catalytic activity" (see page 63),
can be applied in the form of a drop reaction for the detection of minimal
quantities of copper in alloys and pure metals. It is not necessary to pre-
pare solutions of the sample. Minute particles of the solid (1 to 3 mg.)
can be tested directly on the spot plate, comparing the results with a blank.
Detection of Small Amounts of Copper in Pharmaceutical Products
or Foodstuffs
It is very often necessary to test for copper in examining the purity
of pharmaceutical preparations, especially extracts and essential oils.
A high copper content is of course not permissible, owing to its toxicity,
but very small amounts (less than 0.001%) are harmless. Even small
amounts of copper are forbidden in preserves.
A rapid method of detection is to ash the sample and then form the
violet Cu-Zn-Hg-thiocyanate (see page 73). Comparison of the intensity
of color with that of a precipitate from a known amount of copper obtained
under the same conditions, gives a fairly accurate estimate of the copper
content.'
IfProcedureAbout 0.2 to I g. of the substance is ashed in a small
porcelain crucible (capacity about 5 ml.), fumed with 2 drops cone, nitric
acid, and ignited until the carbon disappears. The ash is then evaporated
to dryness with a drop of cone, hydrochloric acid, and the residue is gently
warmed with a further drop of hydrochloric acid, and taken up in 2 ml.
water. The solution is then poured into a test tube, and about 50 mg.
ammonium fluoride are added to mask the effect of iron that is almost
always present. The further procedure follows the directions on page 73.
Detection of Traces of Copper in Water*
The copper in extremely dilute solutions can be adsorbed on CaFj or
talc. The Fe+^^-SjOs test can then be applied to the adsorbent (see
p. 65).
Detection of Lead in Tin Platings' and Enamels"
The tinned surface to be tested is first washed free from grease with
alcohol and ether. Then a drop of cone, nitric or acetic acid is placed on it
F. L. Hahn and G. Leimbach, Ber., 56, 3870 (1922).
T . Feigl and P. Krumholz, Pharm. Presse, B, I (1934).
' F . Feigl, op, cit. (this text, page 2), page 236.
A. Bobierre, Compt. rend., 80, 961 (1875); J. Fordos, ibid., 80. 794 (1875).
" J . Grfinwald, Oesterr. Ghem.-Ztg., 14, 271 (1911); see also M- Egorov, Chem.
Abstracts, 33, 9187 (1939).
428 VII. APPLICATIONS OF SPOT BBACTIONS
and the specimen carefully heated until the acid is evaporated. The gray
fleck that remains may contain lead nitrate or acetate as well as metastan-
nic acid. It is treated with a drop of 5% potassiiun iiodide solution. In
the presence of lead (dawn to 1%) yellow needles of ledd iodide are formed.
A thin yellow-green tiiit indicates the presence of not more than the small
amounts of lead, whicli are always present in commercial tin.
When testing enamels for lead, the surface is spotted with cone, nitric
acid, evaporated to dryness, and then moistened with a drop of 10%
potassium iodide solution.
Detection of Lead in Alloys and Crude Metals^'
Lead can be detected quickly in alloys and crude metals by means
of the very sensitive reaction with sodium rhodizonate (see page 56).
Alloys containing no, or only a little, tin can be tested by merely treating
the sample -with a buffer solution (pH = co.3) and sodium rhodizonate.
The red lead rhodizonate'is formed if not less than 0.3% lead is present.
When testing alloys containing much tin, violet stannous rhodizonate may
be formed and hide any lead rhodizonate. Consequently, with such
alloys, or crude tin, the sample must be treated previously with nitric acid.
SnOa-aq is formed; it does not react with sodium rhodizonate.
^Procedure(Alloys up to 12% tin). A few fragments are removed
by means of a fine file. The particles are washed with ether to remove the,
grease. The test is made on a spot plate. Three drops buffer solution
are added, and the solid and liquid kept in agitation for 2 minutes by blow-
ing into the suspension through a pipet. One drop sodium rhodizonate
aolVLtiotL la then, added^ but not stirred in. A. red precipitate or color
appears if the alloy contains lead. A blank test, using 3 drops buffer
solution and 1 drop reagent, should be made when testing alloys very low
in lead. The blank becomes completely colorless after a few minutes.
The filings may ^'so be igdited in a microcrucible with access to the
air. After cooling, the residue is spotted with buffer solution and^ sodium
rhodizonate.
Either of these procedures will reveal with certainty as little as 0.3%
lead.
^Procedure(Alloys rich in tin) A few fine filings are treated in a
microcrucible with several drops of nitric acid, evaporated, and then weakly
ignited. The cold residue is treated with 1 drop buffer solution and 1 drop
sodium rhodizonate. Red lead rhodizonate appears. ,
Reagents: 1) 0.2% sodium rhodizonate solution
) Buffer solution: 1.5 g. tartaric "acid and 1.9 g. sodium
bitartrate in ICK) ml. watei" (pH 2.79)
"F. Feigl and H. A.- Suter, Ind. Bug. Chem., Anal. Ed., H, 840 (1942); F. Feigl
and N. Braile, Chemist-Analyst, 32, 52 (1943).
Crude and pure metals (Zn, Mg, Al, etc.), that are soluble in sulfuric
acid, can be tested for lead as follows: A little of the metal is dissolved in
dilute sulfuric acid and the solution evaporated to fuming (SO3). The
residue is taken up in hot water and filtered through a small paper. After
washing free of acid, the filter paper is spread on a porcelain or glass plate,
and spotted with buffer solution and sodium rhodizonate. The appearance
of a red fleck indicates the presence of lead sulfate, and consequently,
of lead.
Detection of Leiad in Ores, IV^nerals, and Pigments"

Lead can be detected directly in ores, and in minerals which contain
no barium or strontium, by means of scarlet-red lead rhodizonate (see
page 56). A little (less than 1 mg.) of the finely powdered sample is
spotted with a drop of buffer solution and a drop of sodium rhodizonate on
a spot plate. The surface of the solid specimen turns red if lead is present.
If it is suspected that barium and strontium are present, the sample must
be fumed with a drop of sulfuric acid. This transformation into sulfates
is necessary because the oxides of these alkali earth metals, as well as
baritmi carbonate, react with sodium rhodizonate. The sulfates, in con-
tradistinction to lead sulfate, do not react.
Lead-bearing sulfidic ores, such as galena, can be tested in the same
way as oxide minerals. However, the following procedure has a higher
sensitivity. A little of the test material is ignited in a microcrucible, and
stirred with a platinum wire. The lead is thus transformed into sulfate.
After cooling, the residue is spotted with the reagent and the buffer solu-
tion. It should be noted that, even in the case of stolzite, the sensitivity
of the test is raised if the specimen is calcined beforehand.
The following minerals and ores gave a positive reaction with sodium
rhodizonate when treated by the foregoing procedure:
GalenaPbS AnglesitePbS04
CerussitePbCOa CrocoitePbCrO*
StolzitePbWOi Lead-bearing zinc blendeZnS, PbS
Zinc oxide or zinc dross can be tested for lead by direct spotting with
sodiiun rhodizonate and buffer solution. A rapid method of detecting
lead in zinc oxide is especially useful if the material is to be used in the
preparation of glass, because lead often enters glass in this way. A little
(0.5 to 1 mg.) of the sample is fumed with sulfuric acid; the residue is
extracted with water; filtered, and the undissolved material on the filter
paper is tested with the reagent solution.
Lead can be detected in pigments, oils, and varnishes by this reagent.
" F . Peigl and H. A. Suter, Ind. Eng. Chem., Anal. Ed., U, 840 (1942); F. Fcigl
and N. Braile, Chemist-Analyst, 32, 52 (1943).
430 VII. APPLICATIONS OF SPOT REACTIONS-
Pigments can be spotted directly; oils and varnishes ^ u s t be ashed before

making the test.
Reagents: See page 57.
Detection of Traces of Lead in Water, Alkali Salts, and Sulfuric Acid"

The decisive detection of traces of lead in water is rather important
from the medical and public health standpoint because small amounts of
lead accumulate in the human organism and are eliminated only slowly.
There is an extensive literature on the detection and determination of small
amounts of lead."
The test for lead described on page 56 has an identification limit of
0.1 y Pb, and consequently, only succeeds with one drop of a solution at a
maximal dilution of 1:500,000. Lead can be detected in solutions of far
greater dilutions if 10 ml. of the sample are treated with some NajHgSj
solution and solid ammonium chloride. Mercuric sulfide is precipitated:
NajHgSj + 2 NH4CI - * 2 NaCl + (NH4)2S + HgS
The precipitate functions as a "trace catcher" for lead sulfide. In other
words, small quantities of lead, which of themselves will not precipitate as
sulfide, are coprecipitated with the mercuric sulfide. If the mixed precipi-
tate is treated With hydrogen peroxide and ignited, the mercuric sulfide is
driven off and lead sulfate remains. This can be recognized by the formaf
tion of red lead rhodizonate when spotted with sodium rhodizonate and
buffer solution.
The following procedure will permit the detection of lead in a dilution
of 1:10,000,000 in 10 ml. water. Lead can be detected in 100 ml. water at a
dilution of 1:100,000,000. These dilutions correspond to 0.00001% Pb
and 0.000001% Pb, respectively. It requires about 20 minutes to carry
out this'procedure for the detection of traces of lead.
f ProcedureTen ml. of Ihe water to be tested are treated with 0.25
ml. Na2HgS2 solution. A partial precipitation of HgS ensues bêcause of
hydrolysis. The precipitation is completed by addition of 0.6 t o 1 g. C.P.
NH4CI and brief digestion. The flocculated precipitate is collected on a
porcelain filtering crucible and washed once with water. Five ml. hydrogen
peroxide are added, and after 3 minutes the liquid is sucked off. The
crucible, together with the wet precipitate, is placed in a porcelain dish
and heated on an electric hot plate until the black mercuric sulfide has
disappeared. The crucible is then ignited gently over a burner for 1 min-
ute. After cooling, the contents of the crucible _are moistened with 5
" F . Feigl and N. Braile, Analyst, 69, 147 (1944).'
"American Water Works Association, Manual of Water Quality and Treatment,
New York, 1940, p. 38.
drops of the rhodizonate solution, the liquid is sucked off, and the excess
of the yellow reagent is bleached by spotting with 2 or 3 drops of the buffer
solution and then with 3 drops water. If the sample of water being tested
contained lead, red particles of lead rhodizonate will remain. They are
quite visible against the white bottom of the crucible.
The quantity of lead rhodizonate formed, and consequently the in-
tensity of the color produced, depends on the lead content of the water.
Therefore, it is possible to compare the intensity of the color of the red
residue obtained in this test with that produced by residues obtained from
various standard solutions. Suitable dilutions are: 1:0.5-10'; 1:1-10';
1:2 10'; - 1:1 -10'. Thus it is possible to estimate the lead content by
colorimetric comparison, which is adequate in many cases.
Reagents: 1) NajHgSj solution: 13.6 g. HgCU are dissolved in 60 ml.
hot water. Solid Na^S, and later NaiS solution, is
added until the initial precipitate of HgS has completely
dissolved. The solution is then made up to 100 ml.
2) NH4CI solid: The salt used mu,st be of highest purity
S) Hydrogen peroxide: 3 % solution
4) Sodium rhodizonate solution: 2 mg. of the salt in 1 ml.
water. The solution must be freshly prepared, since it
gradually undergoes oxidative decomposition on stand-
ing. The solution is stable for 2 days if stored in a
refrigerator
0) Buffer solution (^JH = 2.79) :1.5 g. tartaric acid and 1.9
g. sodium bitartrate in 100 ml. water
The foregoing method of detecting traces of lead can also be used
in the examination of certain chemicals of high purity. One to 5 g. of the
sample are dissolved in 10 ml. water. The procedure just described is
used. Many alkali salts of the highest purity were- tested for traces of
lead by this method. The packages bore labels reading, "Heavy metals
as Pb . . . 0.0003%," " . . . 0.0005%," respectively. Colorimetric determina-
tion of lead by the procedure given here showed values between \ and ^
of the indicated lead content. When identical quantities of the same
salt, coming from different sources, are tested by this method, it is often
possible to discover the source by the lead content. It is remarkable that
alkali sulfates generally show a higher lead content than other alkali salts.
The lead content of acetates usually is less than -^ of the indicated amount
of heavy metals. The same is true for magnesium sulfate -of the highest
purity. Sulfuric acid can be tested for lead by this method. The sample
is evaporated, and the residue treated with sodium rhodizonate and buffer
solution.
432 V n . APPLICATIONS OF SPOT HBACmONS
Detection of Lead in Bismuth Compounds''

When solutions of lead or bismuth salts are treated with alkali
hypobromite, lead peroxide and higher oxides of bismuth afe formed.
These products react with benzidine acetate to give benzidine blue (see
page 55). However, if bismuth salts are heated alone with alkali hy-
droxides, a yellow precipitate forms, which is probably BiO(OH), and this,
when once formed, is not converted into higher bismuth oxides on treat-
ment with hypobromite. This resistance is applied in the detection of
lead in bismuth salts. The following procedure is recommended in the
examination of pharmaceutical bismuth preparations (e.g., bismuth sub-
gallate, -tannate, -sahcylate).
f ProcedureOne g. of the sample is ashed in a porcelain crucible
and the residue taken up in cone, nitric acid and evaporated to dryness.
Ten drops water and 20 drops 3 iV sodium hydroxide are added, and the
mixture boiled for 1 or 2 minutes. The spot test on paper for lead, given
on page 56, may be carried out with 1 or 2 drops of the supernatant alka-
line liquid without filtration.
Detection of Tin in Minerals, Metallic Objects, etc.
The very sensitive cacotheline reaction, described on page 87, may be
applied for the rapid and certain detection of tin in minerals." A few mg.
of the powdered substance, mixed with sodium carbonate and potassiimi
cyanide, is melted on a Wedekind magnesia spoon or on a stick of magnesia.
Reduction to metallic tin takes place:
SnOs -I- 2 KCN = 2 KCNO + Sn
The melt is dissolved in a little hot cone, hydrochloric acid (CATTTION:
HCN is liberated). The solution is tested for tin by treatment with
cacotheline, either in a test tube or on paper impregnated with the reagent
(see page 88).
The test has been tpplied in the analysis of the following minerals."
Cassiterite (Sn02) from Schlaggenwald
Stannite (Cu2FeSnS4) from Zinnwald and also from Cornwall
Teallite (PbSnS2) from Santa Rosa, Bolivia
Cylindrite (PbSn6Sb2S2i) from Poop6
Franckeite (Pb3Sn2Sb2S2i with 1.1% Ge) from Poop6
If tin is to be detected in metals, alloys, etc., a drop of cone, hydro-
chloric acid is placed on the surface of the sample, and stirred with a
platinum wire to accelerate solution of the tin tpjorm SnCU. A drop is-
F. Feigl and A. Singer, Pharni. Presse, 8, 37 (1935).
"Studies with R. Novdcek.
"Specimens from the State Natural History Museum, Vienna.
DETECTION OF MOLYBDENUM 433
placed on filter paper and treated there with a solution of cacotheline.

In the presence of tin, a red color forms.
Another test that can be applied to alloys containing much tin, and
to tin-plated metals, and to tin itself, is based on the formation of violet
stanirous rhodizonate.''
If such materials are treated with a tartrate buffer solution (pH =
ca. 3) and a solution of sodium rhodizonate, stannous tartrate is formed.
It immediately reacts with the reagent and forms dark violet stannous
rhodizonate. Unlike inorganic stannous salts, the rhodizonate does not
undergo autoxidation under the test conditions. Consequently, the
continued action of the buffer solution and the reagent gradually produces
considerable quantities of the colored tin rhodizonate. The test cannot be
used for the detection of small amounts of tin in the presence of much lead,
because the latter forms red lead rhodizonate (see page 56).
TfProcedureOne drop of the buffer solution, and 1 drop sodium
rhodizonate are placed on a flat surface of the sample. No immediate
reaction is observed when the solutions are stirred, but after 3 or 4 minutes,
the spotted area becomes slightly gray. The intensity increases and the
color becomes dark violet after about 6 minutes. If the surface of the
metal is scratched with a steel needle and then spot-tested with the two
solutions, the furrows turn dark violet within 3 minutes. It is also feasible
to treat 1 to 3 mg. of cuttings, in a depression of a spot plate, with the
solutions. The surface of the particles turns dark violet after a few
minutes.
Reagents: 1) Sodium rhodizonate, 0.2% solution
Buffer solution (pH = 2.79): 1.5 g. tartaric acid and
1.9 g. sodium bitartrate in 100 ml. water
Detection of Molybdenum in Tungsten Ores and Technical Materials'^
The very sensitive and specific color reaction for molybdates with
potassium xanthate, described on page 93, may be applied for the detec-
tion of a very small inolybdenum content in tungstic acid or tungsten
oxides (e.g., in scheelite, CaW04, an important source of tungstic acid).
If ProcedureA sample of about 0.1 to 2.0 g. is digested with the
least possible voliune of cone, sodixun hydroxide in a small crucible and
acidified with a drop of phosphoric acid. Soluble complex phosphotungs-
tic and phosphomolybdic acids are formed. A few crystals of potassium
xanthate are then added. In the presence of molybdates, a dark violet to
red color forms, according to the molybdenum content. The color dis-
appears on standing.
Molybdenum can be detected in steels without removing cuttings
"F. Feigl and N. Braile, Chemist-Analyst, 32, 56 (1943).
"K. Agte, H. Becker-Rose, and G. Hoyne, Z. angew. Chem., 38,1124 (1925).
434 VII. APPLICATIONS OF SPOT HEACTIONS
I
by subjecting the sample to an oxidizing etch with nitric acid. The result-
ing molybdic acid is absorbed in filter paper, which isi then tested by the
xanthate reaction.^" 1
Differentiation between Palladium and Platinnm Foil^'
A drop of an alcohol solution of iodine is placed on the foil, and
allowed to evaporate in the air. The formation of a brown-black fleck
of Pdl2 indicates the presence of palladium. The stain disappears on heat-
ing to redness, as the Pdl2 decomposes into its elements. Palladium that
has been electrolytically deposited on metals can also easily be identified
in this way. Platinum produces no stain.
Detection of Nickel Plating and Nickel in Alloys

A nickel content may be rapidly detected by means of the TschugaefT
dimethylglyoxime reaction (see page 114).
llProcedureOne or 2 drops cone, nitric acid is placed on the sample
and left for 1 to 2 minutes. The solution is then taken up on a strip of filter
paper and held over a dish of ammonia in order to neutralize the excess
acid. A drop of acetic acid is placed on the paper, and the moist portion
spotted with a drop of saturated alcohol solution of dimethylglyoxime.^'
In another method of testing for nickel in alloys, the surface is freed
of grease with ether, and a drop of a solution of 0.5 g. dimethylglyoxime
in 5 ml. 98% alcohol and 5 ml. ammonia are added. A pink fleck of
nickel di^nethylglyoxime is formed and may be made clearly visible by
rubbing a piece of filter paper on the stain. The test is more sensitive if the
tested portion of the surface is oxidized by the action of a blowpipe flame,
before treating it with the reagent.^'
Detection of Trace;^ of Nickel in Cobalt Salts'*

The detection of nickel with dimethylglyoxime is quite selective and
very sensitive. The test fails, however, in ammoniacal or acetic acid
solutions containing small amounts of nickel in the presence of much cobalt
because cobalt ions also react with dimethylglyoxime with formation of
soluble brown compounds of bi- and trivalent cobalt. Dimethylglyoxime
is thus consumed by the cobalt and is not available to react with the nickel,
since the solubility of the reagent is quite limited. Furthermore, the color
"M. T. Petrov, Chem. Abstracts, 31, 2120 (1937). /
" E . Merck, Prufung der chemischen Reagenzien auf Reinheit, 4th Ed., Darm-
stadt, 1931. * -''7
"A. Bianchi and E. di Nola, Chem. Zentr., 1910,11, 913.
"V. Fortini, Chem.-Ztg., 36, 1461 (1912).
" F . Feigl and H. J. K&pnlitz&a,Mikrochemie (Emich Festschrift),1930, p. 128;
Z. anal. Chem., 82,417 0^30). ^
DETECTION OF TRACES OF NICKEL IN COBALT SALTS 436
of the solution, which is often dark brown, makes it very difficult to see small
amounts of the nickel precipitate. Finally, the nickel dimethylglyoxime is
very appreciably soluble in the solution of the cobalt dimethylglyoxime
compound. For these reasons, for a long time it was impossible either to
detect or determine nickel in cobalt salts by the dimethylglyoxime reaction
in ammoniacal or acetic acid solutions, when the proportion of nickel to
cobalt was less than 1:100 for an amount of nickel of 0.03 mg.
These difficulties may be avoided and Ni may be detected in the
.presence of any given amovmt of Co. A simple device accomplishes this
end. The procedure consists in converting both the Ni and Co to the
complex cyanides KsNi(CN)<and K3Co(CN)8, by the addition of potassium
cyanide and hydrogen peroxide. Formaldehyde is added and the di-
methylglyoxime reaction is then carried out. The complex ion Co (CN)
IS unchanged by formaldehyde, so that the cobalt is left in a form inactive
towards dimethylglyoxime, whereas the K2Ni(CN)4 is decomposed by
formaldehyde and alkali, with the formation of the potassium compound
of glycolic nitril^* and nickel hydroxide. The latter reacts at once with
dimethylglyoxime.
The chemical changes occuiring in this test are:
(a) Conversion of nickel and cobalt into the complex salts:
Co+++-2'CN-= Co(CN)2
Co(CN)j + 4 -KCN = E:4CO(CN),
2 K4Go(CN)6 + HjOs = 2 KsCoCCN)^ + 2 KOH
Ni++ + 2 C N - = Ni(CN)s
lfi(CN)2 + 2 KCN = K2Ni(CN)4
(b) Decomposition.of the complex nickel sali; by formaldehyde:
KjNKCN)* + 4 CH2O 4- 2 KOH =
/ O K [potassium salt of
Ni(OH)2 + 2CH3<^ Uhe nitrile of giy-
N D N [colic acid
(c) Precipitation of nickel dimethylglyoxime:
Ni(0H)2 + 2 C4HN202 = Ni(C4H7N202)2 + 2 H2O
The following procedure involves the complete course of this series of
reactions. It permits the detection of Ni in preparations of cobalt which
were hitherto taken to be nickel-free, even those labeled "for analysis."
"Compare A. Prins, CAm. Weekblad,27, 191 (1930), regarding the mechanism
of the precipitation of nickel dimethylglyoxime from alkali cyanide solution con-
taining formaldehyde.
436 VII. APPLICATIONS OF SPOT BEACnONS
When traces of nickel are to be detected, a comparison test should be car-

ried out with an absolutely nickel-free cobalt salt. Thepreparation of such
salts is described below. ,
1[ProcedureA sample (about 0.05 to 0.06 g.) of the water-soluble
cobalt salt is placed on a spot plate. A similar quaiitity of a nickel-free
cobalt salt is placed in the adjacent depression. Each is dissolved in 1 or 2
drops of water and treated, drop by arop, with a cone, solution of potassium
cyanide, with stirring, until the initial precipitate is redissolved. . Then 1
or 2 drops hydrogen peroxide are added, in order to convert into the cobaltic
compound, and the mixture stirred until the solution becomes bright yellow
(color of the Co(CN)r ions. This occurs in a few minutes. A few mg.
dimethylglyoxime (tip of knife blade) and then formaldehyde (a few drops)
are added and the mixture stirred. In the presence of nickel, the solution
turns orange-red, or a red precipitate appears. The nickel-free parallel
test remains yellow. Very small color differences, due to traces of nickel,
may be distinguished by comparing the tests.
Reagents: 1) Saturated potassium cyanide solution
2) 3% hydrogen peroxide solution
S) 40% formaldehyde solution
4) Solid dimethylglyoxime
Preparation of practically nickel-free cobalt salts.** Ten g. of a
salt containing as little Ni as possible are dissolved in water and treated,
while warm, with a cone, solution of KCN until the initial precipitate re-
dissolves. The solution is clear atfd greenish yellow. Then 3 % hydrogen
peroxide is added to convert to K3Co(CN). The mixture is boiled for a
few minutes, when the solution should be honey-yellow, if the change
has not taken place, more peroxide should be added. If a slight precipi-
tate has formed, it should be filtered off. The filtrate or solution is boiled
down until it becomes viscous. An excess of solid dimethylglyoxime is
added, and 40% formaldehyde*is poured into the lukewarm solution, with
vigorous stirring. On cooling, nickel dimethylglyoxime and solid dimethyl-
glyoxime precipitate. After standing for an hour, the suspension is filtered
and the (nickel-free) filtrate is evaporated to dryness over a sand bath.
It is cautiously heated further, with continuous stirring, until the mass
begins to char and appears quite black. After cooling a little, it ,is mixed
to a paste with a little warm water. Then cone, hydrochloric acid is added
and the suspension heated for 1 to 2 hours over the water bath. The
massisdiluted with water and filtered. The filtrate is saved. The residue
is dried, ignited, made into a paste with water, treated with cone. HCI,
diluted, and filtered. The twofiltratesare then united. Alkali is added and
Co(OH)2 prebipitates. It is thoroughly washed, dried, and converted to
"F. Feigl and H. J. Kapulitzas, Z. anal. Chem., 82, 417 (1930).
DETECTION OF IBON 437
oxide by ignition. Reduction in a current of hydrogen produces metallic

cobalt. The washed oxide or the metal can be dissolved in acids. Crys-
tallization delivers nickel-free cobalt salts. These are necessary for the
parallel tests prescribed in the foregoing procedure.
Detection of Zinc in Plated Metals
A drop of 2 2V siilfuric acid is placed on the surface to be tested, and
allowed to attack it for about a minute. The drop is then taken up on
filter paper soaked in dilute copper sulfate solution. The fleck on the
paper is then treated with a drop of ammonium-mercury thiocyanate
solution. Zinc is revealed by a violet color (see page 73).
When the fleck is red, owing to ferric thiocyanate from large amounts
of iron, a drop of ammonium fluoride solution is added. This discharges
the thiocyanate color, so that the violet of the zinc-copper-mercury-silver
thiocyanate becomes clearly visible.
Reagents: 1) Copper sulfate paper. Quantitative filter paper is
impregnated with a 0.1% solution of copper sulfate and
dried
2) Ammonium-mercury thiocyanate (for preparation see
page 73)
Detection of Traces of Iron in Fluorides"
The usual thiocyanate reaction is not applicable to the detection of
small amounts of iron in fluorides, because the trivalent iron is present in
solution as the complex FePV . The Fe+++ ionic concentration delivered
by this complex is insuflScient for the formation of Fe(CNS)3. The same is
true for the Prussian blue reaction. The a,y-dipyridyl or a,a'-phenan-
throline reaction described on page 122 may be used without difficulty, if
the iron is converted beforehand into iron (II) salts. Since'HjS is without
appreciable effect on FeFT ,, it is advisable to treat the solution first with
ammonium sulfide, whereby iron sulfide is formed, and then to acidify in
the presence of a, a'-dipyridyl. Ferric ion produced by the acid is reduced
by the HjS formed simultaneously, in spite of the presence offluorideions,
and is immediately taken up as the red ferro-dipyridyl ion, which is com-
pletely stable toward fluoride ions.
^ProcedureOne ml. of the test solution is placed in a parafiined
porcelain crucible. A drop of anamonium sulfide is added, and after 1
minute a hydrochloric acid solution of a,a'-dipyridyl added. According
to the iron content, a red to pink color appears.
In this way as little as 4 -y Fe may be detected in 1 g. potassium
fluoride.
" F . Feigl and H. Hamburg, Z. anal. Chem., 86, 7 (1932).
438 Vll. APPLICATIONS OF SPOT REAC!TIONS
Detection of Traces of Iron in Mercury Salts"

The thiocyanate test, which is usually applicable', is not suitable for
detection of iron in the presence of large amounts of mercury salts. The
thiocyanate ion added is consumed in the formation of the slightly disso-
ciated Hg(CNS)!!, or of double thiocyanates of mercury. The Prussian
blue reaction is uncertain, owing to the formation of yellow mercury ferro-
cyanide, though this test may be unproved by adding sodium chloride (with
solution of the mercury precipitate). The a,a'-dipyridyl test as given
here is simpler.
f ProcedureOne or two drops of the' test solution is heated with a
like volume of reagent solution, a little solid NasSOj, and NaCl. In the
presence of traces of iron, a pink color appears at once. The NaCl is
added to form Na2HgCl4, in order to prevent the separation of the white
insoluble double salt of HgCU and a,a'-dipyridyl.
Detection of Small Amounts of lion in Alumina and Pyrolusite^^

The sensitive Q;,a'-dipyridyl test for iron, described on page 122, may
be used for the detection of the slight iron content in alumina and pyrolu-
site, if care is taken to dissolve and reduce the iron to Fe(II) salts.
If ProcedureA quantity of alumina (size of pea) is finely powdered
and fused with potassium bisulfate in a porcelain crucible. The melt is
dissolved in water, and sodium sulfite and 1 or 2 drops of an acid solution of
dipyridyl are added. When iron is present, a pink color appears.
. A similar amount of pyrolusite is powdered and dissolved by warming
with a little hydrochloric acid plus 3 % hydrogen peroxide. Sodium sulfite
and a little of the solid reagent are added to the solution. A more or less
intense pink results, according to the amount of iron present.
Detection of Chrdmium in Rocks and SteeK ^

The sensitive diphenylcarbazide reaction for chromates, described
on page 128, affords a certain test for even traces of chromium in very
small samples of rocks.^'
IfProcedure(Rocks) A pin-head sized splinter of the rock sample
is ground to a fine powder in an agate mortar and mixed with four times
its bulk of a mixture of equal parts of sodium potassium carbonate and
sodium peroxide (or sodium potassium carbonate and potassium chlorate).
When a red hot platinum wire is dipped once or twice in this oxidation
mixture, sufficient is removed to melt into a transpareat brad, in which any
" F . Feigl and H. Hamburg, Z. anal. Chem., 86, 7 (1932).
"Studies with R. Nov&oek.
DETECTION OF URANIUM IN MINEIULS 439
chromium is converted into chromate. The melt is cooled and dissolved

in 1 or 2 drops of sulfuric acid (1:1), on the spot plate, and a drop of 1%
diphenylcarbazide solution is added. A violet to pink color forms accord-
ing to the amount of chromium present in the sample. It is necessary to
carry out a blank test only when testing for very small amounts of chro-
mium, or when an old reagent solution is used, which may itself be slightly
colored (yellow to pink).
Chromium was decisively detected in the following powdered minerals
in 3 to 4 minutes:
Peridotite, 0.19% CrjOj
Olivinic tfinite, 0.04% CrjOj
Piterite, 0.11% CnOi
Smaragdite, 2.30% CrjOs
Gangue and fuchsite, 0.24% CrjOs
Pyrope (magnesia-alumina garnet), 1.8-2.4%
Chromium was also detected in the following unanalyzed minerals
from various sources: fuchsite, serpentine, chromodiopside, chromochlorite,
wavellite.
[Steel) The surface of the specimen is cleaned with emery paper.
This prepared surface is treated with 2 or 3 drops of a mixture made from
equal volumes of nitric acid, sulfuric acid (1:1) and water. After 3 min-
utes, a drop is removed by means of a fine pipet, and evaporated in a por-
celain crucible. The residue is ignited gently. Sodium peroxide (tip of
knife blade) is added and the mixture fused until no more bubbles form.
The cooled melt is acidified with sulfuric acid (1:1) and tested for chromate
with diphenylcarbazide solution.
Detection of Uranium in Minerals'"

The potassium ferrocyanide test for uranium, described on page 157,
may be applied to the detection of the element in minerals {e.g., broeggerite,
samarskite, etc.).
^ProcedureA pin-head sized sample isfinelyground and fused with
sodium carbonate or potassium sodium carbonate in a loop of a platinum
wire in the blowpipe flame. On cooling, the melt is evaporated to dryness
with hydrochloric acid on a platinum crucible lid. The residue is moistenfed
with a drop of the acid and diluted with a little water. The further proce-
dure is that described on page 157.
When carrying out the spot test for uranium in minerals, precautions
must be taken when, as frequently happens, titanium is present. With
potassium ferrocyanide, this gives a yellow stain which gradually turns
" N . A. TananaeS and G. A. Pantschenko, Z. anorg. allgem. Chem., IBO, 164
(1926),,
.1
brown. In such cases it is advisable to mix a drop of the test solution with
ammonia on a watch glass, warm gently, and acidify with acetic acid. The
uranyl hydroxide goes into solution, while the titanium^ hydroxide remains
behind. The precipitate is best separated by centrifuging, and the titani-
um-free solution can be tested for uranium.
Detection of Titanium in Minerals
The chromotropic acid reaction of titanium salts, described on page
151, can also be applied for the detection of titanium in minerals (rutile,
kaolin, monazite, etc.), after the TiOa in them has been converted to
Ti(S04)2.
TfProcedure"'*A pin-head sized sample isfinelypowdered and mixed
with 3 to 4 times its bulk of potassiiun bisulfate and fused on a platiniun
foil. The melt is transferred to a watch glass, rubbed with a little water,
and placed on filter paper impregnated with chromotropic acid. When
titanium was present, a red to brown red color appeared, according to the
amount.
The test is even more sensitive if a drop of a hydrochloric acid solu-
tion of stannous chloride is added to the whole melt on the watch glass,
and then a few drops of chromotropic acid are added. In the presence of
titanium, not only the solution, but also the undissolved, particles are
tinted red.
It is both better and simpler to proceed as follows, especially when
testing for very small amounts of titanium.'' The finely powdered sample
is mixed with a few drops of cone, sulfuric acid in a microcrucible or test
tube and heated to fuming. After cooling, a small particle of solid chro-
motropic acid is added and the mixture warmed gently. When titanium is
present, a more or less intense violet color appears.
For the detection of traces of titanium La silicates^ such as glass,
it is advisable to fume a few mg. of the powdered sample with 2 or 3 drops
of hydrofluoric acid in a platinmn spoon, then to heat with 2 or 3 drops of
cone, sulfuric acid. After rinsing the contents of the spoon into a test tube
containing a little cone, sulfuric acid, the test with chromotropic acid may
be carried out, as described.
Detection of Magnesium in Silicate Rocks
The very sensitive magnesium test, using p-nitrob^nzeneazo-a-
naphthol, described on page 173, affords a rapid method for the detection
of magnesium in silicates (talc, asbestos, e t c . ) . ' '
*N. A. Tananaeff and G. A. 'Pantsohenko, Z. anorg. allgem. Chem., 160, 163
(1926).
"F. Feigl and H. Kj,Ballaban, unpublished stupes.
DETEC?nON OF ALKALI METALS IN SILICATES 441
UProcedureA few mg. of the finely powdered sample are mixed

with sodium potassium carbonate and fused in a loop of platinum wire.
The bead is dissolved in 1 or 2 drops hydrochloric acid (1:1) on a spot
plate; a drop of 2 iV NaOH and one of an alkaline solution of the reagent
are added. A blue precipitate or color, compared with a blank, indicates
magnesium.
The procedure to be used in the presence of large amounts of iron
and aluminum is described on page 175.
Detection of Potassium in Silicate Rocks'^
The presence or absence of potassium is often characteristic of certain
members of the two main classes of silicate rocks. For instance, sodium
and potassium felspars are distinguished in the class of the anhydrosilicates.
Among the metasilicates, only the leucites contain potassiimi, and among
the orthosilicates, only certain members of the nepheline group contain
potassium (or cesium). Likewise, among the hydrosilicates, which include
zeolites, mica, serpentine, and talcs, only certain varieties contain po-
tassium.
It is not possible to detect potassium directly in silicate rocks, since
the samples almost always are complex silicates in which the potassium is
not bound ionogenically. However, silicates can be decomposed by
fuming with hydrofluoric acid plus cone, sulfuric acid (conversion ofSiOj
into gaseous SiFi). Subsequent ignition produces sulfate. The residue
will contain any potassium. It can then be detected by reaction with
dipicrylamine (see page 178).
^[ProcedureA little (several mg.) of the rock is pulverized and
treated in a platinum crucible or spoon with several drops of hydrofluoric
and cone, sulfuric acid. Solid ammonium fluoride may be used in place
of the hydrofluoric acid. When no more acid fumes are evolved, the
sample is ignited briefly, allowed to cool, and the residue scraped from the
reaction vessel with a nickel spatula. The test portion is placed on a strip
of orange-red dipicrylamine paper, moistened with 1 drop water, and dried
in a current of heated air. The paper is then bathed in 0.1 N nitric acid.
If potassium is present, a red fleck is left on the paper which is turned bright
yellow by the acid. The preparation of the dipicrylamine paper is de-
scribed on page 180.
Detection of Alkali Metals in Silicates''
The chlorides, nitrates, and fluorides of all the metals are converted
to carbonates, oxides, or the free metal by evaporating to dryness with
"Compare F. Feigl, op. cit. (this text, page 2), page 207.
N. A. Tananaeff, Z. anorg. allgem. Chem., 180, 80 (1929). 29
442 VII. APPLICATIONS OP SPOT EEACTIONS
oxalic acid, followed by ignition. After taking up the ignition residue in

water, the filtrate will only react alkaline to litmus jvvhen either calcium
oxide or the carbonates of the alkali metals are present. If the ignition
with oxalic acid is followed by treatment with amnionium carbonate to
convert any calcium oxide to carbonate, then an alkaline reaction to litmus
indicates alkali metals.'^
^[ProcedureA finely powdered sample of the silicate is decomposed
by fuming with hydrofluoric acid on the lid of a platinum crucible. After
the silicon fluoride and excess hydrofluoric acid have volatilized, the metal-
lic fluorides are left. The dry residue is moistened with 2 or 3 drops of
hydrochloric acid, and about 1 ml. water and a little solid oxalic acid are
added. The mixture is evaporated to drjmess and then heated to redness.
The evaporation and ignition with oxalic acid is repeated. The residue is
then moistened with a cone, solution of ammonium carbonate and evapo-
rated to dryness, but not heated to redness, lest the calcium carbonate
should be converted back to oxide.
The residue is rinsed into a centrifuge tube with a little water. The
suspension is warmed and centrifuged. The clear supernatant liquid is
evaporated on a platinum lid and then ignited at a dull red heat, to convert
any magnesium carbonate to the oxide. The residue, after ignition, is
moistened with a little water and carefully warmed. The alkali carbonates
go into solution, but magnesium oxide adheres to the platinum lid (usually
in the form of a small stain). A drop of the perfectly clear solution is
removed with a capillary and placed on litmus paper. If the paper turns
blue, it indicates the presence of an alkali metal in the silicate.
When only traces of the alkali metal are present, the litmus paper
does not turn blue at once. The first drop causes no color change, but
on adding further drops in the same place, the center of the moist portion
remains ahnost unchanged, butia pale blue circle is visible on the periphery.
In this way, a content of as little as 0.2% of the alkali may bejdetected,
e.g., in kaolin.
Differentiation between Magnesite and Dolomite or Braunerite^^

Niunerous slightly soluble magnesium compounds (oxide, hydroxide,
carbonate, phosphate, etc.) are colored a deep red upon heating with an
alcoholic-alkaline solution of diphenylcarbazide. The deep red color is
stable and persists even after boiling with water. This cbloration with
diphenylcarbazide is probably due to an, adsorption phenomenon similar
to the magnesium color reaction described on page 172. The color appears
"Alkali metals can be detected in mixtures of salts by this oxalate method.
itails consult thftôriginal paper.
F, Feigl, Z. am. Chem., 72,113 (1927); M^SOQ (1928).
MAGNESITE AND DOLOMITE 443
clearly even in a mixture of 1 part magnesium carbonate and 200 parts

calcium carbonate, yet it does not appear at all when the magnesium
carbonate is in the form of dolomite MgCOj CaCOa. This masking of the
magnesium diphenylcarbazide reaction is clearly due to the fact that
dolomite may be regarded as the calcium salt of a magnesium carbonato com-
plex,'^ Ca [Mg(C03)2]. In this, the magnesium is a constituent of a com-
plex anion, and therefore has lost its normal reactivity in the same way as
iron in complex ferro- or ferricyanides. Magnesite and dolomite can
therefore be readily distinguished by a simple color reaction that can be
carried out as a spot test.
Support for the assumption that the particular structure of dolomite
is responsible for the masking of the diphenylcarbazide reaction for mag-
nesium is given by the behavior of the double carbonate FeCOs-MgCOs,
which is kno^vn as braunerite. This mineral, which is isomorphous with ,
dolomite, behaves like the latter toward diphenylcarbazide: it gives no
reaction for magnesium. If dolomite or braunerite are ignited, the dolo-
mitic linking is destroyed and there results a mixture of metal oxides, in
which magnesium can be detected with diphenylcarbazide.
1[ProcedureOne or 2 drops of a hot alcoholic alkaline solution of
diphenylcarbazide is placed in a depression of a spot plate and a pin-head
sized sample of the rock added. After 5 minutes, the colored solution
is pipetted out and replaced by hot water, and this method of washing
continued until no more coloring matter goes into the water. If the
sample is magnesite, or if it contains magnesite particles, a red-violet
product remains. When dolomite is present, or the magnesium is in
dolomitic combination (braunerite), no color results. The magnesium
can then be identified by taking a fresh pin-head sized sample and igniting
it on a platinum crucible lid. The dolomitic linking is destroyed and the
ordinary reactive magnesium hydroxide is formed. This can be identified
in the manner previously described.
This method of differentiating the minerals has been tested on many
carbonate and magnesia minerals." In certain cases the magnesite or
dolomite nature of the mineral was recognized, although it had been
wrongly classified from its habit. The diagnosis from the diphenylcar-
bazide reaction always agreed with that deduced from the quantitative
analysis carried out later.
The procedure can also serve to identify small amounts of non-
dolomitic magnesium, in chalk. The magnesia content Avas definitely
established in a limestone of the composition: 0.49% MgO, 64.02% CaO,
1.77% FejOa + AI2O3, 0.23% SiOs, and 32.27% loss on ignition.
"Compare F. Ephraim, op. cit. (page 93), page 805.
" F . Feigl and H. Leitmeier, Chem. Abstracts, 22, 2903 (1928). Compare R.
Novdcek, Veda pHrodni, 14, 267 (1933).
444 VII. APPLICATIONS OP SPOT HBACTIONS
Detection of lime in Magnesite^^

Lime is a deleterious ingredient in magnesite and frequently it is
desirable to have a rapid method of detecting its presence in samples of rock.
Raw or unbumed samples can be tested by means of the lake formed by the
action of calcium carbonate with alizarin. This appears very quickly if a
weakly acidified reagent solution is used, whereas magnesium carbonate
remains unaltered because of its resistance" to dilute acids.
procedureA particle of the rock, preferably with a polished sur-
face, is dropped into boiling reagent solution. The places containing
lime turn violet, the magnesite areas oecome yellow.
Reagent: 0.1% solution of sodium alizarin-sulfonate in N/15 HCl
Calcite and dolomite, that is, the undecomposed carbonates, may be
distinguished in caustic burned magnesite by spotting or spraying the
sample (grains or surface) with indicators. Phenolphthalein or thymol-
phthalein may be used. The active earth oxides formed by the burning
of the carbonate produce red or blue, respectively. Magnesite dissociates
at 420 C, while calcite and dolomite lose carbon dioxide only at 700 to
900 C , leaving calcium oxide. Accordingly, magnesium can be detected
in causticized magnesite with phenolphthalein, while calcite and dolomite
are still inactive. The caustic burned magnesite turns red-violet, the
harmful ingredients themselves remain uncolored and acquire merely an
accessory coloration from the magnesia dust and indicator.
Some of the calcium in caustic magnesite, however, is present as
active CaO and this reacts like MgO with these indicators. The active
lime (CaO) can be detected in daustic burned magnesite in the presence
of magnesia (MgO) if a buffer is mixed with the indicator. The alkalmity
of the MgO is thus decreased so much that the indicator responds solely to
the CaO. A solution of ammonium citrate and thymolphthalein is suitable.
^[ProcedureThe specimei^, on a watch glass, is raoistened with
several drops of N/3 ammonium citrate solution and then spotted with
th3Tnolphthalein. Within a few seconds CaO grains turn blue, whereas
MgO and CaCOs grains remain unchanged. This procedure can also be
used to distinguish CaO from CaCOa.
Differentiatioit between Calcite and Aragonite'^

The sensitive test for 0H~ ions due to their participation in the re-
action
Mn++ -f. 2 Ag+ -h 4 OH- = Mn02 + 2 i ^ - f 2 HjO
" F . Sehwarz, Mikrochim. Acta, 8, 126 (1938).
" F . Feigl and H. Leitmeier, Chem. Abatracta, 29, 3263 (1935). Compare R.
Nov46ek, Veda pHrodni, 14, 267 (1933).
CALCIUM STTIPATE (oTPStJM ANB ANHYDRITB) 445
(blxck precipitate or color, see NH3 test, page 184), may be used to give a
good and sensitive method of differentiating between calcite and aragonite.
The solubilities in water of these two modifications of CaCOa differ slightly,
aragonite being the more soluble. The reactions when CaCOa is suspended
in water are:
CaCO, =i GaCO, *=i Ca++ + CO7-
8olid disaolved
COT- + 2 H , 0 ?:* H,CO, + 2 OH- or COT"- + H , 0 *^ HCOj + OH"
Aragonite gives rise to more OH" ions than calcite, and on treating a solid
or powdered sample with an aqueous solution (containing Ag+ and Mn++
ions, the 0H~ ion concentration is sufficient to give the 0H~ reaction
(blackening) after | to 1 minute. Calcite only gives a slight gray color
after 10 minutes, and only after several hours does this color deepen to the
black developed by aragonite in about 2 minutes.
This differentiation reaction can also be carried out on thin sections.*'
If magnification is used, the slightest occurrence of calcite and aragonite,
in stalactite sections for example, can readily be detected by the blackening
of the aragonite aggregates.
^ProcedureA small heap of the powdered mineral is placed on a
watch glass on white paper, or on a spot plate, and treated with a drop of
the reagent solution. After about 2 minutes the mass is examined for any
blackening. If this is apparent, aragonite is present.
Reagent: One g. solid Ag2S04 is placed in a solution of 11.8. MnS04-7
H2O in 100 ml. water, and boiled. After cooling, the suspension is filtered
and 1 or 2 drops dilute NaOH solution are added. The precipitate is fil-
tered off after 1 to 2 hours. The solution keeps if stored in dark bottles.
The reagent for 0H~ ions can also be used to show that basic salts
are formed by partial hydrolysis and loss of acid on heating sodium and
potassium fluoride. MgCla behaves analogously. For this test, a small
amount of the sample is melted in a loop of platinum wire and the bead,
when cool, is placed in the reagent solution. The bead is then blackened
by the action of the basic salts present.*"
Identification of Calcium Sulfate (Gypsiun and Anhydrite)

Calciimi sulfate can be identified, in the absence of other slightly
soluble alkali earth sulfates (and lead sulfate), by its action with an acidi-
fied solution of mercuric nitrate (see page 301). Light yellow basic mer-
curic sulfate is formed. This test** requires the absence of all materials
that react with the reagent, such as oxides, carbonates, balides, sulfides,
*F. Feigl, unpublished studies.
"G. DenigSa, Bull. soc. ehim., 23, 36 (1918).
446 VII. APPLICAOTONS OF SPOT BEACmONS
etc. Furthermore, it cannot be applied if the sample has a color which

hides the yellow basic mercuric sulfate.
Another test of wider application*^ is based on the reaction:
CaS04 + Pb-H- -> PbS04 + Ca+î
The lead sulfate is then identified by the sensitive specific reaction with
sodium rhodizonate (see pages 56 and 429).
Strontium sulfate acts like calcium sulfate. In contrast, barium
sulfate, whose solubility product is less than that of lead sulfate, does not
react with lead nitrate.
The following procedure can be used for the. direct identification of
calciimi sulfate in the absence of difficultly soluble calcium salts of acids
that form sUghtly soluble lead salts (sulfides, sulfites, phosphates, ar-
senates). If these are present, the procedure must be modified (see
page 447).
^ProcedureA piece of quantitative filter paper is placed on the
bottom of a Gooch or sintered glass filtering crucible.and wetted. Some
particles of the sample are placed on the paper and spotted with 2 or 3
drops of the Pb(N03)2 solution. After 1'minute, -the'liquid is sucked off.
The excess reagent is removed*' by washing with 0.2 A'' nitric acid (2 ml.)
and then with 3 ml. water or alcohol. The acid and water (or alcohol)
should be added drop by drop, while atgentle suction is applied to the cru-
cible. After washing, the paper is placed on a glass plateand spotted first
w'ith sodium rhodizonate and then with the buffer solution. If the sample
contains calcium sulfate, a red spot is left, or the material on the paper
turns deep red, due to the formation of lead rhodizonate.
Reagents: 1) 2 % Pb(N03)2 solution mixed with an equal volume of
0.2 N HNO3
2) 0.2% sodium rhodizonate (2 mg. in 1 ml. water).
The solution ^ u s t be freshly prepared j^see page 431)
S) Buffer solution (pH = 2.79): 1.5 g. tartaric acid.and 1.9
g. sodium bitartrate in 100 ml. water
The foregoing procedure will reveal the presence of CaSOi used as
filler for paper, provided Al2(S04)3 is absent. The test is carried out on
the ash yielded by several mg. of the paper. The mineral barite (BaSO^)
can be tested for CaS04. The procedure will reveal gypsum in a mixture
F. Feigl and N. Bmle, Chemist-Analyst, 33, 76 (1944),
"The washing with dilute nitric acid is essential. If omitted, the paper retains
considerable quantities of lead, which react with the rhodizonate evenîn the absence
of PbSOi produced by CaSO^. The retention of lead by filter paper is due to the
hydrolysis of Pb(NOs)j solutions followed by adsorption tSf the hydrolysis product
(basic lead salt) by the paper. This basic salt is destroyed by the acid wash liquid.
GYPSUM AND ANHYDRITE 447
of BaSOi and CaS04 (1500:1). The adulteration of flour with gypsum

cai. be proved by testing the ash.
Superphosphate can be distinguished from phosphate fertilizers
containing no calcium sulfate. The sample (0.1 to 0.5 g.) is fumed twice,
in a porcelain crucible, with 1 ml. cone. HCl. Alcohol is added, and the
suspension is filtered. The contents of the filter are thoroughly washed
with alcohol and then tested with Pb(N0)2, as described.
Differentiation between Gypsum and Anhydrite"

Calcium sulfate occurs in minerals either as gypsum CaS04-2 H2O,
or as anhydrite CaS04. When either of these is presented in the pure state
without any adhering moisture, they may simply be differentiated by the
evolution of water vapor from gypsum when heated in an ignition tube.
When the sample is moist, this test fails, of course, or drying is essential
before making this test.
A better and more rapid differentiation is based on the fact that
gypsum, as the hydrated compound, is more readily soluble in water than
anhydrite. At 100 C , the solubility of CaS04-2 H2O is 0.167% and
CaS04 only 0.067%.'** Even at room temperature the solubilities differ
markedly. Accordingly, gypsiun reacts much more rapidly with sodium
carbonate than anhydrite:
CaS04 + NajCOa t=> CaCOs + Na2S04
AVhen a solution of sodium carbonate, r,eddened with a little phenol-
phthalein, is used, the gypsum decolorizes it rapidly and the anhydrite much
more slowly. This can be used to distinguish between these two forms of
calcium sulfate.
^[ProcedureA few mg. of the samples are finely ground and placed
in adjacent depressions on the spot plate and moistened with 2 or 3 drops
of a sodium carbonate solution that is reddened with phenolphthalein.
On stirring with a platinum wire, gypsum causes an appreciable lightening
of the color change in 1 to 2 minutes and complete decolorization in 4 to 5
minutes, compared with 15 minutes and 45 minutes with powdered an-
hydrite.
The sample in bulk may be tested by placing on it 1 or 2 drops of the
sodium carbonate solution, but the difference is not so pronounced in
this case.
Reagent: 4% sodium carbonate solution containing 3 drops of 2 %
alcoholic phenolphthalein
"K. Feigl and V. Demant, unpublished studies.
"A. E. Hill, / . Am. Chem. Soc, 66, 1071 (1934).
448 VII. APPLICATIONS OF SPOT BEAC!TION9
I
Orienting Tests of Glass

(o) Test for earth and heavy metal oxides.*'^ Aidrop of 10% hydro-
fluoric acid immediately frosts glass that is rich in these oxides. The sam-
ple can be tested for boron, sodium, and potassium by the flame color.
The original paper should be consulted regarding methods of testing for
the other metals after the etching with hydrofluoric acid.
Many of the spot tests described in this book may also be used for the
identification of the constituents of glass.
(&) Identification of glass containing hases.^^ A rough scratched
portion of the glass to be tested is covered with a drop of a watei^-ether
solution of iodoeosin, CMHSIÔJ. This acid is converted by the alkali of
the glass to its sodium salt, Na2C2oH6l406, which is insoluble in ether, and
sticks to the glass as a red film that is easy to see after the surface is rinsed
with ether. This treatment leaves quartz glass colorless, and the red color
(water-soluble) indicates a glass containing basic oxides.
Reagent: 0.5 g. iodoeosin is dissolved in 13 ml. 0.1 iV NaOH in
a separatory funnel, 120 ml. water and then 15 ml. 0.1 N
H2SO4 are added. The dyestuff precipitates. The yellow-
red mixture is vigorously shaken with 1 1. ether and the
dyestuff goes into solution. The layers are separated, and
the ether layer is washed 3 times with 30 ml. portions of
water. The ether solution of the reagent is kept in dark
bottles
The sensitive reaction of 0H~ ions in the test for ammonia (page
184), and also used for distinguishing between calcite and aragonite
(page 444):
Mn++ -f 2 Ag+ -F 4 OH" = MnO^ -f- 2 Ag -|- 2 HjO
may be applied to powdered gl^ss as a rapid means of ^detecting any
content of free basic oxide.*' A small heap of the powdered glass, (a
fragment weighing a few mg. is enough) is treated with the reagent solution
either on a spot plate, a watch glass, or a Wedekind magnesia groove, and
observed for any development and intensity of gray color. The mixture
can be further treated with an acetic acid solution of benzidine,' which
reacts with the MnOj formed (see page 134). A more or less deep blue
results, according to the alkalinity of the glass.
The folloAving siunmary shows the result of testing for alkali in differ-
ent types of glass:*' _ -
" P . Mylius and E. Groachuff, Chem. Abstracts, i, 1798 (1910).
'P. Mylius, Z. anorg. allgem. Chem., 56, 233 (1907).
" P . Feigl, Mikrochemie, 13, 139 (1933).
'Y. Kondo, Mikrochim. Acta, 1,157 (1937).
DETECTION OF FREE METALS IN OXIDES 449
Jena gerSte light gray

Jena normal 16 gray
Jena-supremax light gray
Jena-Duran almost negative
Lead glass gray
Murano light gray
Kavalier dark gray
Pyrex almost negative
Various optical glasses gray to dark gray
The microchemical spot test can be applied to reveal alkali given off
from different kinds of glass. Small samples (splinters, etc.) are enough.
This test is very useful in testing the chemical resistance of glass."" It
should be noted that the particle size of the glass powder used may affect
the result. Furthermore, when the glass is cooled, there sometimes is an
increase in alkali concentration on the surface layers."
Detection of Free Metals in Oxides, Printing on Paper, etc."

Metal oxides, such as ZnO, CuO, CdO, PbO, Pb304, prepared by
heating the metal in contact with air, often, still contain some free metal.
This was protected against complete oxidation because the surface was
coated with a layer of the oxide. In contrast, metal oxides prepared by
calcination of carbonates, nitrates, etc., never contain free metal. Conse-
quently, *he detection of free metal in oxides can be used to establish the
purity of the sample (particularly of ZnO), and it also will sometimes give
information as to the origin of the oxide.
The reaction of free metals with'phosphomolybdic acid (see page 273)
can be used for rapidly detecting free metal in ZnO and other oxides. This
test can also be applied to metal dusts and dusts of alloys on wrappings,
printed paper, etc. The basis of the test is the formation of the highly
colored molybdenum blue by the action of this acid with free metals and
alloys.
^ProcedureAbout 10 mg. of the zinc oxide to be "tested are placed
in a depression of a spot plate. Without stirring, 3 drops phosphomolybdic
acid and 1 drop dilute sulfuric acid are added. The zinc oxide dissolves
slowly. Molybdenum blue is formed wherever traces of metallic zinc
occur. It is quite visible against the undissolved zinc oxide and the white
background of the spot plate. If the oxide contains only a little free metal,
blue particles or isolated dots are seen. If the sample is quite impure, no
"Compare W. Eitel, M. Pirani, and K. Scheel, Olasstechnische Tabellen, Berlin,
1932, page 509.
" E . Reser, Tech. wiss. Abhandl., Osram-Konzern, 2, 277 (1931).
" F . Feigl and G. Dacorso, Chemist-Analyst, 32, 28 (1943).
localized reduction is discerned, but the entire-liquid turns blue or blue-

green. When two varieti^ of ZnO are to be compared with respect to
their content of metallic zinc, it is best to test four portions of each in
adjacent depressions and to count the blue dots. Representative figures
are thus obtained. j
Litharge (PbO) and red lead (Pb304), as well as other metal oxides,
can be tested for free metal by this procedure. It is preferable to substitute
dilute nitric acid for the sulfuric acid, when testing litharge because the
sample dissolves faster. It is remarkable that practically all samples of
T?hzOi give a positive reaction for metallic lead by this test, despite the
fact that they contain quadrivalent lead.
If prints on paper, wrappings, etc., are to be tested for powdered
metals, dusts of alloys, etc., it is merely necessary to place a drop of phos-
phomolybdic acid on the paper and to note the formation ot a blue col-
oration. ,
Reagent: Saturated water solution of phosphomolybdic acid'
Procedure for Testing Woods Impregnated with Solutions of Salts ^'

Spot tests can be applied to investigate the nature of the chemicals
used in the preservation of woods, such as of telegraph poles, powerline
towers; railway ties, etc. The mineral salts most commonly used are
mercuric chloride, copper sulfate, zinc chloride, and sodium fluoride.
Whenever possible, a complete transverse section of the wod should
be used for the test. The core of a bore made with a Pressler growth
borer may also be used. When a drop of the reagent solution is placed
or sprayed on to the material the depth of impregnation may be seen.
The spot tests should be carried out on wood that has been half-moistened
either with a damp cloth or by standing for some hours in aii atmosphere
saturated with water vapor. Sprinkling with water must be avoided lest
the Impregnating material be washed away.
^Procedure1) Mercuric chloride. Spot with ammonium sulfide
(mercuric sulfide formation). Wood that has been impregnated for a
long time will give the reaction more clearly if it is previously moistened
with dilute hydrochloric acid.
S) Zinc chloride. The test depends on the liberation of iodine from
potassium iodide solutions by zinc ferricyanide. The reagent solution is
a mixture of equal volumes of 1% potassium ferricyanide solution, 1%
potassium iodide solution, and 5% starch solution. The layer impregnated
with zinc chloride turns deep blue, when the reagent is sprayed on the
specimen, or if a drop is applied. .- ^
"See F . Moll, Z.. angew- Chem., 38, 73 (1925).
TESTING LEATHER 451
S) Copper sulfate. Impregnation with copper sulfate, now very

seldom used, may usually be identified by its grass-green color alone (due
to copper tannates). On adding a drop of 1% solution of potassium ferro-
cyanide, a brick red to brown-red color appears, due to copper ferrocyanide.
If the color later turns dirty greenish blue, it indicates that the copper sul-
fate contained some iron sulfate.
4) Sodium fluoride. The test depends on the reaction of sodium
fluoride with iron (III) salts to give colorless iron fluoride NaaFeFe;
only an excess of iron salt is revealed by the color reaction with potassium
thiocyanate. Higher concentrations of sodium fluoride (from 2 % up-
ward) may be identified by spraying or applying a drop of red, freshly
prepared, solution of iron thiocyanate,^* and observing the decolorization.
The following reaction, depending on the formation of Prussian blue,
is sharper and more permanent. The wood is sprinkled first with a 5%
solution of potassium ferricyanide, dried, and'then a 5% solution of ferrous
a;mmonium sulfate is added. A dark blue is formed in the portion of the
wood that is not impregnated with sodium fluoride.
When small amounts of the impregnating substance are to be detected,
or if the distribution is to be more accurately followed, other sensitive
tests for the compounds listed may be used to advantage. (See the appro-
priate sections.)
Testing Leather to Find Method Used in Tanning

(Mineral-Tanned Leather)"
In determining the method used in tanning of mineral-tanned leathers,
it is necessary to test the sample for certain inorganic compounds. The
most common mineral tanning compounds are Cr salts; sometimes alumi-
num salts are used, and more rarely, iron salts. These salts may also be
used in combination. Spot tests can be used for the detection of these
mineral tanning agents. The size of the sample of leather necessary is
then so small that it may be taken from manufactured products (shoes,
small leather articles) without causing any appreciable damage.
(a) Detection of chromium. A small sample (less than 1 mg.) is taken
with a razor from the article to be examined. This is best cut from the
inside of shoes and other manufactured articles, as dyes and finishes for
leather occasionally contain chromiimi, and so lead to error. The sample
taken is ashed in a porcelain microcrucible, which takes only an instant for
Isuch a small sample. Then a small heap of sodium peroxide is added and
the mixture heated to complete fusion; the chromium is converted into
chromate. After cooling, the melt is dissolved in the crucible in a few
H).6 g. KCNS and 0.7 g. Fei(S04)i 18H,0 made up to 200 ml. with water.
"K. Klanfer, Mikrochemie, 9, 34 (1931).
452 Vir. APPLICATIONS OF SPOT EEACnOWS
drops of sulfuric acid (1:5) and I or 2 drops of an alcoholic (about 1%)

solution of diphenylcarbazide are added. A deep violet appears if chro-
mium is present. \
{h) Detection of iron. A small piece of leather (about 1 mg.) is ashed
in a microcrucible and then evaporated with a drop of nitric acid, ignited
again and fused with a crystal of potassium bisulfate. When cold, the
melt is dissolved in 1 or 2 drops of dDute hydrochloric acid and a drop of a
solution of potassium or ammonium thiocyanate added. A red color
indicates iron.
(c) Detection of aluminum. Aluminum may be detected either by the
formation of the aluminum alizarin lake (1) or by thefluorescencereaction
with morin (2).
A small sample of the leather is ashed in a microcrucible, and the
residue fused with a crystal of potassium bisulfate. The melt is dissolved
in a few drops hot water and the solution tested for aluminum.
1. Alizarin test. A drop of the test solution is placed on dry filter paper
that has been impregnated with potassium ferrocyanide. Any iron or
chromium present at the same time is held back in the paper, while the
aluminum diffuses through the capillaries and accumulates in a circular
zone. A drop of a saturated alcoholic solution of alizarin is added and the
paper is held over anamonia. The violet color of ammonium alizarinate
then appears. In the presence of larger amounts of aluminum, the straw-
berry red of the aluminum alizarinate can be seen at the same time. How-
ever, if the filter paper is warmed (held briefly near a flame or placed in a
hot air oven), the violet ammonium alizarinate is decomposed due to
volatilization of ammonia, and the red aluminum lake color becomes
clearly visible.
2. Test with morin. A drop of the solution of the melt is treated in a
microcentrifuge tube with 2 drops of a warm, approximately 2 N sodium
hydroxide solution, centrifuged, and the clear solution acidified with a
few drops 2 N acetic acid. Finally a drop of a saturated methyl alcohol
solution of morin is added.
In the presence of aluminum, a green fluorescence appears.
Chemical Identification and Determination of Age of Ink Writing"
Inks may be divided into three classes according to the nature of the
coloring matter: /
Iron gallate inks contain ferrous and ferric saltsy-tannin and gallic
acid, free mineral acids (hydrochloric and sulfuric), and'acid water-soluble
triphenylmethane. dyestuffs.
"O. Metzger, W. Hess, and H. llahl, Beiirige zur kriminalisiiache Sympto-
matologie, Grax, 1930. Coffiê also these writers, Z. ingsw. Chem., 44, 645 (1931).
CHEMICAL IDENTIFICATION OF INK WKITING 453
Logwood inks contain logwood extracts whose dyestuff hematoxylin

is oxidized by chromates to hematein, with which the chromic salt formed
gives lake colors.
Dyestuff inks contain various coal tar dyes.
The characteristic constituents of the first two types of ink can be
detected by spot reactions on paper to which the ink has been applied.
The principle of the method is based on the conversion of the sub-
stance to be identified into suitable insoluble compounds, with simultaneous
decomposition of the dyestuff of the ink, and tofixihe insoluble compounds
on the paper in the position of the original lines of writing. These color-
less, or often barely visible, precipitates adhere firmly to the paper, and
can be converted into colored compounds by means of suitable spot reac-
tions, and hence are made visible. The reactions can be carried out either
as genuine spot tests, or as reactions "in glass" (in vitro), that is, a sample
of the paper is put in a beaker and covered with a large amoimt of the re-
agent. This has the advantage that portions of wTiting of varying inten-
sity can be observed simultaneously. Paper withstands even long treat-
ment with dilute acids, alkalis or sodium hypochlorite.
In order to test for iron, for example, an alkaline oxidizing medium is
used, the iron separates as insoluble ferric hydroxide that is firmly held
on the paper. The excess sodium hypochlorite can be washed off with
sodium thiosulfate and distilled water. The iron hydroxide can be made
visible in the position of the writing by various means, e.g., with thiocyanic
acid, a-nitroso-/3-naphthol, potassium ferrocyanide, or ammonium sulfide.
When a positive reaction for iron is obtained in writing made with logwood
and dyestuff inks, it should be remembered that any iron present, may be
derived from the steel pen.
In order to test mk for chromium, the writing is destroyed with a
drop of 0.5 N NaOCl containing 2% barium chloride. The chromium
is thereby converted into insoluble barium chromate, which can be spotted
with diphenylcarbazide (see page 128).
In testing ink writing, the chloride and sulfate content is an important
criterion of the kind of ink, since iron gallate and logwood inks may be
differentiated in this way. The chloride can be detected in iron gallate
and logwood inks by the following procedure: 1% silver nitrate is added to a
10% solution of sodium nitrite until a large precipitate appears, which is
redissolved in 10% nitric acid. A strip of the wTitmg is placed in this
solution. The chloride in the ink is converted into insoluble silver chloride,
the body of the ink dissolves, and the coal tar dy? is decomposed by the
nitrous acid. The ink is decolorized in about 15 minutes. The excess
silver nitrate is washed out of the paper with 1% nitric acid, which takes
about 5 minutes. The silver chloride retained on the paper is then reduced
to black metallic silver by adding a mixture of 1 part 35% formalin solution
and 10 parts 2% sodium hydroxide. Finally, the paper is washed several

times with distilled water and dried..
When carrying out the chloride test on dyestuff jinks, oxidation with
nitrite is usually incomplete, and potassium permanganate must be used,
although it gives poorer chloride images than the nitrite. The paper is
placed in a 1% silver nitrate solution containing 1% of free nitric acid,
and a few drops of a 2% KMn04 solution are added. After the ink has
lost its color, which should take not more than 1 minute, the manganese
dioxide that has precipitated on the paper is dissolved in 2% nitric acid, to
which a little solid hydrazine sulfate is added as a reducing agent. The
remaining silver nitrate is completely removed by treating with 1% nitric
acid for 5 minutes longer. The rest of the procedure is the same as for
gallate inks as described.
With violet inks, and especially concentrated copying inks, the time
required for oxidation with potassium permanganate is too long. The
dyestuff is therefore dissolved by immersing the writing in a mixture
containing 10% perchloric acid, 5% nitric acid, and 1% silver nitrate.
The violet dye turns yellow. After 5 minutes the reaction is stopped, so
that the paper is not attacked too much. If the dye has not completely
dissolved, it can be treated with potassium permanganate. Otherwise
the silver nitrate is washed out with 1% nitric acid, rinsed with water,
and reduced with the formalin mixture, etc.
In'order to test all kinds of ink for sulfate, a strip of the paper with
writing on it is treated with a solution containing 4% lead nitrate, 4%
free perchloric acid, and a few drops potassium permanganate. The sulfate
in tê ink is converted into lead sulfate, with simultaneous destruction of the
dye. The excess lead nitrate is washed out with water saturated with lead
sulfate. To reduce and decompose the precipitated manganese dioxide, a
few crystals of hydrazine hydrochloride are added, and the specimen is
then washed with distilled water. The lead sulfate is converted into dark
brown lead sulfide with a solution of 2% sodium sulfide and 2% sodium
hydroxide. To prevent the reaction of any sulfate Avith the lead salt in
the paper (derived from the size) it is immersed in distilled water for 5
minutes before carrying out the test.
If writing containing chlorides is tested in this manner, the' writing
reappears in the original position as metallic silver ("chloride image of the
writing"). Conclusions as to the age of the writing may be drawn from
the form of chloride image or from the distribution of the chloride around
the writing. This information may be of considejafele importance in legal
and criminological work. Details are given in the original paper.
PAPEB AND COAL ASH 455
Detection of Fixed Alkalis and Ammonia in Alkali Cyanides"

Before free alkali can be detected in alkali cyanides by a color change
of an indicator, it is necessary to remove the CN~ ions, as these react alka-
line owing to hydrolysis. This is readily done by adding HgClj; undisso-
ciated Hg(CN)2 is formed.
^[ProcedureA small piece of the solid sample or a drop of a solution
is stirred on a spot plate with a drop of a cone, mercuric chloride solution,
saturated with sodium chloride. (The latter prevents hydrolysis of HgClj
through the formation of the complex NajHgCU.) A drop of phenol-
phthalein is added, or a strip of litmus paper dipped in. Free alkali
causes a red or blue color, respectively.
An approximation of the alkalinity may be obtained with the ap-
paratus for the colorimetric determination of pH as described on page 475,
or a pH meter can be used.
Alkali cyanides are often contaminated by" ammonium salts.''
The reaction for ammonia described on page 184 is used to detect them.
The production of ammonia due to hydrolysis of the cyanide:
KCN + 2 HaO = HCOOK + NH,
is prevented by adding a few crystals of HgCU to a drop of the test solution
in the gas apparatus before the addition of the sodium hydroxide. Undis-
sociated, soluble Hg(CN)2 is formed.
Detection of Alkali Earths and Alkali in Paper and Coal Ash^

The reaction: 2Ag+ + Mn++ -f 4 OH" = 2 Ag -f MnOj -f- 2 HjO
may be used for detecting very small amounts of free alkali. The extreme
sensitivity of the test is due to the ease of determining the formation of the
Ag-Mn02 adsorption compound (see page 184). This reaction is especially
useful in the examination and differentiation of ash derived from different
kinds of paper, coal, and charcoal.
In the examination of paper ash, a small strip (about 2 X 3 mm.) of
the paper is ashed on a crucible lid until it has become as near white as
possible. The ash is treated with a drop of the reagent solution. The ash
turns gray or black at once, or in a few minutes, according to the amount
of alkali present. The ash of cigarette paper, newspaper, writing paper,
and qualitative filter paper turns black at once owing to the high alkali
content, but the ash of quantitative filter paper shows hardly any reaction.
"Studies with H. E. Ballaban.
'*W. Bottgerj "Qualitative Analyse anorganisoher Verbindungen." in Berl-
Lunge, Chemisch-iechniache Uniersuchungsmethoden. 8th ed., Springer, Berlin, Vol.
I, 1932, page 132.
Y. Kondo, Mikrochim. Acta, 1, 154 (1937).
456 Vn. APPLICATIONS OP SPOT BBAC?nONS
When testing the alkali contei^t of coal ash, a sample of the coal
(about 0.1 g.) is ashed on a crucible lid. When cold, the ash is treated
with a drop of the reagent. Results of the examination of coal from
different sources are sho%vn in Table 36. I
In order to determine the amount of the water-soluble alkaline con-
stituents of ashes, it is advisable to shake the ash from about 0.1 g. of coal
or charcoal for several minutes with 10 ml. water; allow to stand for 24
hours and then centrifuge. A drop of the solution is then evaporated on a
frosted slide and spotted with the reagent. Hard coal and brown coal
were found to contain very Uttle soluble alkali, while wood charcoal had a
high alkali content. The reaction may be appUed to the rapid examination
of small samples of ash to indicate its origin, for instance whether from hard
or brown coal, or wood charcoal.
TABLE 36
Type of coal or charcoal Color of ash Result of reaction
Bone charcoal Gray Strongly positive

Activated charcoal, granular (Kahlbaum) Almost white Very slight
Activated charcoal, granular (Aussig
Chem. works) Red-gray Slight
Charcoal for decolorization (Kahlbaum) Red-gray Strongly positive
Acid washed blood charcoal... Yellow-gray Slight
Spongy charcoal Dark gray Very strongly positive
Hard coal White Strongly positive
Hard coal Pink Positive
Brown coal Gray
Beechwood charcoal Gray Strongly positive
Reagents: 2.87 g. Mn(N03)2-aq is dissolved in 40 ml. water and

mixed with a solution of 3.39 g. AgNOs in 40 ml. water,
and diluted to 100 ml. Dilute sodiuni hydroxide is then
added drop by drop until a black preci^pitate^separates.
This is filtered off. This reagent will keep when stored in
dark bottles
The reaction with nickel dimethylglyoxime equilibrium solution (see
page 478) can be applied with excellent results for the detection of alkaline
earths and alkalis in ashes.
Detection of Ammonium Salts in Chemicals

The testing of the purity of chemicals*" often prescribes tests for
ammonium salts. This can be done reliably byrneans of the procedure
" E . Merck, PrSfung der chemiachen Reagemien auf Reinheit, 4th ed., Darm-
stadt, 1931.
HSTSBOaENEITISS IN UANinrACTCBED UBTALS 457
given in detail on page 184. This reaction [ammonia on AgNOr-Mn(NOj)j

solution ] is best carried out on one drop of the saturated solution of the
sample.
Imprint and DeTeloping Procedure for Chemical Identification
of Heterogeneities in Manufactured Metals, Minerals, etc."
The sensitive tests for metals and metalloids described in the previous
sections of this book can be applied not only as spot methods employing
drops of a test solution or particles of the solid sample. They also render
practicable a special technique, that is called the imprinting and developing
procedure. This enables the operator to make localized detection of vari-
ous materials.
The imprinting procedure consists in the use of gelatin paper which
has been impregnated with a reagent that is sensitive and specific for the
element to be detected. The prepared paper is pressed moist on to a
smooth meta,l surface, and left there for 5 minutes.
The substance being detected reacts with the reagent in the paper,
and the colored reaction product forms a definite image. After removing
the paper from the surface it can be seen whether the test is positive, and
also, from the localized dispersion on the print or image, the distribution
of certain materials in the test metal itself may be determined. This
procedure is used when the test substance reacts directly with the reagent
and gives a colored product. This isfixedin the gelatin layer and appears
in the finished print, as a mirror image, in those places in which the test
material resides in the sample. The use of ordinary paper generally gives
less satisfactory results, as sometimes the images are indistinct and less
permanent. The gelatin layer adds to the clarity of the print, and occa-
sionally inclusions not visible to the normal eye are quite clear in the print.
This improvement in visibility is due to the capillary diffusion and spread-
ing of the reaction product, from its point of origin, into the gelatin layer or
filter paper. The resulting magnification in the print is not sufficient to
interfere with the localized detection, and there is no danger of distortion.
The print is taken on ordinary glossy gelatin paper, such as is
used in photography (but without silver bromide). The paper must have
a glossy surface in order to give the best contrast, and must of course
be free from the substance tested for. A blank test is necessary to estab-
lish this fact.
The gelatin paper of suitable size is immersed in the appropriate
reagent solution for about 3 minutes, allowed to drain, and placed on the
prepared sample of metal. The gelatin paper should be drawn on to the
"M. Niesaner, Mikrochemie, 12,1 (1932); G. Gutzeit, M. Gyain, and R. Galopin,
Compi. rend. soc. phya. hist, nat., Oenive, 60, 192 (1934); T. Hiller, Schweit.
mineralog. peirog. MM., 17, 88 (1937).
30
458 ' VII. APPLICATIONS OF SPOT REACTIONS
metal rapidly from the side to avoid air bubbles, which lessen the clarity of
the print. It is best to press down the paper thenjwith stiff cardboard
and to leave it in position for about 5 minutes'. '
Another method of taking a print is to place the moist impregnated
gelatin paper on a sheet of glass and press the piece of metal directly on
to it, avoiding bubbles. This procedure is used most generally, especially
with pieces of metal of the size used for the usual optical examination.
It should be noted that gelatin paper is especially attacked by
strongly acid solutions. In such cases filter paper with small pores {e.g.,
S & S 602, hard) may be used successfully.
This method of preparing prints depends on the direct reaction of
the solution of the specific reagent on the paper with the substance to
be detected. If this is impracticable, then a similar developing procedure,
attains the same end. In this procedure, the element to be detected is
taken up on the paper with a suitable solvent, and after removing the paper
from the metal surface, the image is developed by bathing it in an appro-
priate reagent solution. Gelatin paper or filter paper soaked in the proper
solvent is used in this procedure. With the precautions used in taking the
ordinary prints, the paper is placed on the prepared metal surface, or in-
versely, the metal is pressed on the paper, removed after not less than 5
minutes and immersed in a solution of a specific rergent for the substance
to be identified. In a short time, the reaction takes place in the portions
of the paper where the dissolved element has become fixed, after diffusion
in the capillaries, and the image develops.
Sometimes an alkaline reaction is necessary for the test, while solution
only takes place in an acid medium. Then, between the solution process
and the development, the paper is rendered alkaline with ammonia vapor,
while acid vapors may be used in the opposite case when an acid reaction is
desired.
The imprinting process is useful both for detecting inKomogeneities
(undissolved metals, nonmetallic components) and also for the detection of
homogeneously dissolved components of alloys, or for a pure metal itself.
Whereas in detecting inhomogeneities, segregations, etc., the inequalities
show up on the print, prints of alloys containing a homogeneous distribu-
tion give an even color over the surface of the paper, the intensity depend-
ing, among other factors, on the amount of the element concerned.
A nimaber of examples illustrating the practical application of the
method for testing metals are given in the following sectionsfl
(a) Identification of sulfur segregations.'^'^ Technical irons and steels
always contain sulfur and phosphorus, which are the cause of the segrega-
tion phenomena. These elements or their chemical compounds present
M. Niessner, Arch. Huttenw., 3, 157 (1929); Mikrochtmie, 12, 16 (1932)..
HETEROGENEITIES IN MANXTFACTtTHED METALS 459
in the various types of iron and steel, such as iron and manganese sulfides,
and iron phosphide, are not usually evenly distributed in the solidified
metal, but are mainly present in deposits of high phosphorus or sulfur
content. The distribution of these metalloids is very important in their
effect on the mechanical properties of the material, and hence on its quality.
Quantitative chemical analysis can only give the mean content of sulfur
and phosphorus, and supplies no detailed information as to distribution.
Methods have therefore been worked out to afford a rapid means of finding
these local segregations.
Metallographic practice employs both the etching*' and the printing
methods. The first method uses etching agents, specific in effect, which
cause characteristic color changes at the points of segregation. In the
imprinting method, the identification is carried out on some material
pressed on to the surface, and not on the metal itself. One procedure uses
silver bromide paper,^* the other employs mercuric chloride paper.^^
In both cases, a sharply defined image is obtained, due to reaction of the
segregation with the silver or mercury salts. With mercuric chloride
prints, black and yellow flecks are formed on the paper. These were as-
sumed to be mercuric sulfide or phosphide. However, a spot test using
the iodine-azide reaction (see page 227 shows that mercuric sulfide is present
in both the black and the yellow flecks.
Sulfide corrosion in the metal machinery can be detected even in its first
stages by applying the iodine-azide reaction. For instance, corrosion in
distilUng apparatus owing to the use of sulfur-bearing oil, etc. is easily
demonstrated.^
lyProcedureA strip of gelatin paper of suitable size is immersed
for 2 minutes in a hydrochloric acid solution of mercuric chloride. The
solution is allowed to drain off and the damp paper is laid on the de-greased
surface to be tested. The paper is gently pressed down with a piece of
cardboard. The mercuric chloride paper is left in contact with the surface
for 4 to 5 minutes, then removed, and washed in running water for about
half an hour, in order to completely remove any excess mercuric chloride.
Insufficient wa!3hing affects the iodine-azide reaction, owing to the forma-
tion of mercuric iodide. Filter paper is used to remove most of the water
from the gelatin paper, which is then dried at room temperature. A drop
of the iodine-azide solution is placed (with asmall pipet) on the spot to be
tested. When the reaction is positive, bubbles of nitrogen are evolved
''E. Heyn, Miii. kaiserl. Malerialprufungsaml, 1906, p. 253; P. Oberhoffer,
Slahl u. Eisen, 33, 798 (1916).
"R. Baumann, Metallurgie, 3, 416 (1906). Compare K. M. Rauner, Chem.
Abslracls, 31. 972 (1937).
E. Heyn, Slahl u. Eisen, 26, 8 (1906).
K. WeisBelbcrg, Petroleum, 31, 7 (1934).
460 VII. APPUCATIONS OF SPOT BBACnONS
at once from the segregation imprint, and are easily visible to the naked eye.
After 3 to 4 minutes, large bubbles have formed, which stay on the paper.
After the reaction has proceeded for 5 minutes, the iodine-azide
solution may be treated with a drop of ammonia. This causes the separa-
tion of black nitrogen tri-iodide in all the portions where there was no
sulfide. The paper is paler where the iodine-azide reaction occurred,
as the iodine was consiuned there, and no formation of nitrogen tri-iodide
can occur. When the sulfur content is very high, the drop is sometimes
completely decolorized. Nonetheless, the bubbles are clearly visible.
Reagents: 1) Iodine-azide solution. 1.3 g. sodiimi azide are dis-
solved in 100 ml. 0.1 N iodine solution
2) Hydrochloric acid-mercuric chloride solution: 10 g.
mercuric chloride, 20 ml. hydrochloric acid (sp. gr.
1.124) and 100 ml. water
S) Gelatin paper. A blank test with the iodine-azide
solution should be carried out before use, in order to be
sure that no sulfur compounds are present in the paper"
(b) Identification of phosphorus segregations.^' The certain identifi-
cation of phosphorus segregations in steel and iron is important, as these
adversely affect the quality of metal. The difference in reactivity of the
MoOj in the complex compound (NH4)3P04 12 MoOj from the behavior of
normal molybdates (see page 67) affords a possible method for the detec-
tion of phosphorus segregations. The difference in behavior is especially
shown toward reducing agents. Molybdates are reduced by stannous
chloride, through the molybdenum blue stage, to the brown or yellow mo-
lybdenum oxide, while the reduction of the complex compound stops at
molybdenum blue. Thus, after attacking a mixture of molybdates and
phosphomolybdates with stannous chloride, molybdenum blue is left,
whereas, in the absence of phosphorus, only the lovver molybdenum oxides,
which are soluble in acids, are formed. ~- ...
IfProcedureFilter paper, of suitable size, is immersed in a nitric
acid-anmionium molybdate solution, allowed to drain, ^ laid on a glass
plate, and the sample section placed on it. After 3 to 6 minutes, according
to the degree of purity of the material, the section is removed from the
paper and placed in a stannous chloride solution (50 ml. stannous chloride
solution, 50 ml. HCl, and 100 ml. water). This solution dissolves the
lower molybdenum oxides and any iron salts taken up by the paper. At
first the imprint is yellow to brown, and after about 3 to 4 miniites, a blue
"Gelatin sometimes contains organic sulfur compounds which react with the
iodine-azide solution. Any reaction of the paper itself, due to its gelatin content,
is 80 slight, as a rule, that there is practically no danger of any confusion with the
reaction of the segregation print.
"M. Niessner, Mikrochemie, 12, 17 (1932).
}
BLECTROGRAPHIC MB?rHODS 461
impression is seen. This indicates the presence of phosphorus. Ph<-

phorus-free areas appear colorless in the print. The intensity of color
varies from light to dark blue according to the amount of phosphorus
present. As the strongly acid stannous chloride solution vigorously
attacks the paper, it is advisable to counteract this by adding a little alum,
which hardens the paper. When the imprint is sufficiently developed,
the excess acid is washed in running water. The paper is then dried. The
appearance of the print shows the distribution of the phosphorus.. A
uniform blue indicates a homogeneous solution, e.g., mixed crystals,
whereas segregations show up as localized blue spots on the print.
(c) Detecticm of copper." The developing process may be used for the
detection of copper in sections of metals if the reaction with rubeanic acid
(see page 70) is applied.
fProcedureThe prepared piece of metal is pressed on gelatin paper'
that has been immersed in dilute ammonia (2:5). After a contact for
4 to 5 minutes, the paper is placed in an alcohol-water solution of rubeanic
acid. Shortly after being swirled in the liquid, the print of the dark
steel-green to black copper rubeanate appears. The finished developed
print is washed for a few minutes in running water and dried.
Reagent: 0.5 g. rubeanic acid dissolved in 100 ml. alcohol; of this
solution 5 ml. are diluted to 100 ml. with water
The limited solubility of copper in iron causes segregations of free
copper to form when excess copper is present. The sites of these are easy
to find by the printing method, as they show up as dark spots on a uniform
gray-green background. Its color is due to the small amount of copper in
homogeneous solution.
The method, as described, may be used, with some modification, for
the detection of smallflawsor microcracks in the iron. The procedure is to
cover the sample of metal with a thin fihn of copper, e.g., by-immersion in
copper anmionium chloride. The surface layer of copper adheres loosely
and can be removed with a little cotton wool. The copper is not so readily
removed from the flaws, which can then be located in the copper print.
Eleetrographic Methods
A very interesting procedure for the detection of metals has been
worked out by Glazunow''' and Jirkovsk^^'; this is analogous to a method
M. mtmaet,Mikrochemie, 12, 20 (1932).
'A. GlMunow, Chem. Abatracta, 26,3456 (1932); 24,6666 (1930); Oesterr. Chem.-
Zi(7., 40, 217(1938).
"R. Jirkovsk^, Chem. Abatractt, 26', 6640 (1931); see also S. I. D'yachkovskil
*nd T. I. Ienko, Chem. Abttracts, 28, 48 (1932); E. Arnold, Chem. Abstractt, tt,
3671 (1933).
462 VII. APPLICATIONS OF SPOT KEACTIONS
described by Fritz.'^ The principle of this "electrographic" procedure is

that the test substance is used as anode with aluminum foil as cathode,
and filter paper moistened with the suitable reagent is placed between
these poles. The reagent paper is not laid directly ot) the alxmiinum foil,
but on another filter paper moistened with KCl or K2SO4 as electrolyte.
This arrangement allows the current to pass more easily. When the circuit
is closed, the metal is dissolved anodically and can react directly with the
reagent in the paper, and the typical color stains form on the paper.
A simple apparatus for such electrographic tests is shown in Figure
45. This consists of an aluminum plate as the negative pole (Al), upon
which is laid first a layer of filter paper moistened with KCl solution, and
then the reagent paper (P) moistened with water or acid. The positive
pole is a copper plate with a copper rod soldered to it. An iron nail or iron
Fig. 45. Set-up for electrographic tests (i actual size)
wire may also be used to lead in the current. The test substance is placed
between the poles; the portion toward the cathode is poUshed flat. A
flashlight battery is used as the source of current. ^ - _
Alloys or minerals that show no appreciable resistance to the electric
current may be tested in this apparatus for metals that can be anodically
deposited. Sections of metallic products may be tested for the location of
constituents without damaging the sample, for the electrical method has
the advantage that in the anodic solution of meta,ls, no acid reagents are
required as in the imprint method. Glazunow has identified inclusions of
sulfides and phosphides in steel by this procedure.
Jirkovsk;^ has used the electrographic method prinârily for min-
eralogical purposes. For example, aggregates of PliS and FeS in a mineral
section can be respectively identified after anodic solution by the sharply
defined yellow or blue fleck on chromate or ferrocyanide paper. Jirkovsk^
H. Fritz, Z. anal. Chem., 78, 418 (1929).
FLUORINE IN BOCKS AND IN MINKRAL WATERS 463
has been able to identify iron in pyrite, marcasite, pentlandite, sternbergite,

and other iron-bearing minerals with ferrocyanide paper. Similarly,
Ni may be detected in minerals with dimethylglyoxime; Co with potassium
nitrite and potassium thiocyanate paper; Cu with ferrocyanide paper;Pb
with potassium chromate paper; Cd with hydrogen sulfide paper; Ag
with chromate and potassium iodide paper; bismuth with potassium
iodide paper; antimony with hydrogen sulfide paper; arsenic with silver
nitrate paper; zinc with ferrocyanide paper, and aluminum with alizarin
paper.
This electrographic method is the inverse of the electrolytic (cathodic)
deposition of metals. The quantitj' of the deposit depends on the particu-
lar single potential; consequently, in a mixture of metals, the least noble
metal is the first to go into anodic solution, the deposition, of course, only
affecting the portions lying on the surface. Where there are inhomo-
geneities, it must be remembered that these constituents can only go into
anodic solution if their resistance is not appreciably greater than that of the
adjacent portions.
Detection of Fluorine in Rocks and In Mineral Waters"

A test for fluorine in minerals is described on page 202 in connection
with the zirconium-alizarin reaction. Further, the fluorine test described
on page 206, which depends on the volatilization of SiF4 and the hydrolysis
of this to silicic acid, which is then identified by the molybdate-benzidine
reaction, may also be applied to the rapid detection of fluorine in samples
of rock and mineral waters. This test is especially recommended when
there is much phosphate present, because then the alizarin test is not
specific (see page 202).
When the rock contains silicic acid, the powdered sample can be
treated directly as described on page 206; otherwise 2 to 4 times its bulk
of quartz sand must be added. When the fluorine is combined with SiOj,
the sample must first be fused with sodium carbonate and the cold melt
tested. The fusion is best carried out in a bead on platinum wire. Car-
bonate and sulfide rocks should be ignited beforehand. Mineral waters
are tested by evaporating samples of 5 ml. to dryness with a pinch of
quartz sand in a small porcelain dish. The residue is tested in the usual
way.
The fluorine was successfully identified using a maximum of 0.1 g.
of the following rocks:
Ignited zinc blende containing about 0.6 to 1.50% fluorine
Andesitoid containing about 0.06% fluorine
" F . Feigl and H. Leitmeier, Mineralog. pelrog. Mitt., 40, 6 (1929); see also
Mikrochemie {Pregl Festschrift), li29, p. 83.
464 Vn. APPLICATIONS OF SPOT BEACTIpNS
Granite-gneiss containing about T. \ 0.02% fluorine

Fleck-amphibolite containing about , 0.01% fluorine
Mineral waters which contain large amounts of'chlorides or iodides
must be mixed with 5 ml. hot saturated solution of AgjSOi, the resulting
silver halide filtered off and the filtrate evaporated with quartz sand.
In this way the following mineral waters were testd:
Mineral water Result of the test for fittorine
Bilin Sauerbrunn definitely positive
Karlsbad Sprudel definitely positive
Mattoni's Oieishuhler (H. Mattoni A.-G.) slightly positive
Tassilo spring (Bad Hall) negative
Ober-Selters mineral spring negative
Hunyadi-Janos bitter water negative
Levico arsenic-iron water negative
In view of the sensitivity of the fluorine test, it can be assumed that the
latter four mineral waters, if they contain any fluorine at all, contain much
less than 0.0001% F.
Detection of Sulfide Snlfnr in Rocks^^

The iodine-azide reaction (page 227) for sulfide sulfur, in which
nitrogen is evolved, may be successfully applied to determine the presence
of sulfide minerals in very small samples.
Neither arsenides, antimonides, tellurides, selenides, nor free sulfur
five the iodine-azide reaction. It should, however, be remembered that
almost all naturally occurring minerals of these types usually contain
small amounts of sulfides.
The test may be carried out in various ways. The powdered sample
is placed in a micro test tube and covered with an iodine-azide solution.
The production of bubbles of nitrogen is looked for. Âlternatively, a
grain of the powdered mineral is transferred, as described on page 229,
to an Emich microcentrifuge tube with a platinum wire and brought into
contact with 1 or 2 drops of an iodine-azide solution; or a drop of the reagent
may be placed on the substance in situ, or on a mark made with the
mineral on a streak plate. The streak should be as broad as possible and
any large particles blown away. The advantage of this streak method is
that the sample of mineral is hardly damaged.
Reagent: Solution of 1 g. sodiiun azide and 1 g. potassiima iodide
and a small crystal of iodine in 3 mUwater: The reagent
solution may be used warm, if desired'
" F . Feigl and H. Leitmeier, Chem. Abstracts, Si. 4480 (1930).
arxrATES m HTDROFLUORIC ACID OR FLUORIDES 466
Detection of Seleninm in Minerals, in Sulfur, and Tellurium^*

The test for selenious acid, described on page 264, which depends on
the oxidation of asym. diphenylhydrazine to the violet quinoneanildiphenyl-
hydrazone, may also be applied to the detection of selenium in minerals.
When testing for seleniimi in sulfides, it is advisable to evaporate to dryness
with cone, hydrochloric acid and perhydrol to convert any hydrogen
selenide liberated along with the hydrogen sulfide into a mixture of seleni-
ous and selenic acids. A number of minerals have been examined by the
procedure given here, e.g., cadmium red, clausthalite, zorgite, etc.
^ProcedureA particle of the fiinely powdered mineral is boiled
in a microcrucible with 3 or 4 drops of perhydrol and 4 or 5 drops of cone,
hydrochloric acid; the process is repeated until nearly all the sample ia
dissolved. The contents of the crucible are then evaporated to dryness in
order to decompose all remaining traces of the perhydrol in the acid solu-
tion. The residue is taken up in 3 or 4 drops of cone. HCl, a few mg. ox-
alic acid are added, and the mixture is evaporated to a damp mass. To
this are added a drop of dilute hydrochloric acid, 2 drops water, and 4
drops reagent solution. A red color appears, either at once or after a few
minutes, according to the amount of selenium present.
The same procedure (but without addition of oxalic acid) can be used
lo detect small amounts of selenium in sulfur and tellurium. An artifi-
cially prepared mixture of selenium with sulfur or tellurium gave a light
red color when as little as 0.001% Se was present in a 20 mg. sample.
Examinations of TeO* for a possible content of Se02 showed that
practically all the materials on the market contained the latter. TeOj
may be purified by long-continued heating at the sintering temperature;
SeOj volatilizes. Samples of Te02 purified by this procedure were mixed
with SeOi to determine the limiting value of the test for Se02 in TeO.
The alkali salts behaved similarly. When 20 mg. were treated with the
reagent in a depression of a spot plate, 0.001% SeOa could still be detected.
Detection of Sulfates in Hydrofluoric Acid or Fluorides

In testing the purity of hydrofluoric acid and fluorides it is unportant
to discover whether any sulfuric acid or sulfate has been left-in the product
frwn the preparation. The usual test with barium chloride is not possible
in this instance, because barium fluoride is sparingly soluble in dilute acids
and BaS04 is incompletely precipitated from strongly acid solutions. The
practice heretofore has been to convert the acid into its alkali salts and then
to test for sulfur (sulfate) by the "hepar method"." The very sensitive
" F . Feijl nd V. Demant, Mikrochim. Acta,l, 322 (1937).
" E . DeuMen, Z. anal. Ckem., 46, 320 (1907).
I
iodine-azide reaction, which is specific for sulfide (see page 229) can be
substituted for the hepar test. It will reveal small jquantities of sulfate
in one drop of potassium fluoride solution,'' ,i
IfProcedureA few grains of calcined sodium carbonate are laid in
the middle of a small strip of quantitative filter paper (0.5 X 3 cm.).
They are moistened with the test solution and dried. The strip of paper is
rolled up and laid on a Wedekind magnesia spoon and heated with the
blow-pipe flame. In order to avoid any error due to the sulfur content of
the gas, an alcohol burner is advisable. The sulfate is reduced to sulfide
by the carbon of the filter paper, so that the reducing flame of the blowpipe
is not essential. After fusing and reducing (the ash should not be quite
white, but should still contain some of the carbon residue of the paper)
the melt is placed in a microcentrifuge tube. The mass, dissolved in 2
drops of water and a drop of iodine-azide solution (preparation see page
228), is added. When sulfide is present, implying sulfate in the original
sample, definite bubbles rise through the liquid.
In this way, 22 y sodium sulfate was readily detected in the presence of
500 times this amount of potassium fluoride.
Even smaller quantities of sulfate can be revealed if a definite volume
of the test solution is precipitated with barium chloride and the precipitate,
(BaSO* and BaFa), dried and reduced to sulfide with metallic potassium
(see page 238). Then the iodine-azide reaction is carried out."
Detection of Sulfate in Inorganic Fine Chemicals''
Formerly, the detection of sulfate in inorganic, high grade chemicals
was only possible when a large sample of the test material was available
for precipitation with a barium salt. About 5 to 10 g. of the test material
was dissolved and observed for reaction with barium chloride. There is
considerable possibility of errors arising in the precipitation..of very small
amounts of barium sulfate from concentrated salt solutions, as" neutral
salts can delay or prevent the separation of barium sulfate. Further,
when the dilution is insufficient, precipitates may form because of concen-
tration effects.
However, the sulfate can be easily detected in very small amounts of
the sample material (see page 238) if the sulfate is reduced to sulfide with
metallic potassium and identified as such with the iodine-azide reaction.
IfProcedureA few mg. of the solid sample along with a particle of
metallic potassium are placed in a glass capillary. The tube is warmed
until the potassium melts. It is then heated strongly and the hot capillary
"Studies with L. Weidenfeld, Dissertalion, Vienna (1980).
"Studies with L. Badian.
" F . Fei^ and L. Badian, unpublished Btudiea.
DETECTION OP ALKALI MONOCHROMATE 467
plunged into a micro test tube containing a few drops of water. After the
capillary has broken, a drop of cadmium solution is added, the mixture
acidified with acetic acid, and iodine-azide solution added. In the presence
of sulfide (implying sulfate in the original sample) nitrogen is evolved.
Reagents: See page 313.
This prdtedure revealed sulfate in 3 mg. sodium chloride, oxalate
carbonate, and nitrate that were labeled "chemically pure."
Detection of Bichromate in the Presence of Alkali Monochroinates^

Alkali monochromates, e.g., Na2Cr04, are without effect on potas-
sium iodide. The oxidation of iodides by chromates with liberation
of iodine only takes place in the presence of hydrogen ions:
2 Cr07~ + 6 r + 16 H+ = 2 Cr+++ + 8 H2O + 3 I2
Hydrogen ions are present in bichromate solutions owing to hydrolysis
(CrjOT" + H2O = 2 Cr07~ + 2 H+). 'The chromic salts, formed on
the reduction of chromate, hydrolyze and, therefore, also react acid. Con-
sequently, potassium iodide is oxidiijed by bichromate solutions and the
liberation of iodine serves to indicate bichromate in the presence of chro-
mate. Furthermore, iodine is liberated more rapidly by the addition of a
mixture of potassium iodide and potassium iodate to a chromate solution
containing bichromate. The reaction:
5 I- -t- lOr + 6 H+ = 3 H2O -t- 3 Ij
then occurs along with the chromate reduction.
IfProcedureA drop of the test solution, or a crystal of the solid
sample, is mixed with a drop-of a KI-KIO3 solution, stirred, and a drop of
starch solution added. When bichromate is present, a distinct blue
appears, at most, after 5 minutes.
Chromate and bichromate can also be distinguished by a procedure
which is less sensitive than the preceding one, but adequate for many
purposes. The test is.based on the action of sodium sulfite.^^ Only
bichromate reacts, the color changes from orange to green, due to the forma-
tion of a chromic salt.
Detection of Alkali Monochromate in the Presence of Alkali Bichromate'^

If a neutral solution of the nickel salt of a mineral acid is treated
with an excess of dimethylglyoxime, the precipitation of.the red nickel
" M . Richter, Z. anal. Chem., 21, 368 (1882).
"L. Rossi and co-workers, Chem. Abstracts, 32, 8301 (1938).
" F . Feigl and N. Braile, unpublished studies.
dimethylglyoxime is incomplete. The clear filtrate is,a saturated solution

of nickel dimethylglyoxime in which the following equilibrium exists:
Ni++ + DH2 ^ Ni(DH), + 2 H+
where i)H is the radical of dimethylglyoxime (DHj). This equilibrium
will be disturbed by the introduction of soluble or insoluble materials that
consume H+ ions, and red nickel dimethylglyoxime will be precipitated
immediately. This fact is the basis of a decisive test for "basic" materials,
using the term in its widest sense, i.e., materials which consume H+ ions
(see page 478).
Alkali monochromates consume H+ ions, reacting with them to form
bichromates:
2 Cr07~ + 2 H+ ?=i CrjOf" + HjO
Accordingly, the addition of an alkali monochromate to the equilibrium
solution results in an immediate precipitation of red nickel dimethyl-
glyoxime. Bichromates show no action toward this reagent. As little as
2.5 7 K2Cr04 can be detected in 1 drop, after evaporation, ofits solution.
The diverse behavior of mono- and bichromate toward this equilib-
rium solution makes it possible to detect quickly the presence of the mono-
chromate in a sample of bichromate. The test is not particularly sensitive,
but it affords the only available possibility of detecting monochromate in
the presence of bichromate without making a quantitative analysis, i.e.,
detiermining the ratio K:Cr.
IfProcedureA drop of 10% KjCrjOr solution is taken to dryness in a
microcrucible. The residue is treated with 1 drop nickel dimethylglyoxime
equilibrium solution (for preparation, see page 479). Red nickel dunethyl-
glyoxime appears if monochromate is present. A blank with a pure
bichromate solution is recommended when small amounts of monochromate
are suspected. ^^^
lAmit of Identification: 18 y KjCrO^ in the preence~"of-6000 7
Detection of Carbonate in Alkali Cyanides, Sulfites, and Solfides"

The carbonic acid test described on page 254 may be applied to the
detection of small amounts of carbonate in alkali cyanides, sulfites, and
sulfides. This test depends on the'decolorization of a drop of carbonate
reddened with phenolphthalein; the carbonic acid forms bicarbonate which
gives no color with this indicator. ^
"F. Feigl and P. Krumholi, Mikrochemie, 8, 131 (1930).
SILICA IN CAUSTIC ALKALIS AND ALKALINE SOLUTIONS 469
It is necessary to prevent any formation of free prussic acid, hydrogen

sulfide, or sulfur dioxide, as these can also cause the decolorization. This
interference may be avoided by adding mercuric chloride to cyanides.
Soluble, but undissociated, mercuric cyanide is formed; it is stable toward
acids. Sulfides and sulfites can be converted by hydrogen peroxide into
sulfate and this product does not interfere with the carbonate test.
^[Procedure(a) Test in the presence of cyanides. About 2 to 3 mg.
of the solid cyanide, or a drop of a cyanide solution (the concentration
should not exceed 5% potassium cyanide), are placed in the apparatus
sho^^^l in Figure 27 (page 31) and stirred with 4 drops of a saturated solu-
tion of mercuric chloride. Two drops of 2 A'' sulfuric acid are added and the
apparatus closed. A decolorization, compared with a blank, if necessary,
indicates carbonic acid.
(6) Test in the presence of sulfides and sulfites. A small piece of the
solid sample or a drop of the solution (the sulfite solution can be saturated,
the sulfide solution about 5%), is stirred with 4 drops of a 3% solution of
hydrogen peroxide (neutral) and the further treatment is the same as in (a).
The presence of carbonate in a drop of a freshly prepared solution of
the following materials was detected by decolorization of the phenol-
phthalein drop, after standing about 10 minutes:
Potassium cyanide, technical and "for analysis" ( 5% solution)^
Sodium sulfide, technical and "for analysis" (10% solution)
Potassium sulfide, technical and "for analysis"... (10% solution)
Sodium sulfite, technical and "for analysis".... (saturated solution)
Detection of Silica in Caustic Alkalis and Alkaline Solutions. Testing the

Vulnerability of Glass and other Siliceous Products to Attack by Alkalis
The sensitive silicic acid test, described on page 252, which depends
on the special reactivity of silicomolybdic acid, may be applied to detect
silica in impure solid caustic alkalis or in basic solutions, which have been
kept for a long time in glass containers. Silica is known to be dissolved
from the walls. This dissolution of silica is very easy to follow in ammonia
water; freshly prepared ammonia solutions contain very little silica.
On long standing, the silica content increases rapidly, so that old and
freshly prepared ammonia solutions may be readily distinguished from
each other by this test. Obviously, the vulnerability of the glass makes
some difference, but seemingly all kinds of siliceous glass are eventually
attacked by alkalis.
^[ProcedureA drop of cone, nitric acid is placed in a microcrucible,
1 or 2 drops of the test solution are added with a loop of platinum, and
stirred. A small piece of the caustic alkali is used. The addition of
molybdate, benzidine, etc., is carried out as described on page 253.
The rapidity of the attack on glass or other .siliceous materials by

caustic alkalis with resulting removal of silica, affords a means of differen-
tiating the various kinds of glass with respect to their alkali resistance.
This may be done by placing 1 or 2 drops of a freshly prepared alkali solu-
tion on the test object {e.g., a test tube laid on its feide, or other suitable
glass apparatus) and allowing it to take effect. The drop is then washed
off into a microcrucible using as little nitric acid as possible, and the silica
test carried out as described on page 253. By varying the strength of the
alkali and the length of attack, data may be obtained for the appraisal of
varieties of glass.
Detection of Silicic Acid in Minerals^^
(a) After fusion ivith sodium potassiîm carbonate. A little of the
powdered mineral is decomposed with sodium potassium carbonate in a
loop of platinum wire; the silicic acid is thus brought into a reactive form.
The bead is dissolved (in a microcrucible) in a drop of 1 iV nitric acid.
Ammonium molybdate solution is added and the rest of the procedure is
that described on page 253.
(b) After conversion into silicon tetrafluoride. As is well known, sili-
cates are converted to volatile silicon tetrafluoride when heated with
fluorides and cone, sulfuric acid:
SiOs -f- 4 H F = SiFi + 2 HsO .
The gas is taken up in a drop of water and decomposes:
3 SiF4 -f 4 H2O = HiSiOi + 2 HsSiF,
producing silicic acid and hydrofluosilicic acid. When ammoniiun molyb-
date is added, these two compounds are converted to silicomolybdic acid,
and can be identified with benzidine (pages 206 and 252).
f ProcedureÂ little of the solid sample is treated in a small plati-
num crucible with a few mg. calcium fluoride. Two drops cOnc. sulfuric
acid are added and the crucible covered with a piece of filter paper on which
is placed a drop of ammonium molybdate solution. The crucible is heated
over a microbumer for about 1 minute and allowed to cool for 3 to 5 minutes.
The ammonium molybdate fleck is then treated with a drop of benzidine
and developed over ammonia. Rocks containing carbonate and sulfide
should be ignited before the test to prevent any frothing of the contents
of the crucible (evolution of carbon dioxide) or reduction of the molybdate
by hydrogen sulfide.
Limit of Identification: 2.6 7 silicic acid. ^
Free silica can be distinguished from bouri3 silica by the diverse
" F . Feigl and P. Krumholz, Ber., 62,1138 (1929); see also Mikrochemie (Pregl
Felsehrift), 1929. p. 83.
PHOSPHATES IN AnNERALS AND ROCKS 471
behavior of finely powdered specimens toward certain dyes. For instance,

a solution of safranin 0 in 30 ml. alcohol and 70 ml. water colors quartz
particles yellow (adsorption), whereas felspar particles are not affected.**
Detection of Boron in Rocks and Enamel*

The test for boron, described on page 258, in which a complex boric
acid ester of p-nitrobenzeneazochromotropic acid is formed, may be
applied to the identification of boron in rocks, etc., after a fusion with
potassium hydroxide. The finely powdered sample is fused with potas-
sium hydroxide in a silver crucible. The cold melt is extracted with a few
drops of water; the solution isfilteredusing the device described on page 37,
and the boric acid test is carried out on the evaporation residue from 1 or 2
drops of the filtrate. - When chromate or permanganate is formed in the
fusion, the procedure described on page 259 must be used.
The color reaction with hydroxyanthraquinones (see page 257), or
the decomposition of methyl borate with alkali fluoride (see page 259),
may be applied to the detection of boron in the melt.
Detection of Phosphates in Minerals and Rocks"

The spot test described on page 250 may be applied for the rapid
detection of phosphates in rocks and minerals. Either a few mg. of
the powdered rock, or a splinter of the solid, are placed on filter paper,
moistened with a drop of ammonium molybdate solution, and held over a
flame for a short time. A drop of benzidine solution is added and the
moist fleck held over ammonia. A brilliant blue forms on the paper either
at or near the position of the sample, sometimes in continuous patches, and
wherever traces of ammonium phosphomolybdate have been formed. A
useful procedure is to carry out the test on a streak plate. The reagents
are applied to the streak.
In many instances, the mineral itself may be treated in situ with
the nitric acid-molybdate solution. The liquid is taken up on a piece of
filter paper and the rest of the test carried out on the paper.
Arsenates, which resemble phosphates also in their geologic habits,
do not give the benzidine reaction, so that no confusion occurs between
the two. It is therefore possible to detect phosphate in arsenates by this
reaction.
The test was applied to 36 minerals from various sources (for details
"A. L. Engel, U. S. Bur. Mines Bepts. Investigations Tech. Papers, 3370, 69
(1938).
"A. S. Komarowsky and N. S. PoluektofF, Mikrochemie, 14, 317 (1933/34).
" F . Feigl and H. Leitmeier, Mineralog. petrog. Mitt., 39, 224 (1928).
472 VII. APPUCATIONS OF SPOT REACTIONS
Bee the original paper). The following powdered rocks, with low apatite
content, gave positive results:
Red Andesite (Gleichenberg, Styria) 3 0.57% PiO.
Gray, thick Andesite (Gleichenberg, Styria) ' 0.35% PjO
Granite (Maissau, Lower Austria) J 0.26% PjOs
Gneiss (Diimstein, Lower Austria) 0.12% PjOs
Fleck-amphibolite (Spitz a. D., Lower Austria) - 0.10% PjOi
Granitic gneiss (Waldviertel, Austria) traces
By varying the test slightly it can also be used to detect or locate
apatite in thin sections and on any polished surface of a rock.
^[ProcedureA small filter paper is impregnated with nitric acid-
molybdate solution. Then, either the mounted section or the piece of
rock is warmed (the section should not be heated so much that the Canada
balsam becomes mobile) and pressed at once on the moist paper and left
for 1 or 2 minutes. The paper is laid with the surface of contact upward
on a second paper soaked in benzidine solution, so that the solution rises
through the paper. The first paper is then held over an open bottle of
ammonia and an exact blue print is obtained of the crystals of apatite in
the section. If the contours of the section have been drawn on the paper,
the exa'ct location of the crystals is known. Even the smallest crystals of
apatite, of whose apatitic nature there may be some doubt, may be identi-
fied in this way, thus amplifying or even replacing the optical examiaation.
Detection of Free Acids and Basic Compounds in Solutions of Aluminum

Salts'^ and of Free Acids in Solutions of Copper and Cobalt Salts"
It is well known that aqueous solutions of pure aluminum salts, e.g.,
AlClj, AliCSO*)}, react acid due to hydrolysis. Consequently, any free
acid present cannot be detected directly by means of iiidicators. The
same is true of solutions of basic aluminum salts [e.g., basic aluminum
acetate A1(0H)(CHC00)2], that react acid due to hydrolysis, in spite
of their basic constituents. ~""^ --
The hydrolysis of the aluminum ion may be masked by the addition
of neutral substances which form complexes. For example, the aluminum
ion can be replaced by alkali ion and can take its place in compounds whose
reaction is neutral. Then, the acid or alkaline reaction of the masked
solution will reveal the presence of free acids or basic aluminiun salts,
since the exchange involves the disappearance of only the alumimmi, and
not the hydrogen or hydroxyl ions. Alkali oxalates are excellent complex
formers for aluminum salts. If sodium oxalate is added to solutions of
aluminum salts there is an instantaneous formation -^ the sodium salt of
"P. Feigl and G. Krausz, Ber., 68, 398 (1925).
"L. Melnik, private communication.
HYDKOGEN SULFIDE IN WATER 473
aluminum oxalic acid, in which the alimiinum is a constituent of a stable

complex anion:
* AlCl, + 3 Na,C,04 = Na,A)(C2O03 + 3 NaCl
AlCl, + HCl + 3 NasCOi = 'NsiM{CiOt)z + 3 NaCl + HCl
A1(0H)(CH,C00), + 3 Na,C,04 = Na,Al(C204)3
+ 2 CHiCOONa + NaOH
These equations show, therefore, that solutions of an aluminum salt,
after masking with oxalate, react neutral, acid, or alkaline, according to
whether a neutral salt, free mineral acid plus neutral salt, or a basic alumi-
num compound was present.
The addition of excess sodium oxalate to solutions of copper or cobalt
salts likewise produces complex double oxalates. Consequently, the pres-
ence of free acid can then be detected by means of indicators.
^Procedure1 or 2 drops of the test solution are stirred on a spot
plate with a few crystals sodium oxalate and then tested with methyl orange
or phenolphthalein for free acid or alkali.
The presence of small amounts of acid in solutions of copper or cobalt
salts can be detected as follows: one drop of the solution is warmed with
several crystals of NasCj04 in a microcrucible. After cooling, the mixture
is tested with litmus paper. The presence of metal oxalates or double oxa-
lates does not interfere with the discernment of the color change. As little
as 0.05% free H2SO4 can be detected in the solution prepared from a
crystal of the copper sulfate being tested.
Detection of Traces of Hydrogen Sulfide in Water*"

As shown on page 227, even slight amoimts of soluble and insoluble
sulfides react with a solution of sodium azide and iodine with evolution
of nitrogen. This sensitive reaction can be intensified, and applied to the
detection of traces of hydrogen sulfide in water, if a localized decomposition
of hydrogen sulfide is arranged. This is accomplished by shaking a water
sample with metallic mercury; mercury sulfide is formed.
IfProcedureA iO ml. sample of the water is placed in a hard glass
test tube or a small stoppered measuring cylinder. It is treated with a
drop of mercury, taken from the mercury dropper described on page 11.
After vigorous shaking, the water is poured off and the drop of mercury
placed on a watch glass. If hydrogen sulfide was present in the water, a
very thin film of mercury sulfide resides on the surface of the mercury. It
is not visible if small amounts of hydrogen sulfide were present, but on
"F. Feigl and L. Weidenfeld, Mikrochemie (Emich Fe*Uchrift), 1980, p. 132.
31
474 VII. APPLICATIONS OP SPOT KBACTIONS
stirring with 1 or 2 drops of a sodium azide-iodine solution it reacts at

once with evolution of nitrogen. Some of the bubbles of nitrogen remain
on the surface of mercury and are clearly visible with a lens.
As little as 0.05 y of hydrogen sulfide can be identified with certainty
in 10 ml. water."
Even smaller amounts of hydrogen sulfide can be detected LQ a larger
volume of water, if the water is shaken, in separate portions, with a drop of
mercury, and this then tested by the iodine-azide reaction.
Hydrogen-Ion Concentration of Aqueous Solutions
The hydrogen-ion concentration of a solution, that is the so-called
actual acidity, is expressed by the hydrogen exponent pH. This figure is
the negative logarithm of the hydrogen ion concentration. Its value can be
determined approximately by means of color indicators. These arc or-
ganic acids or bases, with two different structural forms, one dissociatmg
(ionogenic) form and a pseudo form. These forms have distinctly different
colors.
^ y using a suitable selection of indicators, with color change inter-
vals at different pH levels (the change is never sudden, but is always grad-
ual) the acidity (pH < 7) or alkalinity (pH > 7) may be found in a drop
of liquid on a spot plate or on indicator paper.
The color change and transformation intervals, etc., for the indicators
generally used are given in Table 37.'''
TABLE 37. INDICATORS
Color Color
Name Change change inter- Indicator solution
val, #H
Tropaelin 0 0 Sharp 1.3- 3.2 0.1% aqueous

Methyl orange.... Sharp 3.1-M 0.1% aqueous
Bromophenol blue Fairly
sharp 3.0- 4.6 Dilute aqueous
Methyl red Sharp 4.2- 6.3 0.2% aqueous
p-Nitrophenol Fairly.
sharp 5.0- 7.0 1% aqueous
Litmus Blue Sharp ' 5 . 0 - 8.0 1% aqueous
Bromothyniol blue Yellow Fairly
sharp 6.2- 7.6 Dilute aqueous
Neutral red Red Sharp 6.&- 8.0 0.1% aqueous
Phenolphthalein. Red Sharp 8.0-10.0^ 0,5% alcoholic
"The methylene blue reaction (see page 230) permits the detection of 2.5 y
HjS in 10 ml. water.
"More extensive tables are given in the various handbooks and in 'texts on
Quantitative analysis.
HYDROGEN-ION CONCENTRATION 475
A "universal" indicator may be used in an orienting determination

of the pH of a solution. This is a mixture of different indicators that give
characteristic color changes at different pH values. Bogen's'' Universal
indicator is a solution of:
0.1 y phenolphthalein
0.3 7 dimethylaminoazobenzene
m 500 ml.
0.2 7 methyl red
absolute alcohol
0.4 7 bromothymol blue
0.5 7 thymol blue
A microdrop of the indicator is added to a drop of the test solution
on the spot plate, and the following shades appear :
Red at about pH = 2.0
Orange at about pH = 4.0
Yellow at about pH = 6.0
Green at about pH = 8.0
Blue at about pH = 10.0
For the rapid measui-ement of pH values it is very advisable to com-
pare the color change in the sample treated with indicator with color charts
on which the tint of the indicator is shown with the corresponding pH
value. An apparatus suitable for this test is described by Todt.'*
The device has a revolving stand with clamps for holding 8 brown
glass containers for the indicators. Each container has a ground glass
stopper at the top and a glass tap at the bottom so that the velocity of
delivery of the drops can be carefully regulated. Each stopper has a
channel bored through it that communicates with a side tube. ^ The latter
is connected by a rubber tube with a central soda-lime tube. This also is
provided with a channelled stopper, and can be opened or closed at will.
As the indicators are sensitive to carbon dioxide, it is important that the
air entering the indicator containers should be carbon dioxide-free.
The base of the stand is a porcelain plate. The revolving upright is
so arranged that there is a lock device at every | of a revolution, so that an
indicator bottle is always directly opposite to the worker, and no further
revolution occurs on turning the tap. The names of the indicators are
marked on the metal bands which hold the containers.
When measuring the pH a drop of the indicator is placed on a spot
plate and 1 or more drops of the test solution added with a dropping pipet.
The specimen is observed to see if the color changes on the addition of
further drops of the test solution. In most cases i to 2 drops of the test
" E . Bogen, Suddeut. Apoth.-Ztg., 68, 308 (1928).
" F . T6dt, Chem. Abstracts, 21, 1560 (1927).
476 Vn. APPLICATIONS OF SPOT REACTIONS
solution are sufficient. Only for poorly buffered, solutions is more of the
test solution necessary to get the proper color. In such cases, distilled
water for instance, a spot plate with large depressions is best. When the
color no longer changes with further addition of the test solution, the vol-
ume ratio is correct. The dilution naturally lowers the depth of color, but a
little 'practice will show whether the actual shade has altered or not. The
color is then compared with the color chart of the particular indicator used,
and the pH value read off. If the approximate pH value of the test
solution is quite unknown, a preliminary test is necessary to decide which
indicator to use. Thus, if a yellow color is obtained with bromothjonol
blue, the pH value lies below 8.0. Then the next indicator in order is used
until one is found that gives an intermediate color. The pH in question
can then be read from the chart.
The following indicators are used:
Bromophenol blue pH!2.8-4.6
Bromocresol green pS. 3.6-5.4
acid region
Methyl red pH 4.4-6.3
Bromocresol purple .' pH 5.1-6.7
Bromothymol blue /.pH 5.8r7.6
Phenol red pH 6.7-8.4
alkaline region
Cresol red pH 7.1-8.8
Thymol blue ,. .pH 8.0-9.6
Orienting Reactions for Judging Samples of Water

The presence of certain elements and compounds is important in
the judging of water samples. Even very small amounts of these may be
detected by spot methods.
In water analysis, very great dilutions usually have to be considered,
and it is therefore advisable, when testing the nature of dissolved material,
either to concentrate the solutions, or, better still, to evaporate tp dryness
and utilize the residue. ^^
Other methods are available for the concentration of certaiii' constitu-
ents. These procedures may be useful-in studying minute quantities of
dissolved materials. Examples of these are Kolthoff's" method for Cu++
and Pb++ by shaking with CaCOi; and Heller's** method for metallic salts
by extraction with solutions of dithizone in CCU (accumulation of complex
metal dithizonates in CCU). Up to the present, there are a number of
compounds for which neither an adsorption medimn nor an extraction
system is available. In this connection the work of Schwab and Jockers"
I. M. Kolthoff, Pharm. Weekhlad, 83, 1739 (1916); cf. N. Schoorl, Z. anal.
Chetn., 88, 328 (1932). - "'1
K. Heller, G. Kuhla, and F. Machek, Mikrockemie, 18, 193 (1936).
"G. M. Schwab and K. Jookers, Naturviisstnichajten, S5, 44 (1937); Z. angew.
CAm., 60, 646(1937).
OBIENTING REACTIONS FOB JUDGING SAMPLES OF WATER 477
is likely to be of great importance. They have shown that chromatographic

analysis," which has proved so fruitful in organic and physiological chem-
istry, may also be applied to inorganic analysis and to the detection of
traces of impurities.
Small electrodes ("needle electrodes") for the electrol3i.ic deposition
of minute traces of metals were used with success,'* and it has been found
that they are suited to localize traces.'"" Following this electrols^tic deposi-
tion, the material may be put into solution and identified in various ways.
Possibly anodic solution or the printing method (see page 457) may be
used to advantage.*"'
The following are a smnmary of sensitive tests for some of these
materials, that are worth considering when examining samples of water
used for technical purposes.
Ammonia. Test with the manganese-silver reaction, see page 184.
Iron. Test with a,a'-dipyridyl, see page 122.
Fluorine. Test by conversion into SiF*.
A few ml. water are evaporated to dryness with a few mg. quartz sand
and treated as described on page 206. In this way as little as 1 -y of
fluorine may be detected in 5 ml. water..
Iodide. Test after oxidation to iodate, see page 199.
Silica. Test with ammonium molybdate and benzidine, see page 252.
Small amounts of phosphate that may also be present in the water
can easily be rendered inactive by adding oxalic acid, after the heating
with molybdate (see page 253).
Calcium. Test with ammonium ferrocyanide, see page 169.
Carbon dioxide. Test with sodium carbonate and phenolphthalein,
see page 254. When waters very low in carbonate are to be tested, several
drope should be used for the test.
Copper. Test by catalytic effect on the iron (Ill)-thiosulfate reac-
tion, see page 63.
Magnesium. Test with p-nitrobenzeneazo-a-naphthol, see page 173.
Manganese. Test with benzidme, see page 134.
Smaller amounts than 0.15 y manganese per drop may be detected"':
100 to 150 ml. water is treated with a few drops sodiimi hydroxide, boiled
'G. Hesse, Z. angew. Chem., 49, 315 (1936), gives a comprehensive review.
See also L. Zechmeister and L. v. Cholnoky, Principles and Practice of Chromatog-
raphy, translated by A. L. Bacharach and F. A.Robinson, Chapman, London, 1941.
H. H. Strain, Chromatographic Adsorption Analysis, Interscience, New York, 1942.
H. J. Brenneis, Mikrochemie, 9, 385 (1931).
"H. Alber, Mikrochemie, 14, 234 (1934).
*"For example, Alber {loc. cit., which includes a description of the apparatus
used) deposited and identified 0.005 y Cu from 5 ml. of electrolyte. This corresponds
to dilution of 1:1,000,000.
F. Feigl, Chem.-Zig., 44, 689 (1920).
and filtered. The calcium and magnesium carbonates thus precipitated by

the carbonate in the alkaU coprecipitate any manganese dioxide formed.
The mixture is filtered through a quantitative filter paper and tested there
with benzidine solution. A blue color indicates manganese. In this way,
1.27 manganese (dilution 1:25,000,000) may be detected.!""
Phosphoric acid. Test with tartaric acid, ammonium molybdate
solution, and benzidine,'"* see page 252.
Nitrous acid. Test with Griess' reagent, see page 248.
Nitric acid. Test with brucine, see page 245.
Sulfurous acid. Test with malachite green, see page 234.
Hydrogen sulfide. Test with iodine-azide solution, see page 227,
or, for the detection of traces, see page 473.
Determination of Hardness of Water; Differentiation of Distilled
and Tap Water
The high sensitivity of the reaction:
2 Ag+ + Mn++ + 4 OH- = 2 Ag+ + MnOj + 2 H2O
provides a test for Ag+, Mn++, and OH" ions (see pages 42, 137 and 184).
Since calcium carbonate (aragonite, see page 444) as well as calcium oxide
react similarly to free alkali, it is possible to distinguish hard from soft
water by this convenient spot test.'"^ The residue from evaporation of a
drop of water after ignition, if necessary, is treated with the reagent, and
the result (intensity of gray or black color) is compared with a test carried
out on water of a known degree of hardness, or on Ca(HC0})2 solutions of
known concentration. In order to ensure that the residues for comparison
shall be of the same size and shape, it is advisable to evaporate the samples
on slides frosted with hydrofluoric acid. The slides must be scrupulously
cleaned with chromic-sulfuric acid and washed with water. Otherwise the
drops run about and it is impossible to obtain the drops of oqual diameter,
which are essential for the comparison with the standards. For this reason,
the same method of placing the drop on the slide must be used for every
sample and standard solution.
In field work, it is suflfiicient to evaporate a drop of water on a crucible
lid, ignite for a moment, and then add a drop of the reagent to the cold
residue. According to the depth of blackening (compared later with a
standard treated in the same way), the water may be graded as hard or
soft. Similarly, distilled water may be distinguished from spring or tap
/
""For the detection of manganese by benzidine in watejcanalysis in connection
with the ammonia test see W. Olszewski, Chem.-Ztg., 47,-273 {1923).
>"See also A. Sulfrian, Chem.-Ztg., 66, 650 (1932).
"Y. Kondo, Mikrochim, Acta, 1, 154 (1937).
mORQANIC AND ORGANIC (BASIC) MATERIALS 479
water. The results of the test may be preserved as a permanent

preparation.
Reagent: for preparation, see page 185
Detection of Inorganic and Organic (Basic) Materials

. that React with Mineral Acids"*
The examination of rocks and minerals, and the chemical testing of a
variety of materials, often require a rapid method of detecting soluble or
insoluble products that react with dilute mineral acids and form the corre-
sponding salts. Materials of this kind, which can be considered as basic,
using the term in its widest sense, include hydroxides, oxides, carbonates,
arsenates, phosphates, fluorides, organic bases, and salts of weak organic
acids.
A very sensitive test for materials that consume acids, and conse-
quently, H+ ions, is furnished by a nickel dimethylglyoxime equilibrium
solution. Nickel dimethylglyoxime can be precipitated completely, only
from ammoniacal or acetic acid solutions. The precipitation is incomplete
from solutions of nickel salts of strong acids [NiClj, Ni(N03)2, NiSO*].
The clear filtrate in these latter cases is a saturated solution of nickel
dimethylglyoxiine presenting the equilibrium:
Ni++ -t- 2 DH2 ^ Ni(DH)2 -f 2 H+
(DH2 = dimethylglyoxime)
This equilibriimi solution (pH = 1.9) reacts with all materials that con-
sume H+ ions, and which therefore disturb the equilibrium. Red nickel
dimethylglyoxime is precipitated and is quite visible even in minute
quantities.
The particular advantage of using this equilibrium solutipn for estab-
lishing the presence of basic materials is that it provides a simple rapid
method, that is also applicable to materials so slightly soluble in water
that they do not affect indicators. Furthermore, minimal quantities of
solid specimens suffice.
The application of the procedure for detecting basic compounds and
materials that are attacked by acids include:
1. Detection of rocks that are attacked by acids (oxides, carbonates,
phosphates, acid-decomposable silicates, etc.).
2. Testing of evaporation and ignition residues (see pages 455 and
478).
S. Detection of potassium chromate in potassium bichromate (see
page 467).
"F. Feigl and C. P. J. da Silva, Ind. Eng. Chew.., Anal. Ed., 14, 316 (1942).
4. Detection of free organic bases, and salts of organic bases with weak
acids, in mixtures with indifferent materials.
IfProcedoreA few grains of the finely powdered specimen are
placed on a white spot plate. One or 2 drops of the equilibrium solution
are added and mixed with the solid by means of a fine glass rod or by
blowing through a glass capillary. According to the yulnerability of the
specimen to the acid in the equilibrium solution, there will be either no
change, or a red color will appear immediately or after several minutes.
Very small quantities can be tested on a slide and the color observed under
the microscope. Portions of rocks and minerals can be scraped loose with a
pen knife and the powder spotted on the solid specimen with the reagent
solution.
The production of the red nickel salt can be seen easily only when
colorless materials are being tested. With colored specimens, it is well to
make blank tests and to use several drops of water in place of the equilib-
riimi solution. ^
The efficiency of the test can be demonstrated with such basic ma-
terials (MgNHJOi, albumen, etc.) as produce no color change with indi-
cators (phenolphthalein). They react promptly with the equilibrium
solution. ^
Reagent: Nickel dunethylglyoxime equilibrimn solution: 2.3 g.
NiS04-aq dissolved in 300 ml. water are treated with 2.8 g.
dimethylglyoxime dissolved in 300 ml. alcohol. The
suspension is allowed to stand for 30 minutes and then fil-
tered. The reagent will keep for several weeks if stored in
tightly stoppered bottles
Detection of Traces of Sulfur in Carbon Disulfide, Ether, other Organic
Solvents, and Motor Fuels*"
Very small amounts of sulfur dissolved iii carbon disulfide may
be identified, after conversion into thiosulfate (a) or sulfide (b), by the
sensitive iodine-azide reaction as described on pages 240 and 227; The
sulfur may be converted into thiosulfate by heating the residue left on
evaporation of the carbon disulfide with an alkaline sodium sulfite solution:
NajSOa + S = Na2S20j. The conversion into sulfide' may be effected by
shaking the carbon disulfide with metallic mercury; mercury sulfide is
formed immediately.
The procedures (a) and (b) may also be applied to the, detection
of traces of sulfur in ether or other organic solvents. A further important
application is in the detection of corrosive sulfur in'inotor fuels."'
" ' F . Feigl and L. Weidenfeld, Mikrochemie {Emich Fettzehrift), 1930, p. 133.
'K. Weisselberg, Petroleum, 81, 7 (1934).
DETECTION OF SULFIDE StJLFUK 481
^Procednre(a) A drop of the sample of carbon disulfide is allowed

to evaporate completely on a watch glass. This may conveniently be
heated on the steam outlet of the apparatus described on page 29. After
evaporation,"' 2 drops of an alkaline solution of sodium sulfite are placed
on the watch glass. It is then heated 2 to 3 minutes on the steamer, and
after cooling, a few drops of an iodine-azide solution are added. If even a
trace of sulfur was originally present, the thiosulfate formed causes a more
or less vigorous evolution of nitrogen.
Ldmit of Identification: 0.5 g. sulfur
Reagents: 1) Alkaline sulfite solution
2) Iodine-azide solution (see page 228)
Even smaller amounts of sulfur can be identified by (b), if a larger
initial volimie of carbon disulfide is taken.
^Procedure(b) About 6 to 8 ml. carbon disulfide are placed in a
hard glass test tube or a measuring cylinder and a drop of mercury is
added with the dropper described on page 17. The contents are then
shaken vigorously. When even very small amounts of free sulfur are
present, the surface of mercury is stained with a black or iridescent film of
mercury sulfide"" which can be identified by the iodine-azide reaction."*
The carbon disulfide is poured off and the drop of mercury is placed on
a watch glass and heated in a current of steam (see page 29) to remove the
last traces of carbon disulfide. The mercury is covered with iodine-azide
solution, and a foam of nitrogen bubbles forms around the drop of mercury.
Detection of Sulfide Sulfur in Animal Charcoal and in Dyes"'

The test for sulfide sulfur, in animal charcoal, for instance, using the
iodine-azide reaction as described on page 227, may be carried out on a
few mg. of sample.
Sulfur dyes, prepared by melting together aromatic amines and
diamines with alkali polysulfides, usually contain organically combined
sulfidic sulfur. They give the iodine-azide reaction. The constitution of
most of these dyes is not known.
A few mg. of the solid sample, which may be dry or moistened with
water, or else a thread or piece of dyed cotton, are treated with a drop of
"It is important that the carbon disulfide should be completely removed, as
CSi can catalyxe the reaction, 2 NaNi + I: = 2 Nal + 3 Nj, due to the intermediate
formation of azidodithiocarbonate. Compare page 417.
"E> Obach, / . -prakt. Chem., 18, 268 (1878), recommended the application of
this sulfide formation to the detection of small amounts of sulfur in CSj.
'"The iodine-azide reaction is positive, even for amounts of HgS too small
to be detected by optical means.
"Compare F. Feigl, Mikrochemie, IS, 1 (1934).
482 VII. APPLICATIOKS OF SPOT BEACTrONS
iodine-azide solution and observed for bubbles of ijitrogen. Woollen

material, which is not normally dyed with sulfur dyes, cannot be tested
in this way, as wool itself gives a positive azide reaction (see page 484).
The following results were obtained with a number of sulfur dyes :
Primuline yellow"' no reaction
Catigen brown 2 R extra vigorous evolution of nitrogen
Catigen brilliant green G evolution of nitrogen
Catigen yellow GG extra very vigorous evolution of ^nitôgen
Catigen black SW extra very vigorous evolution of nitrogen
Catigen indigo CL extra very vigorous evolution of nitrogen
Catigen violet 3 R very vigorous evolution of nitrogen
Detection of Free Sulfur in Solid Inorganic and Organic Products"^
The procedure described on page 277 for the detection of free sulfur
through the formation of acid-resistant thallium polysulfide on the spotted
area involves a protective layer effect. It can be employed also to reveal
the presence of uncombined sulfur in insecticides, pharmaceutical materials,
and the like. A preliminary extraction of the dry sample, finely powdered
if possible, with carbon disulfide or pyridine is necessary. Often it is
desirable to subject the sample beforehand to treatment with hydrochloric
acid in order to remove acid-soluble constituents. The residue is then
dried at 105 C. Any amorphous sulfur is thus converted into the crystal-
line form, which is soluble in carbon disulfide (see page 277). The extrac-
tion can be made in a microextraction apparatus. One drop of the clear
extract is placed on black, freshly prepared thallium sulfide paper. The
solvent is allowed to evaporate, and the paper is then placed in dilute
nitric acid. If sulfur is present, a brown-red or light brown fleck, depend-
ing on the quantity, is left at the site of the spotting. The rest of the paper
turns perfectly white.
Vulcanized rubber can be tested for imcombined sulfur. A particle
of the sample is kept in contact with carbon disulfide for 42 or 3 minutes
in a test tube. A drop of the liquid is transferred to thallium sulfide paper.
A distinct fleck of polysulfide remains after treatment with acid.
The following procedure will reveal free sulfur in sulfide ores, gas
purifying masses, etc. Several mg. of the dry, finely pulverized sample
are placed on thallium sulfide paper and moistened with 2 or 3 drops car-
bon disulfide, applied at short intervals. After the solvent has evaporated,
the dry powder is brushed off the paper which is then placed in dilute acid.
A dark fleck develops if free or extractable sulfur was present. In this
way, considerable quantities of soluble sulfur were shown to be present in
"'Primuline yellow (base) is one of the few sulfur dyes whose constitution
has been elucidated. As a mixture of di- and trithiazo compounds, all of its sulfur
is in etherlike combination. Its negative response to the iodine-azide test conforms
to this structure.
"F. Feigl and N^ Braile, Chemint-Anaiyst, SS.JSS (1944).
DETECTION OF TRACES OF CAHBON DISULFIDE 483
pyrite, marcasite, and galena; only traces of sulfur could be detected

in zinc blende.
Sulfur dissolved in organic liquids can be detected by placing a drop
of the solution on thallium sulfide paper, which is then treated with acid.
This test can be used to determine the completion of a sulfur extraction
with organic liquids. The latter process is often used in the quantitative
determination of sulfur, or for the purification of precipitated sulfides
(HgS,'MoS,,etc.).
Distinction between Acid and Basic Dyes"'

Dyes that are predominantly basic are soluble in melted stearic acid,
while predominantly acid dyes are soluble in melted urea. These proper-
ties are connected with the electropolar nature of the substances (salt or
solvate formation). This behavior may be applied as a quick and simple
means of differentiating these two classes of dyes.
UProcedureUrea and stearic acid are melted in a test tube, a
grain of the dye is added, and the mixture well shaken. When the two
layers separate, one will be colored. If the under layer (urea) is colored, an
acid dye is present; the upper layer (stearic acid) is colored, a basic dye
is present.
An excess of dye should be avoided; otherwise both layers are some-
times colored.
Detection of Traces of Carbon Disalfide in Benzene and Carbon
Tetrachloride'"
Crude benzene and carbon tetrachloride usually contain a small
amount of carbon disulfide; in crude benzene, about 0.1 to 0.2%, and in
carbon tetrachloride 0.1 to 3.5%. The carbon disulfide enters benzene
due to its preparation by the distillation of hard coals containing sulfur.
The presence of carbon disulfide in carbon tetrachloride arises from its
preparation from carbon disulfide by chlorination:
CSj + 2 SjCU = CCI4 -f- 6 S
Contamination by carbon disulfide may be detected by the reaction
described on page 418. It is based on the acceleration of the formation of
sulfide from carbon disulfide and alkali, in the presence of formaldehyde.
The sulfide can be detected by the precipitation of lead sulfide from a
plumbite solution.
^ProcedureTwo or three drops of the benzene or carbon tetrachlo-
ride is mixed on a spot plate with 1 or 2 drops of a strongly alkaline plumbite
"D. Reichinstein, Helv. Chim. Acta, 20, 882 (1937).
" ' F . Feigl and K. Weieselberg, Z. anal. Chem., 83, 101 (1931).
solution and 2 drops 40% formaldehyde solution (formalin). A dark ring

of lead sulfide is formed at the boundary between the organic solvent and
the water layer if carbon disulfide is present. Any hydrogen sulfide must be
removed before carrying out the test. This removal |is described on
page 419.
Detection of Lead Tetraethyl (-phenyl) in Motor Fuels^^^
Certain organometallic compounds (alkyl, aryl, carbonyl, and acetyl-
ide metallic compounds) are added to mineral oils, as even small amounts
have a decided effect on certain undesirable reactions. They usually
decrease the velocity of the reaction. These substances are used chiefly
as antiknock agents in motor fuels and as antioxidants in hydrocarbons.
Since lead tetraethyl (phenyl), which is most frequently used, is very vola-
tile and is also extremely toxic, a sure test for this compound has important
practical significance. The following test is easily applied to gasoline and
other motor fuels.
^ProcedureOne or two drops of the gasoline are placed on filter
paper and held in ultraviolet light for about 30 seconds until evaporation
is com.plete."' A drop of a freshly prepared 0.1% solution of dithizone in
chloroform is then placed on the paper. If Pb(C2Hs)4 or Pb(C6H6)4 is
present, a deep red stain (see page 57) results; in the absence of lead salts,
the paper remains green. When the gasoline is highly colored it should be
decolorized beforehand by shaking with activated charcoal.
Oils usually have a deep color of their own. When they are tested for
lead salts, 100 to 150 ml. oil are mixed with 3 % benzene and steam-dis-
tilled. The lead test as outlined is then carried put on the distillate.
Alternatively, a drop of a gasoline containing Pb(CjHs)4 is shaken with
a 1% aqueous solution of potassium cyanide and exposed to ultraviolet
light for a few seconds. A drop of dithizone solution is then placed on the
liquid surface."'
Traces of nickel carbonyl in benzene solutions may be detected by
an analogous method (using ammonia water and dimethylglyoxime, or
rubeanic acid).
DiiFerentiation of Animal and Vegetable Fibers""

Vegetable fibers are free from sulfur, but those derived from animal
sources contain sulfur compounds in the cysteine components of the protein.
These compounds possess an SH group, which can accelerate thp iodine-
" ' B . Steiger, Petroleum, 33, 27 (1937).
"H. Kieiastedt, Z. angew. Chem., 42, 1107 (1929), states tKat this tretinent
results in the decomposition of organo-lead compounds, with depostion of acid-
soluble flocks.*
"B. SteigerfMikrochemie, 23, 227 (1937).
"F. Feigl, Mikrocktmit, 14, 7 (1934). ^
DETECTION OF OXALIC ACID IN LEATHER 486
azide reaction. Hence, wool and cotton may be differentiated by applying

the iodine-azide test, as described on page 227.
UProcedureThe fiber, or small piece of woven material, is moist-
ened with a drop of water or acetone on a watch glass, and treated with
1 or 2 drops of the iodine-azide solution (for preparation, see page 228).
After a little while, the wool fiber is covered with little bubbles, while the
cotton fiber shows none. Cotton fibers are colored dark violet owing to the
adsorption of iodine, but the color of the bubbling wool fiber remains
unchanged. Bleached or unbleached cotton may be used in the test; both
are colored violet in the test, with no bubble formation. Half-wool mix-
tures give a positive response, thus revealing the presence of animal fibers.
Test for Esters in Mixtures of Hydrocarbons'^^

Fats and fatty oils, that are esters of glycerol, may be identified by
the,glycerol reaction described on page 408 (identification of acrolein).
Esters of other alcohols, such as waxes and resins, which give no glycerol
reactionj^ may be detected by the test for esters described on page 358.
[conversion to hydroxamic acids followed by the formation of iron (HI)
salts ]. The presence of waxes and resins in mineral oils may be determined
by means of this reaction.
The hydroxamic acid reaction gives the following colors with the
waxes and resins:
Beeswax violet-brown , "Soromin" (syn-
thetic ester) violet
Carnauba wax dark brown-violet Balsam Tolu brown-green
Candelilal wax... .lilac Colophony brown-green
Montan wax green-yellow Congo copaL brown
Detection of Oxalic Acid in Leather'^

Oxalic acid is very often used for bleaching vegetable-tanned leathers.
It is therefore sometimes important to be able to detect oxalic acid in
finished leather products. The test by the formation of aniline blue, as
described on page 403, is suitable for this purpose. It can be carried out
directly on a small piece of leather, or on the sole of a finished shoe, for in-
stance. The intensity of the color reaction indicates whether traces or
appreciable amounts of oxalic acid are present.
IfProcedureA little diphenylamine (about 0.02 g.) is placed on
the leather and pressed down with a thick glass rod. The reagent is melted
by heating from above with a very smallflameand carefully kept in fusion
for about 1 minute. Then, 2 or 3 drops alcohol are gently dropped on.
The piece of leather is placed where it is exposed to as much light as pos-
"F. Feigl, V. Anger, and O. Frehden, Mikrochemie, 16, 18 (1934).
K. Klanfer and A. Luft, Mikrochim. Acta, 1,142 (1937).
486 VII. APPLICATIONS OF SPOT BEACTIONB
sible. The appearance of a blue color indicates oxalic acid. When oxalic
acid and diphenylamine are melted together in ai crucible, the blue color
appears immediately on the addition of alcohol,-but in the test on the
leather the color develops only after some time, \yhen considerable oxalic
acid is present, the blue forms after about 1 to 2 hours, but for very small
amounts, 10 hours standing is necessary. The development of the blue
is accelerated by light; samples kept in the dark remain unchanged for days.
Tests, for Added Materials and Undesirable Admixtures in Organic
Substances
It is often important to be able to detect certain impurities that
may have been added to organic products, as well as undesirable by-
products that have not been removed. This branch of testing is especially
necessary in the examination of foods and drugs and cosmetics, when a
harmful impurity or unscrupulous adulteration must be detected quickly.
If the impurity or adulteration is inorganic, the numerous tests described
in Chapters 11 and III are available. These tests should usually be carried
out on the ash or acid extract of the sample. In testing for organic sub-
stances, many of the tests described in Chapter VI may be applied. A few
pertinent examples are discussed here.
(a) Detection of formic acid. Formic acid should not be present in
wood vinegar, as it is injurious to health. This acid (which has a definite
antiseptic action) is also an inadmissable fermentation product in fruit
juices, jams, marmalade, honey,'etc. If permitted at all, the quantity
should be slight. Formic acid may be detected as described on page 397
[formaldehyde chromotropic acid]. If the products are colored or had
color added to them, they should be decolorized (if necessary after solu-
tion) before carrying out the test. Animal charcoal can be used to remove
the color.
(6) Detection of glycerol. The test for glycerol described on page 408
has many applications. This depends on a color reaction of acrolein,
which is readily formed by the removal of a molecule of water from glyc-
erol. Since glycerol, in the form of a glycerol ester of various organic
acids, is a constituent of all plant and animal fats, beeswax or lanolin
{adeps lanae anhydr.), for instance, may be tested to find whether they
contain any admixture of plant or animal fats, which should not remain in
a first-rate product. . The glycerol reaction may be used successfully to
detect fats in cloudy or' dark products. The rapid djctection of pure
glycerol is often useful in testing cosmetics, andrfurther in testing wines
and liquors, which often contain glycerol, as" an "illegal sweetening agent.
(c) Detection of citric and malic adds. The detection of citric and
malic acids is important in testing fruit vinegar, as this commodity should
always contab these acids. As both citric and malic acids are hydroxy-
ADMIXTUBES IN ORGANIC SUBSTANCES 487
carboxylic acids, with the carboxyl groups in the 1,2-positions, the reaction
for this group, as described on page 360, may be applied as a simple and
rapid means of testmg "fruit vinegar."
(d) Detection of pyridine. A test for pyridine is useful as a rapid means
of identifying denatured alcohol, as pyridine is often used as the denaturing
agent. The test for tertiary ring bases (see page 392) and also the test for
pyridine (page 414) may be applied to detect rapidly slight amounts of
pyridine in a small sample.
(e) Detection of saccharine. Saccharine is often used as a substitute
for sugar, as it is 600 times as sweet. It may be used illegally in wine,
spirits, fruit juices, jams, and honey, and so its detection is very important
in food analysis.
Saccharine is the imide of o-sulfobenzoic acid
^ ^ s a\
NH
and behaves as an imide in the rhodamine reactions described on page 375.

It also reacts analogously to the anhydrides or imides of acids with carboxyl
groups in the 1,2-position, and condenses with resorcinol (see page 360).
Twofluore!;centcompounds are formed. A little of the sample is heated
with sublimed resorcinol and cone, sulfuric acid to 130 C. The reaction
product is taken up in water and made alkaline. A deep yellow-green
fluorescence results, that is visible even in daylight. Another portion of
the sample is fused withfluoresceinchloride and zinc chloride, and the melt
is taken into solution. Viewed in the light of a quartz lamp, it shows a
bright yellowfluorescencewhen acid, and a dark yellowfluorescencewhen
alkaline. A beautiful rose-violetfluorescenceappears as the neutral point
is traversed and flocculation occurs at the same time.
(f) Detection of rancidity in fats.^^^ A characteristic property of ran-
cid fats is that they contain varying quantities of organic peroxides, alde-
hydes, and hydroxy fatty acids. Peroxides in fats may be readily detected
by a spot test. This involves the conversion by peroxides of 2,7-diamino-
fluorene in the presence of hemin to blue meriquinoid oxidation products
(see pages 242 and 424).
llProcedureA drop of the light brown reagent solution is placed
on spot paper followed by a little of the sample material. After a short
time, in the presence of peroxides, the stain turns blue. The intensity of
color varies with the peroxide content.
""O. Frehden, Mikrockim. Acta, 2, 214 (1937).
488 VII. APPLICATIONS OF SPOT BijACTIONS
When testing fats, the sample may be n i b b ^ diiêctly on to the fleck

of reagent with a glass rod. Preferably, a satujrated solution is prepared
in a little peroxide-free ether or petroleum ether. The blue color with the
reagent appears when the sample is rancid. Usually, 'the blue stain has a
green to blue-green center, whict appears to be ^ mixed color between the
blue oxidation product and its yellow to red-brown condensation products
with the aldehydes.
Reagent: 100 mg. 2,7-diaminofluorene and 5 mg. hemin in 6 ml.
glacial acetic acid (freshly prepared)
Application of Spot Tests in the Examination of Powder and Explosives'^*

Black powder, which contains large amounts of nitrates, may be
tested for nitrate with a drop of the aqueous e:(tract. The test given on
page 243 can be used. Similarly the chlorate ion of chlorate explosives
may be detected by the reaction on page 221. The residue from burned
black powder always contains thiosulfate, thiocyanate, and sulfide. Even
traces of these may be identified by the iodine-^zide reaction (page 227).
The test given on page 184 may be used for the detection of ammonium
salts (NH4NO3).
Aromatic polynitro compounds (picric acid^ trotyl) may be identified
by the test on page 323 for m-dinitro compounds.
Azides can be detected by the reactions of hydrazoic acid discussed on
page 215. Free sulfur can be detected in explosives and powders by the
procedures given on pages 480 and 481.
Explosives that contain esters of nitric a,cid (nitrocellulose, nitro-
glycerin, tetranitropentaerythrite, etc.) are reduted to nitrites by a simple
procedure, and identified as such (see page 248).
^ProcedureA few mg. of the sample is niixed on a spot plate with
an acetic acid solution of sulfanilic acid and a-naphthylamine. A little
zinc dust or Devarda's alloy is added. After a few mmulesr-thejolution
(or solid) is colored bright red by the resulting azo dye.
Reagents: 1) Zinc dust (or Devarda's alloy)
2) Solutions of sulfanilic acid^ and a-naphthylamine in
acetic acid (see page 248)
Esters of nitric acid may also be detected, in threads of textiles.
Microscopic examination will reveal admixtures ()r nonimpregnated cotton.
When nitrates and insoluble nitro compounds ^re to be detected in the
presence of each other, an aqueous extract should be prepared. After
centrifugmg or filtration, the clear solution is tested for ritrate, and the
residue after reduction, for nitrite.
"*A. A. Awam, MtfcrocAtm. Ada, 3,283(1837).
VIII. BIBLIOGRAPHY ON THE APPLICATION
OF SPOT REACTIONS FOR SPECIAL
SCIENTIFIC OR TECHNICAL PURPOSES
The following listing, which makes no pretense at being complete, includes
books andpapers dealing wholly or in part with spot reactions. The present volume
either does'not refer to the content of these publications or refers to them only cur-
sorily. Some of the entries have valuable suggestions or information regarding the
use of spot reactions in the most varied fields. Others contain statements of general
or special significance for the theory and practice of spot test analysis.
A. JOURNALS
Adamovich, L. P., and Zagorulko, A. lA. Rapid detection of vanadium in steel
without spoiling the sample. Chem. Abstracts, 37, 1346 (1943).
Aloy, J., Valdigu^, A., and Aloy, R. Transformations induced by solar light in pres-
ence of uranium compoundscharacteristic reactions of strychnine, morphine,
codeine and formol. Bull. soc. chim., 39, 792 (1926); Chem. Abstracts, 20, 29S2
(1926).
Alvarez, E. P. Color reactions of pyroracemic acid with a- and /3-naphthol in sulfuric
acid solution. Chem. News, 91, 209 (1905).
Arnold, E. Testing objects plated with metals. Chem. Abstracts, 27, 3671 (1933).
Ashburn, G., and Reedy, J. H. Specific test for vanadium. Ind. Eng. Chem., And.
Bd., 17*63(1945).
Atkinson, J. V. Detection of metallic driers in varnish and oils by spot test analysis.
PaM Oil Chem. Rev., 106, No. 1,10, 22-23 (1943).
Augusti, S. Microoolor test for the manganous cation. Ann. chim. applicata, 24,
635 (1934).
Berraz, G. Electro-capillary Analysis. Ayiales inst. investigaciones dent, nae.,
13, 67 (1943).
Bontinck, E. Hepar test in analysis of natural and artificial ultramarine and other
pigments containing sulfur. Z. anal. Chem., 116, 182 (1939).
Boyd, T., Degering, E. F., and Shreve, R. N. Relative values of certain azo deriva-
tives of 8-hydroxyquinoline as analytical reagents. Ind. Eng. Chem., Anal. Ed.,
10, 606 (1938).
Brinker, H. C., Color test for oils and resins, using Hirschsohn reagent for choles-
terin. Ind. Eng. Chem., Anal. Ed., 17, 130 (1945).
Brdning, A., and Schnetka, M. Chemical detection of traces of metal in gunshot
wounds. Chem.-Ztg., 61, 827 (1937).
Busch, H. Advances in detection of minute quantities of materials. Z. angew.
Chem., 46, 124 (1933).
Chaletzki, A. M. Use of spot tests in examination of several medicinals. Pharm.
u.Pharmakol. (Russian) 1937,15; Chem. Zentr., 1938, III, 353.
Clarke, B. L., and Hermance, H. W. Paper as a medium for analytical reactions.
Ind. Eng. Chem., Anal. Ed., 9, 292 (1937); 10, 591 (1938).
Corbett, R. B. Spot test for the separation of alximinum bronze from manganese
bronze. U. S. Bur. Mines Rept. Investigations Tech. Papers, 3786, (1944).
Costeanu, N. D. Detection and determination of silver microchemically and with
aid of filter paper impregnated with reducing solutions. Mikrochemie ver.
Mikrochim. Acta, 26, 170 (1939).
489 32
490 Vni. BIBLIOGRAPHY /
Davies, W. C. Scheme for qualitative chemical analysis employing spot tests.

J. Ghem. Education, 17, 231 (1940). '
Duke, F. R. Color test for the carboxyl group. Ind. Eng. Chem., Anal. Ed., 16,
110 (1944). 'I
Duval, C , and Mazars, G. Drop reaction for the halogens. Com.pt. rend., 207,
862 (1938). '
D'yachkovskil, S. I., and Isaenko, T. I. New method for qualitative analysis of
acids. Chem. Abstracts, 26, 48 (1932).
Eck, P. N. van. Benzidine as reagent for aldehydes. Pharm. Weekhlad, 60, 1204
(1923).
Eck, P. N. van. Macro-microreactions. Pharm. Weekblad, 62, 369 (1925); 63, 913
(1926); Chem. Abstracts, 19,1828 (1925).
Edeler, A. Ground glass for spot testing in solvent extractions. Ind. Eng. Chem.,
Anal. Ed.,16,282 ilMZ).
Edge, S. R. H. Determination of true pH in paper. World's Paper Trade Rev.,^7,
1336,1376(1932).
Edwards, W. T. Detection of nickel; spot test for high conductivity copper alloys.
Metal Ind., 65, 329 (1944).
Eegriwe, E. Reactions and reagents for detection of organic compounds. Z. anal.
Chem., 89,121 (1932); 95, 323 (1933); 100, 31 (19^5).
Eegriwe, E. Microchemical detection of certain phenols. Mikrochemie, 23, 173
(1937). . , /
Erametsa, 0 . Sulfosalicylic acid as reagent for detecting oxalic acid. Chem. Ab-
stracts, S7, Q20S (1943).
Evans, B. S., and Higgs, D. G. Spot tests for the detection of alloying elements in
steel. Analyst, 70, 75 (1945).
Feigl, F. Spot and color reactions as microchemical methods. Mikrochemie, 1, 4
(1923).
Feigl, F. Spot reaction experiments, I-XI. J. Chem. Education, 20, 137, 174, 240,
298, 300 (1943); 21, 294, 347, 479 (1944); 22, 36, 342, 558 (1945).
Feigl, F., and Ribeiro, O. Microreaction for vitamin Bi. Rev. soc. brasil. quim., 2,
1 (1942).
Feigl, F., and da Silva, C . P . J . Identification of acid groups in organic compounds.
Bol. ministerio agr. Brazil, Lab. produgdo mineral.. No. 5 (1942).
Fenton, H. J. H. Reagent for identification of urea and certain other nitrogen com-
pounds. / . C/iem. Soc.,83,187 (1903). ,,^
Ferjantschitsch, F. A., and Ugniwenko, M, G. Spot procedure for detection of tungs-
ten in ores. CAem.^toracts, 33,4904 (1939).
Fleury, G. Characteristic reaction of morphine. Ann. chim. anal. chim. appL,
6, 417 (1901).
Frankel,E. Use of spot analysis in laundry operations. Deut. Waeschereizfg., Si,
410, 421 (1932). /
Frehden, O., and Huang, C.-H. Microdetection of morphine and heroin in urine by
spot reactions. Pftarm. Monafsh., 18, 73 (1937).
Frehden, O., and Huang, C.-H. Detection of free chlorine in air, water, bleaching
agents, detergents, etc. Mikrochemie ver. Mikrochim. Acta, 26, 41 (1939).
Fritz, H. New procedures for carrying out electrolytical spot tests. Mikrochemie,
19, 6 (1935); 21, 47 (1936); 22,.34,168 (1937); 23, 61ti937); 24, 22, 171 (1938).
Galopin, R. Chemical differentiation of polished metallic minerals by contact
method. Compt. rend. soc. phys. hist. nat. Genive, 52, 264, 257 (1935); Chem.
Abstracts, 80, 6670 (1936).
4 y'
Vin. BIBLIOGRAPHY 491
Galopin, R. Chemical differentiation of metallic minerals by imprint method.

Schweiz. mineralog. petrog. Aft., 16 (1936); CAem. Abstracts, 30, 7499 (1936).
Garre, G. New method for determining defects in zinc coatings on iron. Chem.-
Zig., 62, 759 (1938).
Glazunow, A. Anodic solution as electrographic method of microanalysis. Oesterr.
Cftem.-Z<g., 40, 217 (1938).
Glazunow, A. Reproduction of macrostructure by electrolysis. Chimie & Indus-
trie, 21,425 (1929); Chem. Zentr., 1930,1,2154.
Glazunow, A. Nondestructive quantitative analysis of alloys. Chimie & industrie,
27, 332 (1932); Chem. Zentr., 1932,1, 3205.
Glazunow, A., and Drescher, E. Electrographic determination of lead in lead-tin
alloys. Chem. Abstracts, 32, 6972 (1938).
Glazunow, A., and Krivohlav^, J. Quantitative electrographic determination of
nickel in nickel steels. Z. physik. Chem., A161, 373 (1932).
Glazunow, A., and Krivohlav^, J. Quantitative electrographic determination of
metals in alloys, especially in steel. Chem. Zentr., 1933, II, 3164.
Glazunow, A., and KrivoWav;^', J. Rapid electiogiaphic differentiation between
nickel- and chrome-plated materials. Chem. Zentr., 1934,1, 734.
Guilhon, J. Test for iron pigments (hemosiderin) in liver. Compt. rend. soc. biol.,
115, 376 (1934).
Gutzeit, G. Use of limit of identification of an element. Helv. Chim. Ada, 23,
17 (1940).
Gutzeit, G. Determination and localization of metallic minerals by contact print
method. Trans. Am. Inst. Mining Met. Engrs., 153, 286 (1943); Chem. Abstracts,
- 37, 576 (1943).
Gutzeit, G., Gysin, M., and Galopin, R. Indirect chemical examination of minerals
in a polished surface by "spotting." Compt. rend. soc. phys. hist. nat. Oenhe,
50,192 (1933); Chem. Abstracts, 28,3339 (1934).
Gutzeit, Q., and Monnier, R. Use of several azo derivatives of hydroxyquinoline in
inorganic analysis. fleZv. CAJ'TO. Acta, 16, 223, 479, 485 (1933).
Gutzeit, Q., Monnier, R., and Bachoulkova-Brun, R. Reagent for magnesium: 5-p-
acetomidophenylazo-8-hydroxyquinoline. Compt. rend. soc. phys. hist. nat.
Genbve, 50, 103 (1933); Chem. Abstracts, 28, 3332 (1934).
Gutzeit, G., and Weibel, R. Use of antipyrine iodide reagent in spot analysis.
Compt. rend. soc. phys. hist. nat. Genhe, 51, 33 (1934); Chem. Abstracts, 29, 2471
(1935).
Gysin, M., and Hiller, T. Examination of tetrahedrites by method of imprints.
Schweiz. mineralog.^petrog. Mitt., 15,289 (1935); CAem. Abstracts, 30, 2135 (1936).
Haitinger, M. Thalleioquin reaction in ultraviolet light. Contribution to fluo-
rescence analysis in microchemistry. Mikrochim. Acta,1,1 (1937).
Hamburg, H. Spot test analysis and its use in examination of brewery water.
Brau- u. Malzind., 25, 23 (1932).
Herraance, H. W. Printing technique in analytical chemistry. Bell. Lab. Record,
18,269(1940).
Hetterich, H. Use of spot reactions in study of pigments of paintings. Mikro-
chemie {Emich Festschrift) 1930, 152.
Hiller, T. Identification of silver in opaque minerals by imprint method. Compt.
rend. aoc. phys. hist. nat. Genbve, 53, 55 (1936); Chem. Abstracts, 31, 3816 (1937);
Hiller, T. Use of imprint method for determination of opaque minerals in section.
Schweiz. mineralog. petrog. Mitt.. 17, 88 (1937).
492 T m . BIBUOGRAFHT
Jirkovsk^, R. Method for detection of small quantities of nickel and cobalt in steels
without injuring the sample. Chem. Abstracts, 26, 5640 (1931).
Jirkovsk^, R. Electrographic methods. AfifcrocAemie, 15, 331 ,(1934).
Jirkovsk^, R. Use of Feigl drop tests for determining purity of assay beads. Chem.
Abstracts, 31, 2957 (1937).
Jirkovsk^, R. Purity tests of assay beads by spot reactions. Mikrochim. Acta, 1,
287 (1937).
Kisser, J., and Kondo, Y. Microchemical detection of di- and trihydric phenols by
spot reactions. Mikrochemie {Molisch Festschrift), 1937, 259.
Kisser, J., and Lettmayr, K. Studies of applicability of spot reactions for quanti-
tative purposes. Mikrochemie, 12, 234 (1932).
Klanfer, K. Application of spot reactions in studies of tanning procedures. Col-
legium (.Stiasny Festschrift), 1937, 178.
Kolthoff, I. M. Acid-Base Indicators. Macmillan, New York, 1937, Chapter XI
(indicator papers).
Kuenkele, F. Study of aniline ink writing. Z. Untersuch. Lebensm., Tl, 596 (1939).
Leonhardt, H. Merck Universal Indicators and Universal Indicator papers. Chem.
Zentr., 1938, II, 2624.
Lemer, M. Detection of gold in platings. Ind. Eng. Chem., Anal. Ed., 16, 416
(1943).
Liebreich, 0 . Method for examination of reactions of animal tissue. Ber., 1, 48
(1868).
Madaus & Co., Jahrbuch, 1933. Chapter on revision o( homeopathic materia medica
(A. Kuhn).
Neuber, F. Qualitative differentiation of asphalts and tar pitches. Ole Fette
Wachse Seife Kosmetik, No. 5, 5 (1938).
Niessner, M. Application of microchemical tests in metallography; correct recog-
nition of sulfur segregations. Mikrochemie, 8,121 (1930), Chem. Abstracts, 24,
4492 (1930).
Niessner, M. Local detection of phosphides in metal sections. Mikrochemie, 8,
339 (1930); Chem. Abstracts,25,893 (1931).
Niessner, M. New methods for chemical identification of minor constituents of
alloys and detection of segregation in metals. Mikrochemie, 12, 1 (1932); Chem.
Abstracts, 26, 5871 (1932).
Niessner, M. Several procedures for microchemical testing of surfaces. Berg-
u. hultenm&nn. Jahrb. montan. Hochschule Leoiben, 84, 104 (1936)^
Palet, L. P. J. Detection of selenium in sulfuric acid. Ann. ehim. anal. chim. appl.,
23, 25 (1918).
Pavelka, F. Significance of free surface as participant in reactions. Mikrochemie,
23, 202 (1937).
Percival, G. P. Mirror used to show spot plate tests. / . Chem. Education, 20, 187
(1943).
Poluektoff, N. S. Detection of rhenium by spot test. Chem. Abstracts, 32, 5724
(1938); cf. also 31, 4617 (1937).
Poluektoff, N. S. Sensitive test for germanium. Chem. Abstracts, 31, 4615 (1937).
Prdt, S. Detection of heavy metals in plants and method of the chromospodogram.
Mikrochemie {Molisch Festschrift), 1937, 342. /
Przibram, E. M. Thread spot methods for microscopic analysiS^f very small amounts
of liquids. Chem. Zentr., 1939,1, 475.
Rhodes, H. T. F: Forensic chemistry and its aids. Chem. Trade J., 8, 286 (1937).
v m . BIBUOGBAPHT 493
Sabetay, S. Antimony trichloride, new reagent for the double bond. Compt. rend.,
197, 557 (1933).
Schafer, H. Qualitative analysis and colorimetric estimates by means of Jena glass
spot plates. Mikrochim. Acta, 1, 144 (1937).
Schemjakin, F. M., and Belokon, A. N. New drop reaction of vanadates and molyb-
dates with a-nitroso-^-naphthol. Chem. Abstracts, 32, 4467 (1938).
Sehiflf, H. Detection of uric acid. Ann., 109, 67 (1859).
Schwarz, G. Photographic silver gelatin paper as reagent in spot analysis. Ind.
Eng. Chem., Anal. Ed., 12, 369 (1940).
Schwarz, G., and Schouwenaars, M. Qualitative analysis of photographic de-
velopers. Natuurw. Tijdschr., 21,137 (1939).
Scriba, F. Detection of small amounts of water. Z. physik. chem. Unterricki, 19,
298 (1906).
Seifter, J., and Trattnqr, H. R. Simplified qualitative analysis of gallstones by spot
reactions. / . Urol., 42, 452 (1939).
Silbermintz, W. A., and Florenzki, K. P. Spot colorimetric procedure for approxi-
mate quantitative estimation of small amounts of vanadium in ores in situ.
Mikroehemie, 18, 154 (1935).
Smith, L., and West, P. Qualitative analysis by means of drop reactions: a sys-
tematic study of interference. Proc. Iowa Acad. Sci., 46, 189 (1939).
Smith, L., and West, P . Interferences occurring with selected drop reactions.
Ind. Eng. Chem., Anal. Ed., 13,271 (1941).
Steigmann, A. Detection of traces of copper in photographic papers. Phot. Ind.,
36, 1365 (1937).
Steigmann, A. Photographically interesting fine chemicals as specific spot test
reagents. / . Soc. Chem. Ind., 62, 42 (1943).
Steigmann, A. Specific test for mercury with dithizone membrane papers. / . Soc.
Chem. Ind., B2,43 ilHZ).
Steigmann, A. Experiments with a cationic wetting agent. J. Soc. Chem. Ind.,
64, 88 (1945).
Sulfrian, A. Determination of phosphate content in pure and boiler waters. Chem.-
Ztg., 66, 650 (1932); Warme, 66, 371 (1932).
Tamchyna, J. V. Relation between sensitivity of reaction and molecular size in the
case of organic reagents. Mikroehemie, 3,229 (1931).
Tananaeff, N. A., and Schapowalenko, A. M. Spot determination of silicic acid in
limestone, dolomite and cement. Chem. Abstracts, 32, 5723 (1938).
Tauber, H. New micromethod for detecting monoses in presence of reducing bioses.
Mikroehemie, 14,167 (1934).
Tauber, H. Sensitive spot reaction for ascorbic acid. Mikroehemie, 17, 111 (1935).
Tauber, H. Color test for pentoses. Proc. Soc. Exptl. Biol. Med., 37, 600 (1937).
Tougarinoff, B. Organic reagents in qualitative inorganic analysis. Ann. soc. sci.
Bruxelles, B60,145 (1930); Chem. Zentr., 1931,1,1321.,
Tougarinoff, B. Qualitative systematic analysis for cations. / . pharm. Belg., 16,
173,189, 205, 223 (1933); Chem. Zentr., 1933,1,3978.
Tougarinoff, B. Two color reactions of rhenium. Bull. soc. chim. Belg., 43, HI
(1934); Chem. Zentr., 1934, II, 1499.
Tunmann, O. Detection of nicotine. Apoth. Ztg., S3, A85 {1918).
Vallender, R, B. Detection of toxic gases and vapors in industry. Chemistry dt
Industry, 17, 330 (1939).
Vavilov, N. V. Color test for bismuth ion. J . Applied Chem. U.S.S.R., U , 356
(1938).
494 Vni. BIBLIOOBAPHT
Velculescu, A. J., and Cornea, J. Detection of iodidea on silver nitrate impregnated

paper. Z. anal. Chem., 94, 255 (1933).
Von Stein, P. Detection of indium in flue dust. Chemist-Analyst, 31, 63 (1942).
Wasicky,R., and Frehden, O. Application of spot tests in examination of medioinals.
Mikrochim. Acta, 1, 55 (1937). I
Weber, F. Spot reactions for approximate determination of vitamin C content of
plants. Proiop/osma, 33, 475 (1939).
Weihrich, R., and Schwertner, F. Testing materials by spot reactions without in-
juring the sample. Arch. Eisenhultenw., 16, 45 (1942).
West, P. A study of interferences in drop reactions. / . Chem. Education, 18,
628 (1941).
West, P., and Smith, L. Field Laboratory; microanalysis by means of portable
reaction kit. J. Chem. Education, 17, 119 (1940).
Wilson, C. L. Microtests for elements in organic compounds (P, As, Sb). Analyst,
65,405(1940).
Winckelmann, J. Several new methods of preparative microchemistry. Mikro-
chemie, 10, 437 (1932); 14, 171 (1934).
Winckelmann, J. Several new methods of qualitative microanalysis. Mikrochemie,
12, 127 (1932).
Winckelmann. J. New method for preparation of spots. Mikrochemie, 16, 203
(1934).
Withworth, C , and Poxon, D. W. Detection of acid or basic substances in damaged
fabrics. Nature, 161, 198 (1943).
Yagoda, H. Applications of confined spot tests in analytical chemistry. Ind. Eng.
Chem., Anal. Ed., 9, 79 (1937).
Yagoda, H. Semiquantitative spot tests by limitation of reaction field. Mikro-
chemie, 2i, 117 (imS).
Yagoda, H. Localization of certain chemical constituents in plant and animal tis-
sues. Ind. Eng. Chem., Anal. Ed., 12, 698 (1940).
Zurbruegg, E. Rapid method for differentiation of various aluminum alloys. Aia-
mtmm,20,196(1938).
B. BOOKS
Bamford, F . Poisons, Their Isolation and Identification. Blakiston, Philadelphia,
1940. ^
British Drug Houses. The Reagents for Delicate Analysis including'Spot-Tesls. 7th
ed., London, 1939.
Davison, E. H. Field Tests for Minerals. 2nd ed.. Chapman & Hall, London,
1940.
Eva.ich,F.,Microchemical Laboratory Manual. Translated by F. Schneider. Wiley,
New York, 1932.
Emschwiller, G., and Chariot, G. Riactions et mithodes nouvelles d'analyses qualita-
lives min&rales. Hermann, Paris, 1939.
Evans, B. S., and Higgs, D. G. Spot Tests for the Identification of Certain Metallic
Coatings and of Certain Metals in Bulk. Heffer, London, 1943.
Feigl, F. Specific and Special Reactions with Particular Reference to Spot Tests Analy-
sis. Translated by R. E. Oesper. Elsevier, New Y-erW, 1940.
Feigl, F. Laboratory Manual of Spot Tests. Translated by R. E. Oesper, Academic
Press, New York, 1943.
VIII. BIBLIOGRAPHT 495
Goppelsroeder, Fr. Kapillaranalyse. Steinkopff, Dresden, 1912.

Haitinger, M. Die Anwendung der Fluorescenzanalysein der Mikrochemie. Haim,
Vienna, 1937.
Herzog, A. Mikrochemische Papierunlersuchungen, Springer, Berlin, 1935,
Hopkin & Williams, Ltd. Organic Reagents for Metals and for Certain Acid Radicals.
4111 ed., Hopkin & Williams. London, 1943.
Kolthoff, I. M. Acid-Base Indicators. Translated by C. Rosenblum. Macmillan,
New York, 1937.
Merck Index, 5th ed., Rahway, N. J., 1940.
Nieuwenburg, C. J. van, and Dulfer, G. Short Manual of Systematic Qualitative
Analysis by Means of Modern Drop Reactions. Centen, Amsterdam, 1933. 2nd
ed., 1935.
Rhodes, H. T. F. Forensic Chemistry. Chemical Pub. Co., New York, 1940.
Rojahn, C. BeitrSge zur pharmazeutischen Analyse. Knapp, Halle, 1937.
Snell, F. D., and Biffen, F. M. Commercial Methods of Analysis. McGraw-Hill,
New York, 1944.
Tananaeff, N. A. Drop Methods of Qualitative Analysis (in Russian). Kharkov and
Kiev, 1934.
Vogel, A. I, Text-book of Qualitative Chemical Analysis. 2nd ed., Longmans, Green,
London, 1941.
Union internationale de chimie. Tables of Reagents for Inorganic Analysis. First
report of the International Committee on New Analytical Reactions and Re-
agents, Akadem. Verlagsgesellschaft, Leipzig, 1938.
IX. TABULAR SUMMARY
1
Of the Limits of Identification^ Attained
hy the Spot Tests
A. INORGANIC ANALYSIS. CATIONS
Reagents oi test reactions Limit of Page

Cation identified identification, y*
Aluminum Morin 0.2 142

Morin in ultraviolet light 0.005 142
Alizarin sulfonic acid 0.65 143
Alizarin 0.15 144
Quinalizarin 0.005 146
Pontachrome blue black 2 147
Ammonium aurin tricarboxylate 0.16 147
Ammonium p-Nitrobenzenediazonium chloride 0.67 182

Litmus paper 0.01 184
Manganese sulfate and silver nitrate 0.005 184
Silver nitrate and formalin (or tannin) 0.05 to 0.1 185
Nessler's reagent 0.026 185
Manganese sulfate-hydrogen peroxide-
benzidine 0.03 185.
Antimony- Zinc on platinum foil 20 83

Phosphomolybdic acid 0.2 84
Rhodamine B 0.5 86
Luminescence 86
9-Methyl-2,3,7-trihydroxyfluorone 0.2 85
Arsenic Stannous chloride 1 79

After reduction to ABH| , 0.05 to 1 80
Silver nitrate ^6 - 82
Kairine-ferric chloride 0.006 83
B&rium Sodium rhodizonate 0.25 165

Induction of precipitation of lead stilfate 0.4 167
Tinting of barium sulfate by perman-
ganate 2.6 167
Tetrahydroxyquinone 5 168
' The limit of identification is given for the most sensitive procedure, if the
reaction may be carried out in different ways. '
Unless otherwise stated, a macrodrop (about.OJOSrml.) is implied.
I n 0.1 ml.
496
XX.. TABVhAS, SUMMARY 4g7
A. INOBQANIC ANALYSIS. CATIONS. Continued
Cation identified Retgenti or test reactions Limit o{ Page

identification, y'
Beryllium Quinalizarin 0.14 147

p-Nitrobenzeneazoorcinol 0.2* 149
Bismuth Cinchonine and potassium iodide 0.14 59

Alkali stannite and lead salt 0.01 60
Luminescence 0.004 62
Potassium chromithiocyanate 0.4 62
Alkali stannite 1 63
Potassium manganese f II) cyanide 10 63
Formation of bismuth oxyiodide 25 63
Quinoline and potassium iodide 1 63
Thioacetamide 7 63
Cadmium Di-p-nitrophenylcarbazide 0.8 76

Ferrous dipyridyl iodide 0.05 74
Di-(5-naphthylcarbazone 0.02 78
Diphenylcarbazide 4 78
p-Nitrodiazoaminoazo benzene 0.25 79
CaI6ium Ammonium ferrocyanide 25 169

Dihydroxytartaric acid osazone 0.01 170
Cerium Hydrogen peroxide and anunonia 0.35 160

Ammoniacal silver nitrate 1 160
Alkaline hydroxide and benzidine 0.18 161
Fhosphomolybdic acid 0.52 161
Oxidation of leuco malachite green 0.03 162
Ammonium naphthoate, anthranilate,
salicylate 162
Cesium Gold-platinum bromide 0.25 182

Potassium-bismuth iodide 0.7 182
Gold-palladium chloride 1 182
Chromium Diphenylcarbazide, after conversion to

chromate
in alkaline solution 0.25 128
in acid solution 0.8 129
Benzidine, after conversion to chromate 0.35 131
Acid alizarin RC 0.6 132
Silver nitrate, after conversion to chro- 6 132
mate
Lead acetate, after conversion to chro- 6 132
mate
In 0.04 ml.
In 0.1 ml.
In OXIOI ml.
498 EC. TABULAB SUMMARY^
A. INORGANIC ANALYSIS. CATION^. Continued
Cation identified Reagents oi test leactions \ Limit of Page

identification, 7
Cobalt a-Nitroso-j3-naphthol | 0.05 109

Rubeanic acid 0.03 112
Ammonium thiocyanate and acetone 0.5 112
^-Nitroso-a-naphthbl ca. 0.005 110
2-Nitroso-l-naphthol-4-sulfomc acid 0.01 113
Copper Catalysis of the ferric salt-thiosulfate 0.02 63

reaction
Benzoin oxime 0.1 65
Salicylaldoxime 0.5 66
o-Tolidine and ammonium thiocyanate 0.003' 67
Phosphomolybdic acid. i 1.3 67
1,2-Diaminoanthraquinone sulfonic acid 0.02 68
Rubeanic acid 0.006' 70
Dithizone / 0.03 72
Benzidine and potassium bromide 0.6 73
p-Dimethylaminorhodanine 0.6 73
8-Hydroxyquinoline and potassium cya- 0.4 73
nide
Ammonium mercury thiocyanate and 0.1 73
zinc salts
Hydrobromic acid 0.15 74
2-Nitroso-l-naphthol-4-sulfonic acid 0.01 74
Phenetidine and hydrogen peroxide 74
Diphenyl carbaz one 0.002 74
Di-OT-nitrophenylcarbazone 0.05 74
Gallium Potassium ferrocyanide ajnd manganese 6> 164

chloride
Germanium Increase of acidity due to mannite 2.5 89

Ammonium molybdate and benzidine"'"^^ -_ 0.25' 90
Hydroxyanthraquinone ^ 91
Gold p-Dimethylaminobenzylidene rhodanine 0.1 100

Benzidine 0.02i<!. 100.
.Reduction to metal 1 100
/
Hydrazine Salicylaldehyde 0.1 186
Hydroxylamine Diacetylmonoxime and nickel salt 1 186

Salicyl aldehyde and copper salt ' 1 187
Conversion into nitrous acid. -' 0.01 189
Reduction to ammonia " 0.1 190
Indium Alizarin or quinalizarin 0.05' 162
' In 0.015 ml. I n 0.025 ml.

In 0.04 ml. I n 0.001 ml.
IX. TABULAR SUMMARY 499
A. INOHQANIC ANALYSIS. CATIONS. Continued
Cation identified Reagents or test reactions Limit of

identification, y* Page
Iron Potassium ferrocyanide 0.05 122

a,a'-Dipyridyl 0.03 122
8-Hydroxyquinoline-7-iodo-5-sulfonic 0.5 124
acid
Potassium tliiocyanate 0.25 124
Dimethylglyoxime 0.04 125
Di8odium-l,2-dihydroxybenzene-3,5- 0.05 126
disulfonate
Thioglycolicacid 0.01 127
Quercetin or quercitrin 3 128
2-Nitroso-l-naphtho!-4 sulfonic acid 0.01 128
Lead Benzidine after conversion to PbOj 1 , 55
Sodium rliodizonate O.I 56
Dithizone 0.04 57
Cadmium-stannous iodide 10 58
Gallocyanine 0.3 58
Carminic acid 1 59
Lithium Complex ferric periodate 0.1 180
Magnesium Alkali hypoiodite 0.3 171
p-Nitrobenzeneazo--naphthol 0.19 173
Titan yellow 1.5 176
p-Nitrobenzeneazoresorcinol 0.5 173
Conversion into magnesium oxide 0.6" 176
Manganese Catalytic oxidation to permanganate
fn acid aoZution O.l 132
in alkaline solution 2.5 133
Periodate and tetrabase 0.001 134
Alkali hydroxide and benzidine 0.16 134
Ammoniaeal silver nitrate 0.05 137
Mercury Diphenylcarbazone 0.1 48
Dithizone 0.25 49
Stannous chloride and aniline 1 50
p-Dimetbylaminobenzylidene rhodanine 0.33 51
Catalysis of the reduction of tin (IV) salt . 0.1 52
by hypophosphites
Catalysis of the formation of alutnina 0.001 53
from aluminum
Copper (I) iodide 0.03 55
Chromotropic acid 100 55
" In 0.005 ml.
5(X) DC. TABinAB SX7MMARY
A. INOROANIC ANAI/TSIB. CATIONS. Continued

' r-
CttioB identified Limit of Page
Reagents or test reactions identification, -y*
t
Molybdenum Potassium thiocyanate and stannous 0.1 92
chloride i
Potassium xantbate 0.04 93
Zinc or cadmium xanthate 0.02 93
Phenylhydrazine 0.13 94
Tincture of cochineal 0.02 94
a,a'-Dipyridyl and stannous chloride 0.4 94
Diphenylcarbazide 2.6 '94
Di -/3-naphthylcarbazone 0.3 94
Nickel Dimethylglyoxime 0.015 114

Dimethylglyoxime and bromine water 0.12 117
Rubeanic acid 0.012" 117
Osmium and 5,11111- Potassium chlorate and potassium iodide 0.005 107
enium Rubeanic acid 0.2 108
Benzidine or potassium ferrocysoide 0.01" 109
Palladium Stannous chloride 0.04" 104

Catalysis of the reduction of phoepho- 0.025 105
molybdates by carbon monoxide
Nickel dimethylglyoxime 0.05 106
Naphthalene-4'-sulfonic acid-l-azo-5-o- 2 107
8-hydroxyquinoline
p-Dimethylaminobenzylidene rhodanine 0.004 107
Diphenylcarbazide and mercuric cyanide 0.6 107
Platinum metala Condensation of hydrogen 0.04 to 0.18" 101

Induced reduction of nickel salts 0.0025 to 1.5 103
Platinum Stannous chloride 0.025 104
Potassium Sodium cobaltinttrite " - 4, , 177'

Sodium cobaltinitrite and silver nitrate 1 178
Dipicrylamine 3 " 178
Silver Manganese nitrate and alkali 2 42

p-Dimethylaminobenzylidene rhodanine 0.02 43
Physical development of silver nuclei 0.005 45
Catalytic reduction of manganese (III) 0.4 to 0.05 47
and cerium (IV) salts
Potassium chromate 2 48
Dithizone ''O.OS 48
Stannous chloride and chromotropic acid 0.1 mg. 48
Stannous chloride 1 48
I n 0.016 ml. " I n 0.002 ml.

H In 0.001 ml. " I n 0.001 ml.
IX. TABULAB BUUMABT 501
A. INOBOANIC ANALTSIS. CATIONS. Continued
CaUon identified Reagents or test reactions Limit of Page

identi&cation, t*
Sodium Zinc uranyl acetate 12.5 176

in ultraviolet light 2.5 177
Strontium Sodium rhodizonate 3.9 169
Thallium Potassium iodide 0.6 119

Benzidine 0.3 119
Phosphomolybdic acid and hydrobromic 0.13" 120
acid
Dipicrylamine 20 121
Ammonium sulfide 0.5 121
Tin Mercuric chloride and aniline 0.6 89

Cacotheline 0.2 87
Flame color 0.03 88
Dimethylglyoxime and ferric salts 0.04 89
Diazine green 2 89
2-Benzylpyridine 1.3 89
. Ammonium phospbomolybdate 0.03 86
1,2,7-Trihy droxy anthraquinone 0.2 89
Anthraquinone-l-azo-4-dimethylaniline 0.01 89
hydrochloride
Titanium Hydrogen peroxide ^ 2 150

Pyrocatechol 2.7 150
Chromotropic acid 3 151
Chromotropic acid and -cone, sulfuric 0.1 152
acid
Tannin and antipyiine 0.2 152
Methylene blue and zinc 0.05 163
Tungsten Stannous chloride 5 94

Diphenyline 6 97
Catalysis of Ti-malachite green reaction 0.1 95
Uranium Potassium ferrocyanide 0.92 157

Fluorescence 0.001 169
Quercetin or quercitrin 3 159
Vanadium Hydrogen peroxide 2.5 97

Formation of iron (II) dimethylglyoxime 1 98
Cacotheline 2 99
Aniline 3 99
Phosphomolybdic acid 0.4' 99
8-Hydroxyquinoline 0.1 100
u i n 0.025 ml.
" III 0.04 ml.
502 rS. aÂBULAR SUMMARY
A. INOBOANIC ANALYSIS. CATIONS. Continued
Cation identified Reagents or test reactions , Limit of Page

identification y'
Zinc Potassium ferrocyanide and diethyl anil- ; 137
Dithizone 0.025 139

Induced precipitation of CoHg(CNS)4 0.2 140
Conversion to Rinmann's green 0.6" 141
Potassium ferricyanide and p-plienetidine 1 141
Uranyl ferrocyanide 0.1 142
Resorcinol 2 141
Zirconium /3-Nitroso-a-napiitliol 0.2 . 163

Alizarin ' 0.5 154
p-Dimethylaminoazophenylarsonic acid 0.1 155
Carminic acid or gallocyanine 0.5 157
5-Chlorobromoamine acid 0.5 157
" In 0.002 ml.

B. INORGANIC ANALYSIS. ANIONS
Anion or substance Reagents or test reactions Limit of Page
identiiied identification, y
Boric acid Tincture of turmeric (curcuma) 0.02 256

Purpurin 0.6 258
Alizarin S 1 258
p-Nitrobenzeneazochromotropic acid 0.08" 258
Decomposition of methyl borate with KF 0.01 259
Increase of acidity with polyhydroxy 0.001 260
compounds
Carminic acid 0.1 261
Sulfuric acid and methyl alcohol 261
Bromic acid Manganese, sulfate and sulfuric acid "40-.-,,^ 222
Carbon dioxide Sodium carbonate and phenolphthalein 4 254

Chloric acid Manganese sulfate and phosphoric,acid 0.05 221
Chromic acid Diphenylcarbazide , 0.5 262

Hydrazoic acid Silver nitrate or ferric chloride 5 215
Hydriodic acid Palladous chloride 1 197

Potassium nitrite and starch 2/5 198
Bromine water _.^-- 6.1 199
Permanganate ^ 0.1 200
Catalytic reduction of cerium (IV) salts 0.05 200
Formation of silver iodide 5 201
Formation of thallous or palladous iodide 202
" I n 0.04 ml.

IX. TABULAR SUMMART 503
E. INORGANIC ANALYSIS. ANIONS. Continued
Anion or substance Reagents or test reactions Limit of

identified identification, y Page
Hydrobromic acid Fluorescein 0.3 to 2 194

Fuchsin 3.2 196
Permolybdate and a-naphthoflavone 1 196
Oxidation to bromine and action on KI 5 197
Copper bromide and sulfuric acid 0.02 197
Hydrochloric acid Conversion to chromyl chloride 0.3 191

Volatilization and formation of AgCl 1 193
Hydrocyanic acid Copper acetate and benzidine 0.25 208

Copper sulfide 1.25 209
Conversion to thiocyanate 1 209
Picric acid 212
Decolorization of starch-iodine 1 212
Copper ferricyauide 212
Hydroferrj cyanic Benzidine 1 218

acid (ferri-cy- Phenolphthalein 0.6 219
anic acid) Induced oxidation of tetrabase 0.1 220
Trithiourea-cuprous chloride 0.9 221
Hydroferrocyanic Uranyl acetate 0.6 215

acid (ferro-cy- Ferric chloride 0.07 216
anic acid) Titanic chloride 60 221
Hydrofluoric acid, Zirconium alizarinate 1 202

Zirconium azoarsonate 0.25 204
Conversion to SiF* 1 206
Etching glass 0.5 207
Hydrogen peroxide Oxidation of lead sulfide 0.04 268

Ferric-ferricyanide 0.08 269
Eeduction of higher oxides of nickel O.OI 269
Gold chloride 0.07 271
Alkali thiocyanate 0.7 271
Potassium cerium carbonate 0.1 271
o-Tolidine 0.025 271
Catalyzed oxidation of phenolphthalein 0.04 270
Luminol 0.5 271
Hydrogen sulfide Sodium nitroprusside 1 226

Catalysis of the iodine-azide reaction 0.3 227
p-Aminodimethylaniline 1 230
Sodium plumbite 1.8 231
Iodic acid Hypophosphorous acid 1 223

Potassium thiocyanate 4 223
Pyrogallol 0.25 224
604 IX. TABULAR 8UUUART
B. INOBQANIC ANALTSIB. ANIONS. Continued
Anion or substance Reagents or test reactions Limit of

identified identification, y Page
Mercuric cyanide Silver nitrate and alkali 5 210

Conversion into HglJ"" and CN~ ions ' 211
Formation iodocyanogen 0.25 211
Nitric acid Ferrous sulfate.and sulfuric acid 2.5 243

Diphenylamine or diphenylbenaidine 0.07 to 0.5 244
Brucine 0.06 245
Reduction to nitrite 0.05 246
Reduction to ammonia 10 247
Nitrous acid a-Naphthylamine and sulfanilic acid 0.01 248

1,8-Naphthylenediamine 0.1 249
Iodide and starch 0.005 249
Chrysean 0.25 250
Benzidine 0.7 250
Ferrous sulfate and acetic acid 2 260
Periodic acid Manganese sulfate and phosphoric acid 5 224

Manganese salt and tetrabase 0.5 224
Formation of complex Cu(ni) periodate 0.5 to 2 225
Permanganic acid Reduction to MnOj 0.5 261
Persulfuric acid Benzidine 0.25 243
Phosphoric acid Ammonium molybdate and benzidine 0.05 250
Selenious and sele- Hydriodic acid 1 263

nic acids Pyrrole 0.5 264
Diphenylhydrazine 0.05 264
Thiourea 2 265
Ferrous sulfate 265
1,8-Naphthylenediamine ~ 1- ^ 266
Thiourea 5 265
Silicic acid Ammonium molybdate and benzidine 0.1 252
Sulfuric acid (sol- Barium rhodizonate ; 5 236

uble sulfate) Precipitation of BaSO* in presence of 2.5 238
permanganate
Decomposition with barium carbonate 5 237
Sulfuric acid (in- Reduction to sulfide with potassium '0.6 238

soluble sulfate) Reduction to sulfide with carbon "^ . 36 239
Sulfuric acid (free) Glucose 8 239

EK. TABULAR SUMMART 505
B . INOROANIC ANALYSIS. A N I O N S . Continued
Anion or substance Reagents or test reactions Limit of Page

identified identification, y
Sulfurous acid Sodium nitroprusside 3.2 231

% Zinc nitroprusside 3.5 231
Induced oxidation of Ni(OH)j 0.4 233
Decolorization of malachite green 1 234
2-BenzyIpyridine 7.2" 236
Reduction of ferric ferricyanide 5 236
Tellurous and tel- Hypophosphorous acid 0.1 266

luric acids Alkali stannite 0.6" 266
Formation of complex cupric (III) tel- 0.2 to 0.5 267
lurate
Ferrous sulfate and phosphoric acid 0.6 268
Thiooyanic acid Catalysis of the iodine-azide reaction 1.6 212

Permanganate, copper acetate and ben- 1 214
zidine
Cobalt salt and acetone 1 215
Thiosulfuric acid Catalysis of the iodine-azide reaction 0.025" 240
" I n 0 . 1 ml. " I n 0.025 ml.

C. INORGANIC ANALYSIS. FREE ELEMENTS
Element or substance Reagents or test reactions Limit of Page

identified identification, r
Carbon Oxidation by fused KClOa 50 281
Halogens Formation of eosin or iodoeosin 1 (chlorine) 276

2 (bromine) 276
6 (iodine) 276
Mercury Palladous chloride 275

Selenium sulfide 275
Metals and alloys Phosphomolybdic acid traces 273

Ferric ferricyanide traces 273
Selenium Conversion into thallium selenosulfide 1 279

Formation of AgsSe 6 280
Sulfur Formation of thallous sulfide 3 277

Conversion into thiocyanate 5 279
Conversion into thiosulfate 279
506 vs.. TABTJLAR 8UMMAET .
D. ORGANIC ANALYSIS. CERTAIN ELEMENTS
Element identified Reagents or test reactions Limit of Page

identification, y
Arsenic Conversion to arsenate 10 to 12 318
Fluorine Conversion to potassium fluoride 100 to 200 312
Halogens Conversion to volatile copper halide 0.25 to 0.5 311
Nitrogen Conversion to ammonia 1 to 3 315

Conversion to cyanide 4 to 12 316
Oxygen Ferric thiocyanate 319
PhosphoruB Conversion to phosphate 1 317
Sulfur Conversion to potassium sulfide 0.3 to 1.2 313

Conversion to silver sulfide 0.05 314
E. ORGANIC ANALYSIS. CHARACTERISTIC GROUPS
Group identified Reagents or test reactions Limit of Page

identification, y
Alcohols Conversion into xanthate 100 to 1000 324

Oxidation to formaldehyde 2.5 to 100 328
Aldehydes Conversion into hydroxamic acid 2 to 100 346

Fuchsin sulfurous acid 1 to 1000 339
o-Dianisidine i 0.05 to 200 340
Azobenzenephenylhydrazine sulfonate 0.1 to 130 341
Peroxidase action on phenylenediamine 0.01 to 60 345
Aldehydes: a,j3- Hydrogen sulfide and sodium pentacyano- -WQ^^ 349

unsaturated and ammine ferroate ~^-
aromatic
Amides and nitriles Conversion to rhodamine dye 20 to 50 375
Amines: primary Conversion to dithiocarbamate ' . 3 to 250 - 368

aliphatic Conversion to rhodamine dye 10 to 30 373
Amines: secondary Sodium nitroprusside and acetaldehyde 0.5 to 100 371

aliphatic Conversion to dithiocarbamate 0.6 to 250 368
Conversion to rhodamine dye ^ 4 to 20 374
Amines: aromatic Coiiversion to rhodamine dye 1 to 400 375

IX. TABULAR SUMMARY 507
E. ORGANIC ANALYSIS. CHARACTERISTIC GROUPS. Continued
Group identified Reagents oi test reactions Limit of Page

identification, y
Aminea: primary Glutaconic aldehyde 0.05 to 2 378

aromatic Sodium pentacyanoaquoferrate 0 1 to 100 381
5-Nitroso-8-hydroxyquinoline 1 to 100 383
Furfural 0.1 to 200 383
Chloranil 0.2 to 200 383
Carbon disulfide I to 5 383
Ethyl nitrite and resorcinol 383
a-Amino acids Conversion to aldehyde 50 to 100 384
Carbony] com- Bisulfite 0.05 to 500 333

pounds
Carboxylic acids Conversion to hydroxamic acids 11 to 100 365
Carboxylic acid Conversion to hydroxamic acids 5 to 10 369

anhydrides
Carboxylic acid es- Conversion to hydroxamic acida 2 to 13 358

ters
1,2-Dicarboxylio Melting with resorcinol 1 to 40 360

acids
o-Dioxo- and oxo- Conversion to diketones 0.5 to 10 335

methylene com-
pounds
Enols Bromine and potassium iodide 80 to 120 332
Hydrazines Sodium pentacyanoammine ferroate 0.12 to 7 385

(hydrazonea and Formation of hydrazones with nzo dyes 1 to5 385
osazones) Selenious acid and a-naphthylainine 0.03 to 2 387
Methyl ketones Sodium nitroprusside 2 to 15 349

Conversion to indigo 40 to 300 351
Nitro compounds Reduction to nitroso compounds 0.25-to 15 322
Aromatic m-dini- Potassium cyanide 1 tolO 323

tro compounds
Nitroso com- Phenol and sulfuric acid 0.4 to 1 321

pounds Sodium pentacyanoammine ferroate 0.15 to 3 321
508 DC. TABULAR SUMMARY
E. ORGANIC ANALTSIS. CHAEACTBBISTIC GROUP?. Continued
Group identified Reagents or test reactions . Limit of Page

identification, y
Oximes and hy- Splitting off hydroxylamine and oxida- 0.03 to 8 352
droxamic acids tion to nitrite '
Phenols 5-Nitroso-8-hydroxyquinoline 1 to 10 329

Nitrous acid and mercuric nitrate 0.5 to 10 330
Nitrous acid and sulfuric acid 329
Pyrrole derivatives Conversion to rhodamine dye 12 to 40 378
Reactive CHi and 1,2-Naphthaquinone-4-sodium sulfonate 0.12 to 12 389

NHj groups
Bnliomc amda Fusion with aikaii to suJte 3 to 20 363
(Sulfinic acids, Conversion into the ferric salt of acethy- 10 to 30 366

Sulfones) droxamic acids
Tertiary cyclic Methyl iodide and 1,2-naphthaquinone- 12 to 100 392

bases 4-sodiuin sulfonate
Tbioketones and Catalysis of the iodine-aide reaction 0.0003 to 15 353

mercaptans
F. ORGANIC ANALYSIS. COMPOUNDS
Compound identified Reagents or test reactions Limit of

identification, y Page
Acetic acid Lanthanum nitrate and iodine 50 397

Conversion to indigo 60 398
Conversion to acetaldehyde 10 to 16 399
Formation of ferric acetate 399
'10-
Ascorbic acid (vit- Reduction of MnOi 0.03 420
amin C) Reduction of phosphomolybdate 0.1 421
Carbon disulfide Catalysis of the iodine-azide reaction 0.14 417

Formaldehyde and plumbite 3.5 418
Carbohydrates Urea, stannous chloride and sulfuric acid 8 to 30 410

(see also reduc- Conversion to furfural 5 to 100 410
ing sugars, page /
409)
vs.. TABXILAB SUMMARY 509
OBOANIC ANALYSIS. COMPOUNDS. Continued
Compousd identified Reagents or test reactions Limit of Page

identification, y
Chloroform Conversion to cyanide 16 395
Citric acid Conversion to citrazinic acid 1 407
Enzymes Alteration of substrate 421
Fonnaldehyde Chromotropic acid 0.14 396
Formic acid Conversion to formaldehyde 1.4 397
Glyceric'acid Naphthoresorcinol and sulfuric acid 10 401
Glycerol Conversion to acrolein 5 408

Catalytic decomposition of oxalic acid 5 409
Glycolic acid 2,7-Dihydroxynaphthalene and sulfuric 0.2 399

acid
Lactic acid p-Hydroxydiphenyl and sulfuric acid 0.5 400

o-Hydroxydiphenyl and sulfuric acid 1 401
Malic acid |3-Naphthol and sulfuric acid 10 405
Methyl alcohol Conversion to formaldehyde 3.6 396
Oxalic acid 2,7-Dihydroxynaphthalene and sulfuric 1 402

acid, after reduction with magnesium
Conversion to aniline blue 5 403
p-Phenylenedi- Oxidation to indamine dye 0.5 415

amine
Phosgene Conversion to diphenylcarbazide 0.5 416
Proteins Ester of tetrabromophenolphthalein 0.35 to 5 412

Hydrolysis to amino acids 1 to 100 414
Pyridine Conversion to glutaconic aldehyde 5 414
Pyruvic acid o-Hydroxydiphenyl and sulfuric acid 3 402
Tartaric acid Gallic acid and sulfuric acid 2 405

^,/3'-Dinaphthol and sulfuric acid 10 406
Tyrosine a-Nitro80-/3-naphthol 0.6 411

AUTHOR INDEX
Beck, G., 88, 142
Becker-Rose, H., 433
Adamovich, L. P., 489 Beckurts, H., 80
Agte, K.. 433 Behr, M., 223
Aguiar, A. de, 249 Beilstein, P., 311
Aickin, R. G., 195 Belcher, R., 165
Ajtai, M., 74 Bellucci, J., 153
Alber, H., 477 Belokon, A. N., 162, 493
Alexejeff, R., 49 Benco, V., 69
Alimarin, J. P., 202 Benedetti-Pilcher, A. A., 141
AUard, J., 335 Berg, R., 264
Almfe, A., 330 Bergmann, E., 400
Aloy, J., 489 Berl-Lunge, 183, 455
Aloy, R., 489 Berraz, G., 489
Alvarez, E. P., 489 Bertagnini, C , 333
Andreasch, R., 44 Besthorn, E., 50
Angeli, A., 346 Bettendorf, A., 79
Anger, V., 2, 321^323, 349, 355, 358-360, Bianchi, A., 434
366, 371, 374, 375, 378, 380, 381, 385, Biehringer, J., 134
407, 412, 414, 416, 485 Biffen, F. M., 495
Angerer, E. v., 45 Biltz, W., 160, 203
Apitzseh, H., 324 Bitto, B. v., 339, 349
Arnold, E., 461, 489 Blancpain, C. P., 85
Artmann, P., 55 Blau, F., 122
Ashburn, G., 489 Blom, J., 189, 246, 248
Atack, P. W., 2, n o , 143 Bobierre, A., 427
Atkinson, J. V., 489 Booker, E., 323
Atta, A. v., 48 Bodecker, C , 231
Aufrecht, W., 167, 238 Boer, J. H. de, 154, 202, 204
Augusti, S., 74, 489 Bottger, W., 110, 183, 204, 233, 294, 500,
Avens, A. W., 243 403, 455
Azzam, A. A., 488 Bogen, E., 475
Boisbaudran, L. de, 160
B Bondi, A., 400
Bontinck, E., 489
Bacharach, A. L., 477 Borgwardt, E., 335
Bachoulkova-Bruh, B., 491 Borsche, W., 323
Badian, L., 52, 53, 238, 259, 266, 312, 313, Boyd, T., 489
315-317, 318 (re(. 12), 466 Braile, N., 239, 277, 279, 428-430, 433,
Baeyer, A.v.,270;351,374 446, 467, 482
Balarew, D., 42,137 Bran, F., 233
Ballaban, H. E., 68, 143, 152, 224, 425, Braun, C. D., 92
426, 440, 455 Brauner, B., 267
Balson, E. W., 160 Braunholtz, W. T. K,,.310
Bamberger, E., 174 Brenneis, H. J., 477
Bamford, F., 494 Brinker, H. C , 489
Barannikov, G. J,, 244 Brunger, K., 66
Barbieri, G. A., 132 BrUning, A., 489
Barbosa, P. E., 121, 178 Brukl, A., 223
Barnebey, O. L., 209 Brunck, 0., 114
Basart, J., 204 Budkewitsch, A. A., 185
Baudisch, O., 2, 2l9, 321 Burckhardt, E., 413
Baumann, R., 459 Burford, G., 300, 308
Baumgarten, P., 246 Burger, M., 40
611
512 AUTHOR INDEX
Burgess, L. L., 177 Dowzard, E., 81

Burkser, E. S., 182 Dragendorff, G., 324
Burnistrov, 8. J., 383 Drescher, E., 491
Busch, H., 489 Drewsen, V., 351 |
Dubsky, J. v., 2, iS9, 260
Duke, F. R., 329, 490
Dulfer, G., 495 '
Cacciapnoti, B'. N., 110 Dulon, R., 335
Cady, L. C , 137 Dunkelberger, T. H., 250
Caley, E. R., 35, 300, 308 Dupont, G., 335
Cardoso, H. T., 420, 421 Duval, C , 100, 298, 490
Cazeneuve, P., 2, 48, 128, 416 Duyk, M.,"133
Chakravarti, S. N., 383 Dwyer, F. P., 79
Chaletzki, A. M., 489 D'yachkovskil, S. I., 461,490
Chamot, E. M., 256
Chargaff, E., 309, 353, 417 E
Chariot, G., 494
Charpentier, G., 270 Eck, P. N. van, 490
Cholnoky, L. v., 477 Edeler, A., 490
Claisen, L., 67 Edge, R., 278
Clarke, B. L., 2,6,310, 489 Edge, S. R. H., 490
Clarke, L., 266 Edwards, W. T., 490
Claus, A., 124 Eegriwe, E., 2, 86, 89, 137, 142, 173, 231,
Cole, H. J., 266 309, 395-397, 399-402, 406, 406, 490
Cone, W. H., 137 Egorov, M., 427
Corbett, R. B., 489 Ehrhart, O., 107
Cornea, J., 201, 494 Ehrlich, P., 389, 393 (ref. Ill)
Costeanu, N. D., 489 Eisleb, O., 67
Costeanu, R. N., 101 Eitel, W., 449
Cucuel, F., 53 Emich, F., 26, 494
Curtmann, L. J., 101,102 Emschwiller, G., 494
Endres, G., 189
D Engel, A. L., 471
Engel, E. W., 173
Dacorso, G., 273, 449 Engelder, C. J., 250
Damour, A., 397 Ephraim, F., 45, 66, 93, 98, 443
Daube, F. W., 256 Erametsa, 0., 490
Davidson, D., 216, 319, 356 Evans, B. S,, 52, 490, 494
Davies, W. C , 287, 490 Evans, M. H., 265
Davison, E. H., 494
Debray, C , 93
Decker, H., 329
Degering, E. F., 489 Falciola, P., 265
Demant, V., 189, 264, 362, 387, 447, 465 Fanetone, R. M., 241
Denigfts, G., 2, 55, 83, 301, 445 Fauconnier, P., 100
Detscheff, P., 66 Feigl, F., 2-4, 5 (ref. 5), 17, 19, 20, 43,
Deussen, E., 465 65, 73, 85, 89,-97, 106, 107, 117, 119,
Dieffenbach, 0., 322 125, 129, 134, 142, 161, 165, 167, 169,
Diels, O., 187
Dieterioh, H., 81 170, 177, 183, 184, 186, 187, 197, 203,
Ditz, H., 112 212, 215, 218, 221, 227, 229, 230, 233,
Dobroljubski, O. K., 153 237, 240, 249, 250, 251, 252, 255, 262,
Dodd, A. S., 260 265, 273, 274, 280, 281, 296, 298, 300,
Doi, K., 92 302, 309, 3l9r334, 353, 363, 410, 423,
Dolgow, K. A., 100, 104 426, 427, 441, 442, 444, 448, 477, 481,
Donau, J., 62, 86 4&4, 490, 494
AUTHOR INDEX 513
Feigl, F., and Anger, V., 366, 371, 380, , and Zappert, R., 327, 329, 330, 333,
407, 412, 414 339, 346, 350, 410
, Anger, V., and Frehden, O., 321, 322, , Zappert, R., and Sanchez, J. V., 352
355, 358-360, 385, 485 Fenton, H. J. H., 490
, Anger, V., and Zappert, R., 349, 371, Ferjantschitsch, F. A., 490
374, 375, 378, 385 Ferla, F., 110
, and Aufrecht, W.,'167, 238 Fetkenheuer, B., 207
, and Badian, L., 52, 53, 259, 312, 313, Filimanowitsch, K. M., 133
315-317,318 (ref. 12), 466 Fischer, E., 50, 230
, and Ballaban, H. E., 152, 224, 440 Fischer, H., 2, 48, 57, 72, 139, 147, 149
, and Barbosa, P. E., 121, 178 Flanders, F., 169
, and Braile, N., 277, 279, 428-430, 433, Fleury, G., 490
446, 467, 482 Florenzki, K. P., 493
, and Cardoso, H. T., 420, 421 Fordos, J., 427
, and Chargaff.E., 309, 417 Fortini, V., 434
, and Dacorso, G., 273, 449 Foulger, J. H., 410
, and Demant, V., 189, 264, 362, 387, Frankel, E., 40, 47, 103, 133, 233, 269,
447 465 271, 490
, and Frankel, E,, 47,103,133, 233, 269, Frank, G., 341, 345, 368, 409
271 Frehden, O., 2, 195, 276, 321, 322, 328,
, and Frank, G., 341, 345, 368, 409 332, 340, 355, 358-360, 383-386, 391,
, and Frehden, O., 391,392,403,408,422 392, 395, 403, 408^10, 414, 422, 485,
, and Hamburg, H., 122, 437, 438 487 490 494
, and Kapulitzas, H. J., 71, 115, 116, Frese'nius,' G. R., 83, 101, 183, 246, 294,
300
118,426,435,436- Fresenius, W., 408
, Klanfer, K., and Weidenfeld, L., 270 Freytag, H., 89, 236, 378
, and Krausz, G., 472 Friederici, L., 103
, and Krumholz, P., 30, 60, 105, 130, Friedlander, P., 371, 386
206, 252, 254, 257, 427, 468, 470 Friend, N. A. C., 335
, Krumholz, P., and Rajmann, E., 45, Fritz, H., 462, 490
100, 107, 155 Furst, K., 328, 340, 383, 396
, and Lederer, F., 48 Funakoshi, O., 73
, and Leitmeier, H., 443, 444, 445 (ref.
39), 463, 464, 471
, and Lenzer, A., 363 G
, and Lettmayr, L., 73 Gaglio, G., 274
, and Miranda, L., 74 Gallego, M., 100
, and Neuber, F., 48, 55, 59, 67, 73, 78, Galopin, R., 457, 490, 491
84,86 Ganassini, D., 194
, and Ordelt, H., 85 Gangl, J., 81
, and Pavelka, F., 170 Gaptschenko, M. V., 63,162
, and Pickholz, S., 107 Garre, G., 491
, and Rajmann, E., 204 Gastaldi, E., 208
, and Ribeiro, 0., 490 Gawalowski, A., 312
, Sanchez, J. V., and Zappert, R., 398 Geilmann, W., 66
, and Seboth, R., 193, 268, 399 Gelei, G., 48, 56
, and Silva, C. P. J. da, 479, 490 Gerngross, O., 411
, and Singer, A., 55, 432 Glazunow, A., 2, 461, 462, 491
, and Stern, R., 109, 132,144, 157 Gmelin, L., 198
, and Suter, H. A., 56, 166, 261, 302, Godbert, A. L., 166
. 428, 429 Goldschmidt, L., 383, 384, 410, 414
, and Tamchyna, J. V., 210 Goppelsroeder, Fr., 1,142,198, 495
, and Uzel, R., 190, 226, 267 Gotthelf, A., 81
, and Weidenfeld, L., 473, 480 Gottlieb, A. L., 224
, and WeiBselberg, K., 418, 483 Greathouse, L. H., 134
514 AUTHOR INDEX
Green, W. F., 108 Hoag, L, E., 159

Greiner, H., 380, 381 H6nel, F., 74, 76, 77, 78, 94
Griess, P., 247, 248 Hofmami, A. Vf., 368, 369
Groschuff, E., 448 Hofmann, K..A., 107, 151, 210, 226, 322,
Griinsteidl, E., 278 349 (ref. 20) 1
GrOnwald, J., 427 Holluta, J., 63 j
Guareschi, I., 196 Holzer,H., 66,100
Guilhon, J., 491 Houben, J., 257
Gutzeit, G., 2, 48, 87, 107, 165, 202, 212, Howden, R., 129
217, 236, 283, 457, 491 Huang, C.-H., 195, 276, 409, 490
Gutzeit, M., 80 Hundesbagen, H., 85:
Guyard, A., 99
Gysin, M., 457, 491
H Ibbotson, F., 129

Ilinsky, M., 2, 109, 154
Haber, F., 233 Isaenko, T. I., 461, 490
Hagen, S. K., 207 Ishidate, M., 185,192, 334, 335, 338
Hahn, F. L., 2, 15, 21, 63, 88, 102, 117,
146,172,173,194,246,248,260,314,427
Haitinger, M., 491, 495
Haken, H. L., 103 Jackson, C. L., 256
Halla, F., 193 Jacoby, K. R., 49
Hamburg, H., 122, 240, 241 (ref. 106), Jaeger, G., 172, 246, 248
437, 438, 491 Jirkovski', R., 461, 462, 492
Hainmett, L., 147 Jockers, K., 476
Hamy, A., 171 Jolles, A., 252
Harrison, A. P., 40 J6n&s, J., 94
Hauser, E., 282 Jones, A. L., 126
Heim, 0.,195,415 Jost, H., 187
Hein, F., 123
Heisig, G. B., 236
Heller, G., 416
Heller, K., 44, 51, 76, 78 (ref. 91), 125, Kamm, O., 177, 310
143, 287, 291, 293, 294, 476 Kappelinacher, H., 30, 99
Henriques, R., 154 Kapulitzas, H. J., 71, 88, 94, 115, 116,
Herfeld, H., 411 118, 192, 211, 235, 242, 426, 436, 436
Hermance, H. W., 6, 489,491 Karlik, B., 157, 159
Hermsdorf, A., 208 Karrer, P., 126
Hernegger, F., 157, 159 Kempf, R., 268 ^
Herter, C. A., 389, 393 (ref. HI) Kersting, R., 245
Herzog, A., 495 Kiemstedt, H., 484
Hess, W., 452 Kirchhof, F., 197
Hesse, G., 477 Kirmreutter, H., 210
Hetterich, H., 491 Kisser, J., 492
Heyn, E., 459 Klanfer, K., 270, 451, 485, 492
Heyne, G., 433 Kniga, A. G/, 219
Hickinbottom, W. J;, 310 Knorre, G v., 2
Higgs.D.G., 490,494 Kocsis, E. A., 48, 55,128,159
Hill, A. E 447 Koenigs, E., 380, 381
Hiller, T., 457, 491 Kohn, C. A., 408
Hinderer, W., 242 Kohn, M., 122, 218, 269
Hinsberg, O., 266 Kolthoff, L M., 2, 53, 56, 112, 113, 174,
Hirsch, G., 6, 212 176, 200, 211,'214, 244, 476, 492, 495
Hirschberg, Y., 400 Komarowsky, A. S., 2, 58, 73, 90, 94, 90,
Hirschel, W. N., 186 148-160, 161, 162, 172, 258, 259, 471
AUTHOR INDEX 515
K(/ndo, Y., 448, 455, 478, 492' Luther, R., 108

Koninok, L. de, 178 Lyons, E., 127
Koppel, J., 93
Korenman, I. M., 148, 172, 309 M
Korenmaim, S. M., 161
Koslowsky, M. T., 214 Maass, Th., 94
KrU, H., 226 Machek, F., 476
Krauskopf, F. C , 92 Maciag, A., 412
Krausz, G., 472 Mahr, C.,62,63
Krings, W., 192 Makris, G. K., 185
Krivohlavi', J., 491 - Malaprade, L., 225, 327
Krohnke, F., 392 Malatesta, G., 100
Kruger, D., 397, 398 Malitzky, W. P., 214
Krumholz, P., 2, 30, 45, 51, 60, 74, Malowan, S., 93
76-78, 94, 100, 105, 107, 125, 130, 140, Manchot, W., 2-13
143, 155, 206, 252, 254, 257, 287, 289, Mann, F. G., 310
427, 468, 470 Marggraff, I., 246
Kuenkele, F., 492 Marshall, H., 132
Kuhla, G., 476 Martini, A., 63
Kui'berg, L., 2, 67, 131, 162, 173, 271 Matwejew, L., 271
Kutschment, M. v., 182 Mazars, G., 490
KuJma, B., 267 Mee, A. J., 126
Kuznetsov, V. J., 89 Meimberg, F., 174
Meissner, H., 88
L Melnik, L., 472
Merck, E., 434, 456
Lang, R., 47, 48 (ref. 14) Mertens, K. H., 180
Langenbeck, W., 271 Metz, L., 227
Langer, A., 54 Metzger, O., 452
Lapin, L. N., 220, 271 Meyer, H., 310, 3U
Lawson, A., 160 Meyer, J., 98
Leoocq, E., 94 Meyer, K. H., 332
Lederer, F., 48 Meyer, R., 249
Le Fevre, R. J., 351 Michaltschischin, G. T., 104
L^ger, E., 59 .Milden, H., 134
Leimbach, G., 63, 427 MiUon, E., 330
Leitmeier, H., 443, 444, 445 (ref 39), 463, Miranda, L., 74
464, 471 Mitchell, C. A., 101
Lenzer, A., 363 Mohlau, R., 338
Leonhardt, H., 492 Moir, J., 208
Lerner, A., 236 Moll, F., 450
Lerner, M., 492 Molterer, H., 216
Lettmayr, K., 73, 492 Monier-Williams, G. W., 244, 245
Lewin, L., 408 Monnier, A., 242
Liebermann, C , 85, 321, 329, 417 Monnier, R., 107, 491
Liebreich, O., 492 Montequi, R., 73, 93. 100
Ligbtfoot, J., 99 Montignie, E., 94
Lindenbaum, S., 85 Morley, J. F., 335
Moufang, N., 87, 88
Linz, A., 85 Mozars, G., 298
Livingstone, R. S., 53 Mtiller, E., 216, 281
Locher, M., 171 Mliller, O., 344
Lochmann, G., 63 MUller, W., 249
Lowe, J., 198 Murray, M. J., 243
Lowe, C. S., 147 Mutnianski, M., 199
Luft, A., 485 Mylius, F., 448
516 AUTHOB INDEX
N Pike, N. R.,151 ,
Pincus, H., 216 '
Nadler, G., 125 Pinkus, A., 132
Neuber, F., 48, 55, 59, 67, 73, 78, 84, 86, Pirani, M., 449
492 Pissarjewsky, L., 160 '
Neudert, W., 378 Plank, E., 271
Neurath, F., 252 Plugge, P. G., 330
Newell, I. L., 87 Poluektoff, N. S., 2, 73, 89-91, 94, 99,
Nichols, E. L., 159 120, 149, 150, 162, 164, 178, 258, 259,
Niessner, M., 457, 458, 460, 461, 492 263, 265, 266, 471, 492
Nietzki, R., 413 Ponndorf, W., 346
Nieuwenburg, C. J. van, 3, 495 Porlezza, C., 60
Nola, E. di, 100, 434 Postowsky, J. J., ^ 4 , 387
Noponen, G. E., 244 Potschinok, C. N., 251
Nordlander, B. W., 275, 276 (ref. 5) Poxon, D. W., 494
Nosaka, K., 412, 424 Prahl, L., 333
Noviiek, R., 129, 217, 241, 432, 438, 443, Prdt, S., 492
444, 445 (ref. 39) Prins, A., 435
Pro6ke, O., 180
O Przibram, E. M;, 6, 492
Obach, E., 481 R
Oberhoffer, P., 459
Occleshaw, V. I,, 48 Rahl, H., 452
Oelke, W. C , 221 Raibmann,' B., 150
Oesper, R. E., 2, 3, 7 (ref. 4), 43, 494 Rajmann, E., 45, 100, 107, 154, 155, 199,
Osterhud, Th., 329 204
OUi, A., 250 Ramakers, L , 132*
Okuma, K., 173 Rappaport, F., 40
Olszewski, W., 478 Raschig, F., 2, 189, 227, 262, 333
Oppenheim, A., 323 Rauner, K. M., 459
Ordelt, H., 85 R4y, Pr., 70, 112, 117
Orelkin, B., 125 RAy, R. M., 70,112,117
Orlow, N., 303 Reckendorfer, P., 234
Ostwald, W., 45 Reedy, J. H.,, 489
Oudemans, A. C , 64 Reichinstein,-D., 483
Overholster, L. G., 157 Reihlen, H., 126, 218
Owetschkin, W., 58 Reppmann, W., 83
Reser, E., 449
Retter, W., 123
Rhodes, H. T. F., 492, 495 "
Paal, C , 103 Ribeiro, O., 490
Palet, L. P. J., 492 Richemont, D. de, 243
Pantschenko, G. A., 92, 95, 99, 152, 158, Richter, M., 467
439, 440 Riegler, E., 182 .
Papisch, J., 159 Rienacker, G., 139
Pavelka, F., 25, 26, 58, 59, 64, 154, 157, Riley, H. L., 335
170, 202, 426, 492 Rimini, E., 346, 408
Pawletta, A., 98 Ritter, F., 193
Pearson, J., 351 Robinson, F. A., 477
Penzoldt, F., 351 Rojahn, C., 495
Percival, G. P., 492 RoUet, A. P., 117 /
Pertusi, C., 208 Romanjuk, A. N., 109 ,
Petraschenj, W. J., 171 Rosenblum, C., 495 "
Petrov, M. T., 434 Rosenheim, A., 112, 150
Pfaundler, L., 323 Rosenthaler, L., 235, 310
Piooard, J., 150 Rossi, L., 212, 467
Pickholz, S., 107, 135, 170, 222 Rothberg, P., lO;, 102
AUTHOR INDEX 617
Roy.M. B., 383 Schwarz, R,, 150

Ruge, U., 271 Schwechten, H. W., 321., 349
Ruigh, W. L., 173 Schwenk, E., 335
Rupp, E., 84 Schwertner, F., 494
Ruttner, T. F., 108 Scriba, F., 493
Seboth, R., 193, 268, 399
Seifter, J., 493
Sensi, G., 141
Sabetay, S., 493 Sexauer, W., 150
Sachs, F., 266 Shemyakin, F. A., 162
Sanchez, J. V., 140, 352, 398, 399 Shreve, R. N., 489
Sandell, E. B., 95, 200 Sieverts, A., 208
Sander, A., 241 Siewert, M., 93
Sarver, L. A., 74, 113,128 Silbermintz, W. A., 493
Sastri, N. B., 421 Silva, C. P. J. da, 479, 490
Saunders, B. C , 310 Simon, L., 408
Savoia, G., 153 Singer, A., 55, 432
Scagliarini, G., 226, 231 Slattery, M. K., 159
Schacherl, R., 228, 229 (ref. 78) Slawik, P., 125
Schafer, H., 23, 493 Slotta, K. H., 49
Schales, 0., 270 Smith, G. F., 329
Schantl, E., 142 Smith, L., 7, 493, 494
Schapowalenko, A. M., 193,197, 208, 221, Snell, F. D., 495
223, 231, 250, 493 Solonina, B., 329
Scheel, K., 449 Sommer, F., 246, 417
Scheinziss, O. G., 63, 152 Sommer, H., 278
Schemjakin, P. M., 493 Sorkin, F. P., 261
Schendel, G., 150 Sottery, C., 147
Scheuing, G., 196, 234, 339 Spiegel, L., 94
Schiff, H., 1, 339, 493 Sreenivasaya, M., 421
Schiff, W., 139 Stahl, W., 261
Schiller, W., 250 Staudinger, R., 310
Schlagdenhauffen, F., 171 Steiger, B., 49, 108, 484
Schlenk, W., 55,134 Steigmann, A., 493
Schleainger, H. J., 124 St6rba-B6hm, J., 92
Schlumberger, M. E., 256 Stern, R., 109, 132, 144, 157
Schmatolla, O., 88 Stone, J., 174, 202
Schmidt, A., 97 Storfer, E., 221
Schmidt, E., 53 Strain, H. H., 477
Schmidt, H., 63 Suitsu, K., 173
Schmidt, J., 242 Sulfrian, A., 477, 493
Schneider, F., 26,,494 Suter, H. A., 56, 166, 261, 302, 428, 429
Schneider, 0., 107 Sutthoff, W., 244
Schnetka, M., 489 Swarte, C. E., 92
Schonbein, C, F., 1, 108, 269, 273 Szebell^dy, L., 2, 74, 94, 141
Schonn, J. L., 150
Schontal, R., 412
Scholder, R., 103
Schoorl, N., 476 Tafel, J., 87, 88
Schouwenaars, M., 493 Tamchyna, J. V., 167, 210, 493
Schroder, E., 242 TananaefE, I., 42, 137
Schroeter, G., 333 Tananaeff, N. A., 2, 7, 42, 48, 50, 58, 63,
Schulek, F., 196 89, 92, 95, 99, 100, 104, 109, 131, 137,
Schultz, G., 97 152, 158, 176, 182, 185, 193, 197, 223,
Schwab, G. M., 476 231, 250, 251, 439-441, 493, 495
Schwarz, F., 444 Tanay, I., 141
Schwarz, G., 46, 493
Tartarini, G., 75
518 AXJTHOH INDEX
Tauber, H., 493 Wang, A. B., 346

Taylor, W. W., 45 Wang, S., 416
Teitelbaum, M., 264 Ward, A., 45 i
Testori, R., 141 Wasicky, R., 340' 494
Thiele, J., 246 Wawilow, N. W., 63
Thoraa, E., 233 Weber, F., 494 |
Thomas, P., 270 Weeldenburg, I. G., 114, 116
Thorne, P., 45 Weibel, R., 491
Thrun, W. E., 147 . Weidenfeld, L., 167, 238, 240, 241 (ref.
Tillmans, J., 134, 244 106),270, 279, 466,473, 480
Todt, F., 475 Weihrich, R., 494 ,
ToUens, E., 346 Weinland, R., 126
Tornow, E., 53 Weisselberg, L., 173, 418, 459, 480, 483
Tougarinoff, B., 493 Weizmann, C , 400
Trattner, H. R., 493 Wenger, P., 2, 85
Travers, A., 132 Werner, A., 2, 66
Treadwell, W. D., 296 Werner, E. A., 119
Treubert, F., 60 Werther, G-, 97
Troger, J., 344 West, P., 7, 493, 494
Trtilek, J., 250 White, C. E., 147
Tschakirian, A., 90 Wibaut J. P., 123
Tschirch, E., 397, 398 Wicke, C , 233
Tschugaeff, L., 2, 114, 125 Wieland, H., 196, 234, 244, 264, 339
Tunmann, O., 493 Willard, H. H., 134, 201, 262
Willink, H. D. Tjeenk, Jr., 123
U Wilson, C. L., 198, 249, 494
Ubbelohde, A. R., 302 Winokelmann, J., 6, 494
Ugniwenko, M. G., 490 Winkler, L. W., 80
Uhlenhuth, R., 68, 70 Withworth, C , 494
Uzel, R., 180, 190, 196, 225, 2 ^ Wolbling, H., 49, 108
Uiumasa, Y., 92 Wohlers, H. E., 167, 238
Woker, G., 345
Wolf, H., 172
WoUner, R., 71, 109
Valdigu6, A., 489
Valkenburgh, H. B. van, 124
Vallender, R. B., 493 .
Vanino, L., 60 Yagoda, H., 2, 7, 167, 494
Vaubel, W., 330 Yoe, J. H., 2, 124, 126, 141, 157, 168
Vavilov, N. v., 493
Velculescu, A. J., 45, 46, 201, 494 Young, Ph., 201, 262 ^ - . . ^
Verhoeff, J. A., 186
Viebook, F., 199
ViUiers, A., 236 Zacharewicz, W., 335
Virgin, J. F., 226
Vitali, D., 222 Zagorulko, A. lA., 489
Vogel, A. I., 495 Zappert, R., 325, 327, 329, 330, 333, 33!,,
Vogel, H. W., 112 346, 349, 350, 352, 371, 374, 375, 378,
Von Steiu, P., 494 385, 398, 410
Voss, K., 411 . Zawidski, J. v., 112
VostrSbal, J., 92 Zechmeister, L., 477
Votodek, E., 234, 339 Zenghelis, C , 86, 105, 18.5
Vrti, M., 225 Ziegler, J. H^ 171
Zimmermann, F., 160
W Zipser, A., 44
Wagner, H., 210 Zurbruegg, E., 494
Walter, E., 126 Zw-icknaêl, K., 79
SUBJECT INDEX
in solutions of aluminum salts, test
Acetaldehyde, fluorescence with o-hy- for, 472
droxydiphenyl, 401 of copper and cobalt salts, detection,
identification, 334, 340, 342, 345, 347, 472
352 substances insoluble in, identification,
reaction with 2,7-dihydroxynaphtha- 300
lene, 400 treatment with, as special expedient, 8
with p-hydroxydiphenyl, 400 Acid alizarin RC test for chromium, 132
and sodium nitroprusside test for Acid amides, detection, 375, 379
secondary aliphatic amines, 371 Acid-insoluble residues, examination by
Acetaldehyde ammonia, identification, spot tests, 282
348 Acid nitriles, detection, 375
Acetamide, identification and fluores- Acid radicals, tests for, 191
cence, 379 Acid sulfide group of metals, tests for, 79
Acetanilide, identification, 378 Aconitic acid, conversion to citrazinic
Acetate (s), interference in hydrogen acid as test for, 407
peroxide test for titanium, 150 Acrolein, conversion to, as test for gly-
in sodium carbonate-phenolphtha- cerol, 408, 485, 486
lein test for carbonic acid, 255 identification, 342, 345, 347
reaction with cobalt salts, 215 reaction with dianisidine, 408
thiocyanate in presence of, 215 sodium nitroprusside and piperidine
Acethydroxamic acid, conversion to iron test for, 408
salt of, as test for sulfonic acids, 366 Action and liberation of gases (vapors),
formation, 366 - 29
Acetic acid, ferric chloride test for, 399 Acyloin compounds, oxidation to dioxo
formation of indigo as test for, 398 compounds, 335
lanthanum nitrate and iodine test for, Afcyloin oximes production of green in-
soluble copper salts, 309
397 reaction with copper salts, 65
"ring test" for nitrites, 250 Adrenalone, identification, 372
sodium nitroprusside and piperidine Adsorption processes in filter paper, 2
test for, 399 Agar-agar, identification, 411
summary of tests, 608 Agate mortars, 12
Acetic anhydride, identification, 361 Air bath, 27
Acetindoxyl, identification and fluores-
cence, 379 Alanine, identification, 384
Acetoacetic ester, identification, 332, Alcohol(3), denatured, test for pyridine
in, 486
351-352 polyhydric, test by oxidation with
Acetofiuorogluoose, detection of fluorine
in, 313 periodic acid, 326
Acetoin, identification, 336 primary and secondary, test by con-
Acetone, cobalt salts reaction with thio- version into alkali xanthates, 324
cyanates in presence of, 214 summary of tests, 506
identification, 334, 336, 345, 351-352 test with ammonium cerium nitrate.
thiocyanates in presence of, 214 329
Acetone dicarboxylic acid, identifica- Alcohol lamp, 40
tion, 351 Aldazines, formation, 186
Acetone oxime, identification, 353 Aldehyde(s), azobenzenephenylhydra-
Acetophenone, identification, 334, 345, zine sulfonic acid test for, 341
conversion to, as test for a-amino
351-352
Aceturic ethyl ester, identification and acids, 384
fluorescence, 376 fuchsin test for, 346
Acetyl acetone, identification, 351-352 identification with fuohsfn-sulfurous
Acid (a), free, detection of mercury in acid, 384
presence of, 51 identification tests for, 342-344
519
520 SUBJECT INDEX
AIdehyde(8), interaction with bisulfite as Alkali bichromate, detection of alkali

test for, 333 monochromate in presence of, 467
p-phenylenediamine oxidation test for, Alkali chlorate as oxidizing agent for
345 carbon, 281 |
reaction with fuchsin-sulfurous acid, solutions, activation, as test for os-
339 mium and ruthenium, 107
with malachite green, 339 Alkali cyanides, carbonate in, detection,
summary of tests, 506 468
test with o-dianisidine, 340 - fixed alkalis and ammonia in, detec-
by formation of alkyl hydroxamic tion, 455
acid, 346 reaction with formaldehyde, 76
by reduction of silver oxide, 346 test for chloroform by conversion to,
with triphenylmethane dyes, 339 395
a,)8-unsaturated and aromatic, identi- Alkali earth metals in organic com-
fication tests for, 350 pounds, 311
test with hydrogen sulfide and so- Alkali ferricyanides as oxidizing agent
dium pentacyanoammine ferroate, for diethylaniline, aromatic amines,
349 and monoazo dyes, 137 '
Aldehyde ammonia, identification, 346 Alkali fluoride, conversion into, as test
for fluorine, 312
Aldehyde bisulfite compounds, identifi- reaction with boric acid, 259
cation, 346 with ferric salts, 113
Aldol, fluorescence with o-hydroxydi- Alkali hydrosulfides, test for in presence
phenyl, 401
reaction with p-hydroxydiphenyl, 400 ,of alkali sulfides, 230
Aldoximes, detection, 352 Alkali hydroxides, in);erference in pyro-
Alicyclic compounds, interference in catechol test for titanium, 151
o-dianisidine test for aldehydes, 341 test for sulfonic acids, 363
Aliphatic methyl ketones, test for, by Alkali hypobromites, reaction with man-
ganese salts, 133
interaction with bisulfi^, 333 Alkali hypoiodite test for magnesium,
Alizarin, reaction with chromium, iron,
and manganese, 144 171
with cobalt, copper, and iron salts, Alkali mercury thiocyanates, reaction
144 with cobalt and zinc salts, 140
with uranium, 144, 146 Alkali metals, fusion with, as test for
nitrogen, 316
test for aluminum, 144 in silicates, test for, 441
for aluminimi in tanned leather, 452 as test for sulfur, 313
for indium, 163-163 tests for, 171
for mercury, 53 Alkali monochromates, in presence of
for zirconium, 154 alkali bichromate,"^detection, 467
Alizarin paper test for aluminum in test for bichromate in presence of,
minerals, 463 467
Alizarin S, as reagent for boric acid, 257 Alkaline earth metals, zinc in presence
test for aluminum, 143 of, 142 .
Alizarin sulfonic acid, see Alizarin S Alkaline earths, nickel dimethylglyoxime
Alkali (s), in alkali cyanides, detection, test for, 456,
455 Alkaline earth sulfates, detection of
and alkali earths in coal ash and in lead sulfate in, 301
paper, detection, 455 iodine-azide reaction for, 238
in glass, test for, 448-449 Alkaline solutions, detection of silica in,
nickel dimethylglyoxime test for, 456 469 /
in organic compounds, 311 storage, 10 _
test for vulnerability of glass and Alkali periodates, reaction with man-
siliceous products to attack by, :469 ganous salts, 134, 224
thallium nitrate test for, in presence of Alkali peroxide as flux, 29
alkali sulfides, 230 Alkali salts, lead in, detection, 430-431
SUBJBCT INDKX 521
AlkaU Btamiite test for telluric and tel- of metals of ammonium sulfide
lurous acids, 266 group, 143-144
Alkali sulfate(8), interference in starch- of nickel, test for, 146
iodine reaction, 198 of other ions, test for, 144
in titanium-malachite green test for of other metals, identification limits,
tungsten, 96 145
Alkali sulfides, alkali in presence of, of uranium, capillary separation
thallium nitrate test for, 230 test for, 146
alkali hydrosulfides in presence of, quinalizarin test for, 146
test for, 230 reaction with potassium ferrocyanide,
conversion of sulfur to, 314 145
Îkali thiocyanates, reaction with hy- reduction of nitrates to ammonia by,
drogen peroxide, 271 247
with iodates, 223 solubility in nonoxidizing acids, 272
Alkali xanthates, test for primary and summary of tests, 496
secondary alcohols by conversion t o , in tanned leather, test for, 452
32i zinc in presence of, test for, 137
Alkaloids, reaction- with tetrabromo- Aluminum activation as test for mer-
phenolphthalein ethyl ester, 418 cury, 5S
Alkyl bydroxamic acid, formation, ae Aluminum block for concentrating solu-
test for aldehydes, 346 tions, 26-27
Alloys, copper in, detection, 426 Aluminum chloride, zinc in presence of,
electrographic test for, 39 141
free, simunary of tests, 505 Aluminum foil as cathode in electro-
tests for, 272 graphic method, 39
Heller method of analyzing, 291 Aluminum oxide in insoluble residue, 303
lead in, detection, 428 Aluminum salts, free acids and bac
manganese, in, detection, 137, 292-293 compounds in, detection, 472
nickel in, detection, 434 interference in alkali hypoiodite test
silver in, detection, 425 for magnesium, 172
solution of, 39 in zinc uranyl acetate test for so-
tin in, detection, 428, 432-433 dium, 176
AUyl alcohol, detection, 326 reaction with 1,2,7-trihydroxyanthra-
Allyl mustard oil, identification, 357 quinone, 89
Alum, interference in starchr-iodine re- as solvent for calcium fluoride, 203
action, 198 zinc in presence of, test for, 139
Alumina, detection by alizarin, 53 zirconium in presence of, test for, 154
iron in, detection, 303, 438 Amalgams, detection, 275
Aluminon test for aluminum, 147 Amides, acid, detection, 375, 379
Aluminum, alizarin S test for, 143 fluorescence, 379
alizarin test for, 144 summary of tests, 506
in alloys, test for, 292-293 Amines, aliphatic, dithiocarbamate test
aluminon test for, 147 for primary and secondary, 368
beryllium in presence of iron and, 148 in presence of aromatic, 369
indium in presence of, test for, 16S primary, detection, 373
interference in ferric-thiosulfate reac- fluorescence, 376
tion for copper, 64 teste for, 370, 376 '
magnesium in presence of, test for, reartion with furfural, 383
147, 175 with p-dimethylaminobenzalde-
in minerals, test with alizarin paper, hyde, 383
463 secondary, detection, 374
in mixtures, test for, 286, 289, 291 fluorescence, 376
morin test for, 142 Bodiimi nitropruEside and acetalde-
pontachrome blue-black R test for,
147 hyde test for, 371
in presence of cobalt, test for, 146 tests for, 370, 372, 376
34
622 SUBJECT INDEX
Amines, aromatic, detection, 375, 377- and hydrogen peroxide test for cerium,
378 160 i
detection of aliphatic amines in liberation as test for ammonium, 183
presence of, 369 manganese sulfate and hydrogen
p-dimethylaminobenzaldehyde as re- peroxide testj for, 185
agent for, 383 manganese sulfate and silver nitrate
nitroaodimethylanjline as reagent test for, 184 i
for, 383 Nessler reaction as teat for, 185, 283
6-nitroso-8-hydroxyquinoline as re- p-nitrobenzenediazonium chloride test
agent for, 383 for, 182-183
primary, glutaconic aldehyde test for precipitating oxides, 22
for, 378 in presence of lead mercury, and silver
sodium pentacyanoaquoferriate salts, 185
test for, 381 red litmus paper test for, 184
tests for, 382 reduction of nitrates to, 247
test by condensation with aromatic reduction to, as test for nitric acid, 247
nitrous compounds, 383 silver nitrate and formaldehyde test
with chloranil, 383 for,^185
with furfural, 383 silver'nitrate and tannin test for, 185
with resorcinol, 383
differentiation between aliphatic and test for hydroxylamine, 190
in water, test for, 477
Jromatic, 375 Ammoniacal silver nitrate, reaction with
fluorescein chloride test for, 371 cobalt, iron, and manganese salts, '
primary, test with carbon disulfide
160
and lead acetate paper, 383
secondary, detection in ethylenedi- as, reagent for reducing sugars, 409
amine, 371 test for cerium, 160
suimnary of tests, 506r-507 Ammonium, ammonia liberation as test
Amino acids, hydrolysis to, as test for for, 183
proteins, 414 in mixtures, test for, 283
reaction with p-dimethylaminobenzal- summary of tests, 496
dehyde, 383 Ammonium anthranilate, reaction with
with furfural, 383 cerium salts, 162
a-Amino acids, summary of tests, 507 Ammonium carbonate group of metals,
test by conversion to aldehyde, 384 tests for, 165
/S-Aminoanthraqujnone, identification, Ammoniiun cerium nitrate, test for al-
377 cohols, 329
o-Aminobenzaldehyde, identification, Ammonium, chloride, identification and
377 fluorescence, 376
p-Aminobenzaldehyde, identification, zinc in presence of, 141
334,343 Ammonium ferrocyanide test for cal-
2-Amino-5-dimethyiaminophenol, action ciimi, 169 ^
on aromatic o-diketones, 338 Ammonium mercury thiocyanate in zinc
p-Aminodiphenyl, identification, 382 as reagent for copper, 73
3-Anuno-4-phenyl-5-thiotriazole, identi- Ammonium molybdate-benzidine test
fication, 357 for germanium, 90
3-Aminophthal hydrazide, see Luminol for phosphoric acid, 250
a-Aminopyridine, identification, 382 for silicic acid, 252
Aminosulfonic acid, reaction with ni- Ammonium naphthoate, reaction with
trites, 246 cerium salts, 162
removal of nitrites by, 246-247 Ammonium phosphomolybdate, conver-
Aminotetrazol, identification, 382 sion of phosphate to, 317
Aminothioamide of thiazole, see Ghrys- reaction with ureates and uric acid, 421
ean reduction ofâstest for ascorbic acid,
Ammonia, in alkali cyamdes, detection, 421
455 test for tin, 86
SUBJECT INDEX 523
Ammonium salicylate, reaction with in mixtures, analysis, 282, 298

cerium salts, 162 summary of tests, 502
Ammonium salts, in chemicals, detec- Anisaldehyde, identification, 334, 340,
tion, 456 342, 345, 348, 350
in explosives, test for, 488 reaction with 2,7-dihydroxynaphtha-
interference, in alkali hypoiodite test lene, 400
for magnesium, 172 Anisaldehyde bisulfite, identification, 348
in benzoin oxime test for copper, 65 Anodic solution, 39
in dipicrylamine test for thallium, Anthranilic acid, identification, 358
, 121 Anthraquinone-l-azo-4-dimethylaniline
in iron periodate test for lithium, 181 hydrochloride as reagent for metal
in quinalizarin test for beryllium, salts, 89 '
148 Anthraquinones, detection, 257
for magnesium, 172 Antimonic acid in metastannic acid, de-
in test for hydroxylamine, 190 tection, 84
in zinc uranyl acetate test for so- Antimony, in alloys, test for, 292-293
dium, 176 detection of tin in presence of, 87
reaction with dipicrylamine, IW dithizone test for zinc in presence of,
with sodium cobaltinitrite, 178 140
tests for, 182 hydrogen-flame luminescence test for,
Ammonium sulfide group of metals, 62, 86
indium in presence of, 163 interference in dithizone test for mer-
tests for, 109 cury, 50
for cations of, 288 9-methyl-2,3,7-trihydroxy-6-fluorone
Ammonium thiocyanate, and acetone test for, 85
test for cobalt, 112 in minerals, test with hydrogen sulfide
reaction with copper, ferric,-and nickel paper, 463
salts, 113 in mixtures, test for, 286, 288
and o-tolidine test for copper, 67 phosphomolybdic acid test for, 84
Amphibolite, phosphates in, detection, in presence of large amounts of tin, 86
472 reduction test for, 83
Analysis, of alloys, Heller method, 291 rhodamine B test for, 86
chromatographic, 477 summary of tests, 496
of mixtures, Gutzeit method, 283 zirconium in presence of, 155
Heller and Krumholz method, 287 Antimony compounds, reaction with
Krumholz method, 289 cacotheline, 88
organic, spot reactions in, 309 Antimony hydride, reaction with silver
Andesite, phosphates in, detection, 472 nitrate, 80
Anglesite, lead in, detection, 429 Antimony oxide, in insoluble residue, 307
Anhydrides of carboxylic acid, identifi- in metastannic acid, detection, 84
cation tests for, 359, 361 Antimony salts, detection of cadmium
Anhydrite, distinction from gypsum, 447 in presence of, 75
identification, 445 detection of tin in, 87
Aniline, identification, 377, 382, 390 reaction, with anthraquinone-l-azo-4-
dimethylaniline hydrochloride, 89
in the mercuric chloride test for tin, 89 with cacotheline, 87
oxidation to aniline black by vanadium with p-dimethylaminoazophenylar-
salts, 99
reduction of mercuric salts in presence sonic acid, 155
of, 50 with xanthone dyestuffs, 86
reduction, of phosphomolybdates by,
Aniline blue, formation, as test for oxalic 120
acid, 403, 485 by stannites, 266
Animal and vegetable fibers, differentia- Antimony sulfide paper, 20
tion, 484 Antimony trichloride, reduction of phos-
Anions, of add radical^, tests for, 191 phomolybdates by, 87
of metallic acids, testg for, 41 Antipyrine-tannin test for titanium, 152
524 SUBJECT INDEX
Apatite in rock-, detection, 472 germanium in presence of, 90

Apparatus, for delivering drops of water, Gutzeit test fol-, 80, 83
16-17- interference, in ferric thiosulfate test
for delivering uniform drops of mer- for copper, 64
cury, 17 in flame color, test for tin, 88
for detecting carbonate and sulfide, kairine test forj 83
30-31 in minerals, test with silver nitrate
gases, 30-32 paper, 463
a gas forming a colored reagent in mixtures, test for, 285, 288, 290
product, 31-32 in organic compounds, 311
a gas at high temperature, 31-32 summary of tests, 506
a gas in presence of other gases, test for, by conversion to arsenate,
30-32 318
minute quantities of gas, 30-31 pentavalent, precipitation by hydro-
for emptying centrifuge tubes, 38 gen sulfide, 80
for heating spots on paper, 32-33 in presence of mercury, detection, 79
for precipitating sulfides by hydrogen statmous chloride test for, 79, 318
sulfide,.30 simup^ry of tests, 496
for redistillation.of water, 40 test by reduction to arsenic hydride
for spot tests, list of, 40 and decomposition with silver ni-
for trAting paper with gases or vapors, trate or gold chloride, 80
29 Arsenic acid, catalytic reduction by
Application of spot tests in preliminary potassium iodide, 80
examination, 294 detection of phosphoric acid in pres-
Aqua regia extract, Gutzeit test in, 286 '' ence of, 251
Aqueous solution or suspension, testa interference in molybdate-benzidine
on, 296 test for gerinanium, 90-91
Arabinose, identification, 328 phosphates in presence of, 261
reaction, with ehromotropic acid, 396 reaction, with benzidine, 263
with formaldehyde, 396 with iodides, 82
Aragonite, distinction from cilcite, 444 with molybdates in acid solution, 250
d-Arginine, detection, 384 Arsenic compounds, in antimony reduc-
Arginylglycine, identification, ,370 tion test, 83
Arnold's base, in the manganese salt- reaction with cacotheline, 88
tetrabase test for periodates, 226 Arsenic hydride, gold chloride test for,
in the periodate test for manganese, 81 ':
134 silver nitrate test for, 80
Aromatic and aliphatic aldehydes, dif^ Arsenic pentoxide, test for arsenic triox-
ferentiation, 341, 346 ide in presence of, 83
Aromatic poljmitro compounds in ex- Arsenic trioxide in presence of arsenic
plosives, detection, 488 pentoxide, test forJ^SS-- ^ _
Arrowroot starch, identification, 411 Arse'nious acid, reaction with iodine, S2
Arsenates, arsenites in presence of, test reduction to arsine, 83
for, 82 Arsenites, interference in test for pal-
interference, in potassium thiocyanate ladium, 106
test for iron, 124-126 in presence of arsenates, test for, 82
in test for palladium, 106 Arsenomolybdic acid, formation, 250
with zirconium-aliiarin test for fluo- formation of benzidine blue by, 251
rides, 202 Arsine, reduction of arsenious acid to, 83
with zirconium sxoarsenate test for Arylhydrazines, test with aelenious acid
fluorides, 206
silver nitrate test for, 82 and a-naphthylamiiie, 387
Arsenic, detection of platinum in pres- Arylhydrazongs, cx-naphthylamine test
ence of, 103 for, 387; 389
ditbizone test for zinc in presence of, Asbestos, magnesium in, detection, 440
140 as medium for spot tests, 8
SUBJECT INDEX 525
Ascorbic acid, in fruit juices, detection, presence of permanganate as test

420 for, 167
. in presence of citric acid, detection, in presence of strontium, detection,
420-421 165-166,168
summary of tests, 503 rhodizonic acid test for, 165
test for, 419 sodium rhodizonate test for, 57, 165
test by reduction of ammonium phos- strontium in presence of, 166, 169
phomolybdate, 421 summary of tests, 496
by reduction of manganese dioxide, tetrahydroxyquinone test for, 168
420 Barium carbonate and phenolphthalein
in urine, detection, 421 test for sulfuric acid, 237
Ashing, apparatus for, 28 Barium rhodizonate test for sulfuric acid,
Aspara^ne, identification, 365 236
J-Asparapne, identification, 384 Barium salts, interference in cerium
i-Aspara^nic acid, identification, 384 salt reduction test for iodides, 201
Asymmetric diphenylhydrazine test for in zinc uranyl acetate test for so-
selenious acid, 264 dium, 176
Atomic groups in organic compounds, reaction with rhodizonic acid, 236
detection, 309 with sodium rhodizonate, 169, 236
Atomizer head for spraying reagents, 21 Bariiun sulfate, precipitation in presence
Auric chloride and palladium chloride, of permanganate as test for barium,
reaction mit rubidium and thallium 167
salts, 182 for sulfuric acid, 238
test for cesium, 182 reduction to sulfide, 238-239
Auric chloride teat for hydrogen perox- test for soluble sulfates, 237
ide, 271 Bases, free organic, detection, 480
Aurintricarboxylic acid, ammonium salt salts of organic, detection, 480
of, see Aluminon tertiary ring, test for, 392
Azides, carbonates in presence of, 255 treatment with, as special expedient, 8
in explosives, detection, 488 Basic compounds in solutions of alumi-
Azidodithiocarbonic acid, formation of num salts, detection, 472
sodium salt of, 417 Basic sulfide group of metals, tests for, 42
1,8-Aziminonaphthalene, formation, 249 Basins for cleaning solution dishes, 11
Azobenzene, detection of nitrogen in, 316 Beeswax, reaction with hydroxamic acid,
Azobenzenephenylhydrazine sulfonic 485
acid test for aldehydes, 341 Beilstein test for halogens, 311
Azo dyes, adsorptive property of mag- Benzaldehyde, identification, 334, 340,
nesium hydroxide for, 173 343, 345, 347, 360
formation, 383, 387 reaction with hydrazine, 186
formation of hydrazones with, as test Benzaldehyde-o-sulfonic acid, identifica-
for hydrazines, 385 tion, 334, 343
o-Benzaldehyde sulfonic acid, identifica-
B tion, 345, 347, 350, 367
Benzal derivatives of amines, reaction,
Balance, rough, 40 375
Balsam Tolu, reaction with hydroxamic Benzamide, identification and fluores-
acid, 485 cence, 379
Bandrowski's base, structure, 345 Benzene, carbon disulfide in, detection,
Barite, calcium sulfate in, detection, 446 483
Barium, as contaminant of filter paper, solutions, detection of nickel carbonyl
18
lead sulfate precipitation as test for, in, 484
167 as solvent, 281
magnesium in presence of, 176 Benzenesulfinic acid, identification, 367
mixtures, test for, 286 Benzene sulf ohydroxamic acid as reagent
precipitation of barium sulfate in for aldehydes, 346
526 SUBJECT INDEX
Benzene sulfone chloride, identifica- by metallic oxides, 233

tion, 368 by oxidizing agents, 208, 242
Benzenesulfo-p-nitranilide, identiiica- with peroxidase, 424
tion, 378 with phosphomolybdic acid, 250
Benzenesulfhydroxamic acid, identifica- with potassium permanganate, 214
tion, 353 with silicomolybdic acid, 251-252,
Benzhydroxamic acid, identification, 353 306
Benzidine, 2 with silver salts, 131
and ammonium molybdate test for with thallic salts, 120
phosphoric acid, 250 ia presence of chlorides, bromides, and
for silicic acid, 252 iodides, 208, 214
2,7-diaminofluorene as substitute for, of cyanides,' 208
242 Benzil, identification, 339, 371
identification, 377, 382 reaction with ethylenediamine, 369
oxidation by cerium, cobalt, silver, Benzil dioxime, identification, 353
and thallium salts, 135 Benzoic anhydride, identification, 361
by chromates, 135 Benzoin, identification, 345
by ferricyanides, 135 Benzoin oxime, formation of green cop-
products of, 55 per salt of, 309
reaction with arsenic and phosphoric identification, 353
acids, 253 test for copper, 65
with cerium, cobalt, manganese, and Benzoylacetic ester, identification, 332
silver salts, 120 Benzoylhydrazide, identification, 386-387
with chromates, 131 Benzylamine, fluorescence, 376
with copper salts, 208 identification, 370, 376, 390
for manganese, 222 Benzylbenzoin oxime, identification, 353
for prussio acid, 214 Benzylidene-p-nitraniline, identification,
with vanadates, 131 378
test for cerium, 161 2-Benzylpyridine, reaction with stan-
for chromium, 131 nous chloride, sulfur dioxide, and
for copper, 73, 208 sulfites, 236
for gold, 100-101 test for tin, 89
for lead, 55, 305 Beryllium, interference in alizarin or
for manganese, 134, 305 quinalizarin test for indium, 163
for nitrites, 250 p-nitrobenzeneazoorcinol test for, 149
for persulfuric acid, 242 in presence of iron and aluminum, 148
for thallium, 119 of magnesium, detection, 148-149
Benzidine acetate, reaction with osmium, quinalizarin test for, 147-148
109 summary of tests, 497
test for ferricyanic acid, 218 Beryllium salts, reaction with morin, 142
Benzidine acetate-copper acetate solu- reaction with quinalizarin, 172
tion, preparation, 208-209 as solvent for calcium fluoride, 203
test for hydrocyanic acid, 208, 317 zirconium in presence of, 154
Benzidine blue, formation, 184-185, 420, Bettendorf test for arsenic, 79
471 Bibliography, 489
by arsenomolybdic acid, 251 Bicarbonate in presence of carbonate,
by bismuth oxides, 432 test for, 255
by cerium salts, 161 Bichromate, interference in tetrabase
by chromates, 131 oxidation test for ferricyanic acid,
by cobalt salts, 131 220
by copper salts, 131, 208 in presence of alkali monochromates,
by germanium salts, 90 detection, 467 '
by gold salts, 100 Biocatalysts, action, 421
by hydrated manganese dioxide, 135 Biological compounds, spot reactions
by lead peroxide, 55 for detection of, 3
by lead salts, 131 Bismuth, in alloys, test for, 292-293
SUBJECT INDEX 627
cinchonine and potassium iodide test hydroxyanthraquinone test for, 257
for, 59 interference in etching test for fluor-
detection of copper in presence of, 68 ides, 207
hydrogen-flame luminescence test for, methyl alcohol flame test for, 261
62 methyl borate and alkali fluoride test
interference in dithizone test for mer- for, 259
cury, 50 p-nitrobenzeneazochromotropic acid
in minerals, test with potassium iodide test for, 258
paper, 463 . in presence of oxidizing agents or
in mixtures, test for, 285, 288, 290 fluorides, 259
potassium chromium thiocyanate test reaction with hydroxyanthraqulnones
for, 62 91
potassium manganocyanide test for, 63 reagents for detecting, 257
in presence of copper, detection, 69-61 summary of tests, 502
of lead, detection, 59-60 test by increase in acidity with organic
of mercury, detection, 59-61 polyhydroxy compounds, 260
quinoline and potassium iodide test tincture of curcuma test for, 256
' for, 63 Borides in insoluble residue, 306
reaction with thiourea, 265 Boron, in enamel, detection, 471
with 1,2,7-trihydroxyanthraqui- in glass, test for, 448
none, 89 in rocks, detection, 471
stannite test for, 60, 63 Braunerite, distinction from magnesite,
summary of tests, 497
442
thioacetamide test for, 63
Broeggerite, uranium in, detection, 439
zinc in presence of, 142
Bromal, identification, 342
Bismuth chloride, reaction with rho-
m-Bromaniline, identification, 382
damine B , 86
Bromates, reaction with diphenylamine,
Bismuth compounds, lead in, detection,
244
432
with manganous sulfate and sulfuric
Bismuth ssklts, benzidine test for, 55
acid, 222
detection of cadmium in presence of, 75
interference in benzidine test for lead, with pyrogallol, 224
Bromic acid, manganous sulfate and sul-
65
furic acid test for, 222
reduction by stamiiteB, 266
tests for, 63 summary of tests, 602
Bismuth subgallate, lead in, detection, Bromides, in chlorides and iodides, d e -
432 tection of small amounts, 196
K s m u t h BubMlicylate, lead in, detec- cyanides in presence of, 209
tion, 432 fluorescein test for, 194
Bismuth BubtannAte, lead in, detection, interference in cerium salt reduction
432 test for iodides, 201
Bi8ulfite(g), i a pretence of sulfites, 236 in ferrous sulfate-sulfuric acid t e s t
test for aldehydes and aliphatic for nitric acid, 243
methyl ketones by interaction with, in hydrogen peroxide test for tita-
333 iiium, 150
Black powder, test for nitrates in, 488 for vanadium, 98
Blood, detection, 424 in oxidation test for manganese, 133
Blood albumin, identification, 414 in silicomolybdic acid test for flu-
Blowing and working glass, equipment orides, 207
for, 40 in mixtures, test for, 283
Bogen's Universal indicator, 475 oxidation t o bromine, 192-194
Bolting powdered specimens, 12 potassium bromide-cuprous bromide
Borate in mixtures, test for, 284 test for, 197
Borax aa solvent for calcium fluoride, 203 in presence of chlorides, fluorescein
Boric acid, carminic acid test for, 291 test for, 195
cochineal fluorescence test for, 94 . of iodides, 195, 202
528 SUBJECT INDEX
Bromides, reaction vrith potassium per- lead, mercury, silver, tellorium,

manganate, 214 and tin salts, detection, 75
tUocyanate in presence of, 214r-215 of copper, detection, 76-78
Bromine, detection, 195 of zinc, detection, 76
interference in chromyl chloride test reaction with sodium rhodizonate, 57
for hydrochloric acid, 193 summary of t ^ t s , 497
in organic compounds, detection, 196 Cadmium chloride, zinc in presence of,
oxidation of bromides to, 192-194 141
and potasBiuni iodide test for enols, 33? Cadmium hydroxide, reaction with di-^-
test for hydrobromic sicid by oxida- naphthylcarbazone, 78
tion to, 194 with di-p-nitrophenylcarbazide, 76
Bromine compounds, reaction with cop- with p-nitrobenzeneazoresorcinol, 174
per oxide, 311 Cadmium red, selenium in, 465
Bromine water, reaction with dimethyl- Cadmium salts, interference in zinc
glyoxime, 117 uranyl acetate test for sodium, 176
Bromocresol green and purple as indica- reaction with anthraquinone-l-azo-4-
tors of hydrogenîoQ concentration, dimethylaniline hydrochloride, ,89
Cadmiiun stannoiodide test for lead, 58
Bromophenol blue as indicator of hy- Cadmium sulfide paper, 20
drogen-ion concentration, 474, 476 Calcite, in caustic magnesite, 444
p-Bromophenylhydrazine, identification, distinction from aragonite, 444
388 Calcium, ammonium ferrocyanide test
Bromothymol blue, as indicator of hy- for, 169
drogen-ion concentration, 474, 476 as contaminant of filter paper, 18
as indicator in test for boric acid, 260 dihydroxytartaric acid osazone teat
Brucine test for nitric acid, 245 for, 170
Burets for delivering drops, 17 magnesium in presence of, 176
Butyl alcohol, detection, 326 in mixtures, test for, 287
Butyraldehyde, reaction with p-hy- reaction with potassium ferrocyanide,
droxydiphenyl, 401 169
Butyrase, detection, 422 summary of tests, 497
Calcium carbonate, reaction with p-ni-
trobenzeneazo-a-najdithol, 174
Cacotheline, formula for, 87 Calcium fluoride, detection, 204
reaction for tin salts, 62 in insoluble residue, 307
test for stannous chloride, 308 as reagent-purifying adsorbent, 64
for tin, 87 solution of, 203
for vanadium, 99 Calcium hydroxide, reaction with p-ni-
Cadmium, in alloys, test for, 292-293 trobenzeneazo-a-naphthol, 174, 176
copper in, test for, 426 Calcium salts, interfe?ence-in,idnc uranyl-
copper in presence of, detection, 68 acetate test for sodium, 176
di-/5-naphthyloarbaione test for, 78 Calcium sulfate, in barite, detection, 446
di-p-nitrophenylcarbazide test for, 76 identification, 445
di-p-nitrophenylcarbazorie test for, 76 mercuriCvnitrate test for, 446
diphenylcarbazide test for, 78 presence as filler for paper, detection,
dithizone test for zinc in presence of, 446
140 Camphoric anhydride, identification, 361
ferrous dipyridyl iodide test for, 74 Camphorquinone, identification, 339
magnesium in presence of, 175 Camphorquinone oxime, identification,
in minerals, test with hytirogen sul- 353
fide paper, 463 Camphorsulfonic acid, identification, 367
in mixtures, testa lor, 285, 288, 291 Candelilal wax,^reaction with hydrox-
p-nitrodiazoaminoazobenzene test for, amic acid*, 485'
79 Capillarity of filter papers, 19
in presence of antimony, bismuth, Capillary effects, 1
SUBJSCT INDEX 529
Capillafy proceasea ia filter paper, 2 commercial, detection of phosgene in,
Capillary separation, of ainmine salts as 417
test for nickel, 118-119 Carbonyl compounds, summary of testa,
for detection of copper in presence of 607
nickel and cobalt, 71 test for, 333
Capillary surface actions in spot analy- Carboxylio acid, summary of tests, 607
sis, 9 teats for, 355
Carbazole, identification and fluores- Carboxylic acid anhydridea, reaction
cence, 379 with hydroxylamine, 359
Carbide carbon, detection, 281 summary of teats, 607
Carbides, carbon in, 303 testa for, 359, 361
Carbohydrates, reaction with sulfuric Carboxylic acid esters, summary of tests,
and gallic acids, 405 507
summary of tests, 508 teat for, 368, 360
test by hydrolysis to furfural, 410 CariuB procedure, 311
tests for, 408 Carminic acid, reaction with zirconium,
Carbon, in coal, potassium chlorate de- 157
crepitation test for, 308 as reagent for lead salts, 59
free, summary of tests, 505 test for boric acid, 261
teat by oudation, 281 Camauba wax, reaction mtb hydrozamic
iu insoluble residue, 308 acid, 485 ,
in organic colnpounds, presence, 311 Casein, detection, 413-414
Carbonate, in. alkali cyanides, sulfites, Casaiterite, tin in, 432
and sulfides, detection, 468 Catalase, detection, 423
apparatus for detection, 30-31 Catalysis of iodine-azide reaction as test
extract, Gutzeit test in, 283 for thiosulfuric acid, 240
interference in pyrocateohol test for Catalytic acceleration, of ferric-thio-
titanium, 151 sulfate reaction as test for copper, 63
in mixtures, test for, 283 of reduction of tin salts as t ^ t lor *
in presence of azides, cyanides, flu- mercury, 52
orides, nitrites, sulfides, sulfites, and Catalytic reduction of cerium salts as
thiosulfates, 255 test for iodides, 200
sodium carbonate and phenolphthalein Catalytic testa for platinum metals, 101
test for, 264 Catalyzed oxidation of phenolphthalin as
test for bicarbonate in presence of, 255 test for hydrogen peroxide, 270
Carbon dioxide, summary of tests, 502 Catalyzed reactions, 2
in water, test for, 477 Cations, of metallic acids, tests for, 41
Carbon disulfide, in benzene and carbon in mixtures, systematic analysis, 282,
tetrachloride, detection, 483 287
hydrogen sulfide in presence of, summary of tests, 496
418^19 Caustic alkalis, detection of silica in, 469
and lead acetate paper test for primary Cellophane as medium for spot teata, 6
amines, 383 Cellophane sluelds, 15
as solvent, 277, 279-281 Cellulose, as contaminant of filter
sulfur in, detection, 480 paper, 18
summary of tests, 508 identification, 411
test with formaldehyde and plumbite teat for permanganate in presence of
solution, 418 chromate, 261
with so(tium azide and iodine, 417 Cementation, 272
Carbonic acid, sodium carbonate and Centrifuge tubes, 25-27, 36-37
phenolphthalein teat for, 254, 468 cleaning, 38
Carbon monoxide, catalytic reduction of suction device for emptying, 38
phosphomolybdates as teat for palla- Centrifuging for sedimentation of insol-
dium and platinum, 105 uble materials, 36
Carbon tetrachloride, carbon disulfide Ceriiuu, ammoniacal silver nitrate test
in, detection, 483 for, 160
630 SUBJECT INDEX
Cerium, benzidine test for, 161 Chemiluminescence, produced by oxidiz-

hydrogen peroxide and ammonia test ing luminol, 271,
for, 160 Cherry gum, identification, 328
interference in pliosphomolybdic acid Chloramine-T as oxi(iizing agent, 194
test for vanadium, 100 Chloranil as reagent for aromatic amines,
malachite green test for, 162 383
manganese in presence of, test for, 136 p-Chloraniline, identification, 377
in mixture of rare earths, 160,162 Chlorate explosives, test for chlorate ion
of zirconium and thorium salts, 162 in, 488
phosphomolybdic acid test for, 161 Chlorate solutions, activation, as test for
in presence of chromates, 161 osmium and ruthenium, 107
of cobalt, copper, manganese, silver, Chlorates, interference in chromyl chlo-
and thallium salts, 161 ride test for hydrochloric acid, 193
of iron, 161 reaction with brucine, 245
summary of tests, 497 with diphenylamine, 244
Cerium perhyAoxide, formation, 160 with manganese sulfate, 221
Cerium salts, catalytic reduction of, as with manganous sulfate, 224
test for iodides, 200 Chloric acid, manganous sulfate and
for silver, 47 phosphoric acid test, 221
interference in benzidine test for summary of tests, 502
lead, 55 Chloride(s), bromides in presence of,
in hydrogen peroxide test for vana- fluorescein test for, 195
dium, 98 chromyl chloride test for, 32
in o-tolidine test for copper, 67 cyanides in presence of, detection, 209
lake formation with quinalizarin, 148 detection of bromides in, 196
oxidation of benzidine by, 135 in ink writing, test for, 453-454
reaction with ammonium anthranilate, interference in cerium salt reduction
162 test for iodides, 201
with anmionium naphthoate, 162 in diphenylcarbazide test for pal-
with ammonium salicylate, 162 ladium, 107
with benzidine, 120 in ferrous sulfate-sulfuric acid test
with hydrogen peroxide, 150 for nitric acid, 243
with quinalizarin, 172 in hydrogen peroxide test for tita-
Cerussite, lead in, detection, 429 nium, 150
Cesiimi, auric chloride, and palladium in oxidation test for manganese, 13S
chloride test for, 182 in silicomolybdic acid test for fluo-
gold platinibromide test for, 182 rides, 207
indium in presence of, 163 iodides in presence of, 201-202
lithium in presence of, 181 mercury in presence of, detection, 61
potassium bismuth iodide test for, 182 in mixtures, test for, 283 '
summary of tests, 497 reaction with potassium permanga-
Cesium chloride, lithium in presence of, nate, 214
181 thiocyanate in presence of, test for,
Cesium salts, reaction with dipioryl- 214-215
amine, 179 Chlorine, development of, in chromyl
Cetyl palmitate, identification, 360 chloride reaction, 192
Chalk, magnesium in, 443 Chlorine compounds, reaction with cop-
Characteristic groups, detection by spot
per oxide, 311
reactions, 6
Charcoal, carbon in, 308 Chloroarsanilic acid, detection of arsenic
detection of alkali in ash of, 456 in, 319 ^
sulfide sulfur in animal, test for, 481 Chlorobromoapdne* acid test for zir-
Charring of organic materials, 239-240 conium, 157
Chelidonic acid, test for, 394 Chlorodinitrobenzene, identification, 326
Chemicals, detection of sulfate in inor- Chloroform, detection of phosgene in
ganic fine, 466 commercial, 417
testing for purity of, 4d simunary of tests, 509
SUBJECT INDEX 531
test by conversion to alkali cyanide, in chromite, detection, 304
395 diphenylcarbazide test for, 128, 192,
Chloronitrobenzene, halogen in, detec- 304, 438
tion, 312 indium in presence of, 164
0-, m-, p-Chloronitrobenzene, identifica- in ink writing, test for, 453
tion, 324 interference in stannous chloride test
Chloroplatinic acid, interference in for arsenic, 79
o-tolidine test for copper, 67 iron in presence of, 125
Choice of procedures in spot analysis, 8 lake formation with alizarin, 144
Chromate-diphenylcarbazide reaction, magnesium in presence of, 175
discharge by hydrogen peroxide and in mixtures, tests for, 286, 289-290
peroxides, 271 in presence of cobalt, copper, man-
Chromate and potassium iodide paper ganese, and nickel, 128
test for silver in minerals, 463 of cobalt, copper, lead, and silver
Chromates, cellulose test for perman- salts, 131
ganate in presence of, 261 of manganese, 131
cerium, in presence of, 161 of mercury, 130
conversion of chromium salts to, of molybdenum, 130
128-lM in rocks, detection, 438
diphenylcarbazide test for, 262 in steel, detection, 438-439
formation of benzidine blue by, 131 summary of tests, 497
interference in alizarin test for alu- in tanned leather, test for, 451
minum, 144 titanium in presence of, 153
in diphenylcarbazone test for mer- zinc in presence of, 137
cury, 49 Chromium chloride, in insoluble residue,
in hydrogen peroxide test for vana- 304
dium, 98 in presence of palladium salts, 103
in phosphomolybdic acid test for Chromium nitrate, zinc in presence of,
vanadium, 100 141
in tetrabase oxidation test for ferri- Chromium oxide in insoluble residue, 304
cyanic acid, 220 Chromium salts, conversion into chro-
oxidation of benzidine by, 135 mates, 128-129
of chromium salts to, 128-129, 133 interference in periodate test for man-
of pyrogallol by, 224 ganese, 134
in presence of permanganates, 261-262 in potassium thiocyanate test for
reaction with benzidine, 131, 161, 208, iron, 125
242 oxidation to chromates, 128-129, 133
with carbazone, 94 reaction with 1,2,7-trihydroxyanthrft-
with diphenylamine, 244 quinone, 89
with diphenylcarbazide, 305-306 as solvent for calcium fluoride, 203
with ferrous sulfate and sulfuric Chromochlorite, chromium in, 439
acid, 243 Chromodiopside, chromium in, 439
with hydrogen peroxide, 150 Chromotrope 2B as reagent in boric acid
with silver nitrate, 82 test, 258
reduction by hydrogen peroxide, 271 Chromotropic acid, reaction with iron,
test for, by formation of silver or lead mercury, silver, and uranyl salts, 152
chromate, 132 reaction with metal salts, 152
Chromatographic analysis applied to in- and stannous chloride test for silver, 48
organic analysis, 477 test for formaldehyde, 395, 397
Chromic acid, as oxidizing agent, 335 for mercury salts, 55
summary of tests, 502 for titanium, 151-152, 440
test for, 262 Chromyl chloride, formation as test for
Chromite, detection of chromium in, 304 hydrochloric acid, 191 .
Chromium, acid alizarin RC test for, 132 test for chloride, 32
in alloys, test for, 292-293 Chrysean solution, reaction with ni-
aluminum in presence of, 145-146 trites, 250
benzidine test for, 131 Cinchonine, test for, 394
5S2 SUBJECT INDEX
CSachonine and potassium iodide test for of iron, 110-111,! 113

bismuth, 59 of uranium, 110^111
Cinnamaldehyde, identification, 340, reaction with dimethylglyoxime, 116
344-345, 348, 360 with potassium'ferrocyanide, 138
CSnnamaldehyde bisulfite, identification, rubeanic acid test lor, 70, 112
348 solubility in aonoxid'uimg acids, 272
Cinnaihic acid, identification, 358 summary of tests, 498
Cinnamoyl formic acid phenylhydrazone, test for manganese in presence of,
identification, 388 133-134
Citral, identification, 342 Cobalt hydroxide, reaction with p-nitro-
Citrazinic acid, conversion to, as test for benzeneazoresorcinol, 174
citric acid, 407 Cobalt and iron salts, nickel in presence
CStric acid, conversion into citrazinic of, 114, 116
acid as test for, 407 Cobalt mercury thiocyanate test for zinc,
detection of ascorbic acid in presence 140
of, 420-421 Cobaltous hydroxide, reaction with
in fruit vinegar, detection, 486 malachite green, 162
glycolic acid in presence of, 400 Cobalt salts, as catalyst in oxidation test
identification, 358, 364 for manganese, 133
summary of tests, 509 cerium in presence of, 161
Citronellal, identificatidti, 342 formation of benzidine blue by, 131
Clausthalite, selenium in, 465 free acids in solutions of, detection, 472
Cleaning, of bottles, 10 interference in ammonium mercury
of centrifuge tube, 38 thiocyanate test for copper, 73
of crucibles, 26 in benzidine test for lead, 65
of micro test tubes, 26 in cerium salt reduction test for io-
of solution dishes, 11 dides, 201
of spot plates, 24 in potassium thiocyanate test for
Clupein, detection, 413 iron, 125
Coal, 281 zinc uranyl acetate test for sodium,
carbon in, 308 176
Coal ash, detection of alkali in, 455-456 mckel in, detection, 434
Cobalt, in alloys, test for, 292-293 nickel-free, preparation, 436
aluminum in presence of, 145-146 oxidation of benzidine by, 135
ammonium thiocyanate and acetone presence jin 1,2-diaminoanthraqui-
test for, 112 none-3-8ulfonic acid test for copper,
chromium in presence of, 128 70
copper in presence of, 71-72 reaction with alizarin, 144
indium in presence of, 163-164 with alkali mercury thiocyanates,
interference in phosphomolybdic acid 140 " - ~-.^
test for vanadium, 100 with ammoniacal silver nitrate, 160
in stannous chloride test for arsenio, with benzidine, 120,131,161
79 with l,2-diaminoanthraquinone-3-
iron in presence of, 125 sulfonic acid, 69
magnesium in presence of, 175 with dimethylglyoxime, 114,126
manganese in presence of, 135 with diphenylcarbazide, 128 .
in minerals, test with potassium nitrite with 2-nitro80-l-naphthol-4-sulfonic
and potassium thiocyanate paper, acid, 128
463 with rubeanic acid, 109,118
in mixtures, tests for, 286,289,291 with thiocyanates in presence of ace-
nickel in presence of, 114-116,118, 435 tone, 214 /
in nickel salts, test for, 112-113 test for thiocyanic acid, 214
nitrosonaphthol test f<>r, 109 Cobalt zincateT formation of, 141
2-mtroso-l-naphthoI-4-8ulfomc acid Cochineid fluorescence test, for bono
test for, 74,113 acid, 94
in presence of copper, 110-111 for molybdenum, 94
SUBJECT INDEX 533
Godein hydrochloride, detection of nitro- in thiourea test for selenious acid,
gen in, 316 265
Colloidal gold solutions, qualitative iron in presence of, 12S
analysis of, 101 magnesium in presence of, 175
Colophony, reaction with hydroxamio manganese in presence of, 136
acid, 485 mercury in presence of, 52
Color, intensity as basis for quantitative in metallic zinc, test for, 426
analysis, 7 in minerals, test with ferrocyanide
of metals and alloys, 272 paper, 463
Colored materfals, apparatus for colori- in mixtures, tests for, 285, 288, 291
metric deterniination, 40 nickel in presence of, 115-116, 118
Colored reaction products, observation, 2-nitro80-l-naphthol-4-sulfonic acid
2a-24 test for, 74
Colorimeter, 40 in pharmaceutical products, 427
Color lakes, 69 pbosphomolybdic acid test for, 67
Columbium, see Niobium precipitation by antimony sulfide
Compounds, insoluble, conversion to paper, 20
water-soluble iodides, 300 in presence of bismuth, cadmium, lead,
Concentration limit, defined, 4 and mercury, 68
Concentration sensitivity, defined, 4 of cobalt and nickel, detection by
Concentrating solutions, 26-27 capillary separation, 71-72
Confined spot test papers, 7 of gold, nickel, and silver, 426
Congo copal, reaction with hydroxamio of hydrochloric acid, 66
acid, 485 of other heavy metals, 72
Coordination compounds, reactions in- reaction with dinitrodiphenylcarba-
volving, 2 zide, 77
Copper, acceleration of ferric-thiosulfate with potassium ferrocyanide, 138
reaction astestfor,63 with rubeanic acid, 70,112,426
in alloys, detection, 292-293, 426 salicylaldoxime test for, 66
benzidine test for, 73 in sections of metals, developing proc-
benzoin oxime test for, 66 ess for, 461 .
bismuth in presence of, detection, solubility in nonoxidizing acids, 272
69-l summary of tests, 498
test with ammonium mercury thio-
cadmium in presence of, detection,
75-78 cyanate in presence of zinc salts, 73
in cadmium, test for, 426 o-tolidine and ammonium thiocyanate
as catalyst, in oxidation test for man- test for, 67
ganese, 133 uranium in presence W iron and, 158
in water, detection, 427, 477
in sodium thiosulfate reduction of Copper acetate-benzidine acetate, prep-
iron, 159 aration of solution, 208-209
catalytic test for, 63, 427 test for hydrocyanic acid, 208, 317
chromium in presence of, 128 Copper acetate-benzidine reaction for
cobalt in presence of, 110-111 cyanides, 395
1,2-diaminoanthraquinone-3-8ulfonic Copper halide, conversion to, as test for
acid test for, 88
diphenylcarbazone test for, 74 halogens, 311
distinction from gold, 101 Copper hydroxide, formation, 76
dithizone test for, 72 Copper-manganese solution as reagent
in foodstuffs, detection, 427 for telluric acid, 268
hydrobromic acid test for, 74 Copper oxide, decomposition of organic
HCl-phenetidine and hydrogen per- components by, 274
oxide test for, 74 Copper salicylaldoxime, formation of,
8-hydroxyquinoline test for, 73 66, 188
interference in dithizone test for mer- Copper salt (s), of benzoin oxime, forma-
cury, 60 tion, 309
534 SUBJECT INDEX
Copper saU(s), cerium in presence of, 161 Cresol red as indicator of hydrogen-ion
complex formation, as test for periodic concentration, 476
acid, 225 Crocoite, lead in, detection, 429
formation of benzidine blue by, 131,208 Crotonaldehyde, identification, 342, 345,
formation as test for telluric and tel- 347 '
lurous acids, 267 Crotonjc acid, identification, 358
free acids in solutions of, detection, Crucibles, cleaningj 26
472 micro, 25-26
interference in cerium salt reduction Crystalline precipitates, microscope for
test for iodides, 201 identification, 40
in dithizone test for zinc, 139 Cumic aldehyde, identification, 343
in indigo test for acetic acid, 398 Cupferron, 2
in kairine test for arsenic, 83 Cupric ferricyanide test for cyanides, 212
in potassium thiocyanate test for Cuprous bromide-potassium bromide
iron, 125 test for bromides, 197
in zinc uranyl acetate test for so- Cuprous halides, interference in tests for
dium, 176 free metals and alloys, 273
reaction with acyloin oxime com- Cuprous iodide test for mercuric salts, 55
pounds, 65 Cuprous salts, dimethylaminobenzyli-
with alizarin, 144 dene rhodanine reaction with, 43, 73
with ammonium thiocyanate, 113 Curcuma, tincture of, test for boric acid,
with benzidine, 131, 161, 208 256
with cacotheline, 52 Curcumin, conversion to rosooyanine,
with dimethylglyoxime, 114, 126 256
with diphenylcarbazide, 128 reaction with metal compounds, 256
with disodium-l,2-dihydroxyben- Cyanide group, reaction with copper
zene-3,5-disulfonate, 126 oxide, 311
with nitrosonaphthol, 110-111 Cyanide ions, test for, 221
with 2-nitroso-l-naphthol-4-sulfonic Cyanides, carbonates in presence.of, 255
acid, 113, 128 copper acetate-benzidine acetate test
with potassium ferrocyanide, 157 for, 208
with rubeanic acid, 109, 118 cupric ferricyanide test for, 212
reduction to copper 6y hypopiosphor- d'etection by copper acetate-benzidine
ous acid, 266 mixture, 395
of phosphomolybdates by, 120 by copper sulfide, ^W
by stannites, 266 by 2,7-diaminofluorene, 395
and salicylaldehyde test for hydroxyl- dissociation of complex, 76
amine, 187 effect on the starch-iodine reaction, 198
Copper sulfate, as reagent for telluric interference in cerium salt reduction
acid, 267 test for iodides, 201
solution, detection of free sulfuric acid in l,2-diaminoanthraquinone-3-8ul-
in, 473 fonic acid test for copper, 69
in wood preservatives, detection, 450- in reduction test for nitrates, 247
451 in sodium carbonate-phenolphthal-
Copper sulfide test for hydrocyanic acid, ein test for carbonic acid, 255
209 in test for ammonium.salts, 183
Copper thiocyanate as reagent for sil- in mixtures, test for, 283-284
ver, 48 nickel in presence of, 117
Cornstarch, identification, 411 picric acid and sodium carbonate test
Corrosion in machinery metal, detection, for, 212
459 in presence of ferro- and ferricyanides,
Cosmetics, adulterants in, detection, 486 iodides, bromides, chlorides, and
glycerol in, detection, 486 thTocyanates, 209
Cotton, differentiation from wool, 485 of sulfides or sulfites, 209
Coumarin, identification, 360 prussic acid and starch-iodine test for,
o-Creeol, identification^ 330 212
SUBJECT INDEX 535
reaction with ferrous sulfate and sul- Dicarboxylic acids, tests for, 364-365
furic acid, 243 1,2-Dicarboxylic acids, resorcinol teat
with formaldehyde, 76 for, 360
Cyanogen, detection by the copper ace- summary of tests, 507
tate-benzidine acetate reaction, 208 Dichloroacetic acid, identification, 358
in mercuric cyanide, detection, 210 Diethanolamine, identification, 370, 372
Cyanogen iodide test for mercuric cya- Diethylamine, detection in commercial
nide, 211 triethanolamine, 371
Cyanogen radical, capillary detection of fluorescence, 376
ions containing, 221 identification, 372, 376
Cyclohexanedione dioxime, identifica- Diethylaniline, identification, 378
tion, 353 oxidation by alkali ferricyanides, 137
Cyclohexanol, detection, 326 Diethylaniline-ferricyanide test for zinc,
Cyclohexanone, identification, 336, 345 137
Cyclopentanone, identification, 336 Diethylhydrazine, asymmetric, identi-
Cylindrite, tin in, 432 fication, 386
Diethyl malonate, identification, 360
D Diethyl oxalate, identification, 360
Decrepitation test for carbon in coal, 308 Diferuloylmethane, see Curcumin
Decylaldehyde, identification, 342 Dihydropyrazines, formation, 369
Desiccator, 12 1,2-Dihydroxyanthraquinone sulfonic
Desoxybenzoin oxime, identification, 353 acid, see Alizarin S
Determination of solubility, 35 Dihydroxymaleic acid, identification, 364
Devarda's alloy for reducing nitrates to 1,8-Dihydroxynaphthalene-3%-disulfon-
ammonia, 247 ic acid, see Chromotropic acid
Developer for silver tests, 46 2,7-Dihydroxynaphthalene and sulfuric
Developing process for detecting hetero- acid test for glycolic acid, 399, 403
geneities in metals, minerals, etc., 2,6-Dihydroxypyridine-4-carboxylic acid,
457 see also Citrazinic acid
for detecting copper in sections of test for, 394
metals, 461 Dihydroxytartaric acid, reaction with
Development of spot test analysis, 1 /J,(S'-dinaphthol, 406
Dextrin, identification, 328, 410 Dihydroxytartaric acid osazone; identi-
Dextrose, identification, 328 fication, 388
Diacetyl, identification, 351-352, 371 test for calcium, 170
Diacetyldioxime, see also Dimethylgly- for differentiation between tap and
oxime distilled water, 170
formation, 186 Di-iodotyrosine, detection, 384
identification, 353 Di-isoamylamine, identification, 370, 372
Diacetylmonoxime and nickel salt test 1,2-Diketones, dithiocarbamate reaction
for hydroxylamine, 186 for, 369
1,2-Diaminoanthraquinone-3-sulf onic reaction with ethylenediamine, 369
acid as reagent for copper, 68 test for oxomethylene compounds by
2,7-Diaminofluorene reaction for cya- conversion to, 335
nides, 395 Dilution of solutions, 11
2,7-Diaminofluorene reagent as substi- p, p'-Dimethoxythiobenzophenone, iden-
tute for benzidine, 242 tification, 356
Dianisidine as reagent for acrolei 408 p-Dimethylaminoazophenylarsonic acid,
o-Dianisidine test for aldehydes, 340 preparation, 155, 205
Diastase, detection, 422 reaction with antimony, gold, and
Diazine green S(K) test for tin, 89 thorium salts, 155
Diazoi)ium salts, oxidation of arylhy-
drazines to, 387 with molybdates and tungstates, 166
Diazotization, 250 with tin and titanium salts, 156
Dibenzoylmethane, identification, 390 test for zirconium, 155, 204
SUBJECT INDEX
Dimethylaminobenz aldehyde, identifica- Dinitrophenol, identification, 326

tion, 345 Di-p-nitrophenylcarbazide test for cad-
p-Dimethylaminobenzaldehyde, identi- mium, 76 ^ I
fication, 343,378 Di-p-nitrophenylcarbazone test for cad-
reaction with amino acids, 414 mium, 76 I
as reagent for aromatic amines, 383 Dioxo compounds, distinction of ali-
p-Dimethylaminobenzylidene rhodanine phatic from aromatic, 334, 338
test for cuprous salts, 43, 73 1,2-Dioxo compounds, conversion to
for gold, 43, 100 nickel dioxime salts as test for ali-
for mercury, 43, 51,100 phatic, 334
for palladium, 43,100,107 identification, 336
for platinum, 43 o-Dioxo compounds, conversion to oxa-
for silver, 43, 100, 425 zine dyes as test for aromatic, 338
2,2'-Dimethyldicyclohexylamine, iden- tests for, 334
tification, 372 o-Dioxomethylene compounds, summary
Dimethylglyoxime, 2 of tests, 507
reaction with bromine water, 117 Diphenylamine, identification, 377
with cobalt salts, 114r-115, 126 reaction with oxidizing agents, 244
with copper salts, 114,126 test for nitric axsid, 244
with ferrous salts, 89, 114 Diphenylamine blue, formation, 403
with palladium, 114 Diphenylbenztdine test for nitric acid,
with persulfate, 117 244
with platinum, 114 Diphenylcarbazide, 2
reagent papers impregnated with, 4nd mercuric cyanide test for palla-
115 dium, 107
test for iron, 126 reaction with magnesium compounds,
^ for nickel, 114, 434 442
IT. minerals, 463 with mercury salts, 130
in presence of oxidizing agents, 117 with molybdates, 94
for vanadium, 98 with molybdenum'trioxide, 305
Dimethylpyrone, test for, 394 with vanadates, 130
^,0'-Dinaphthol and sulfuric acid test for test for cadmium, 78
tartaric acid, 406 for chromates, 262, 305-3(
Di-0-naphthylcarbazone, reaction with for chromium, 128, 192, 304, 438
molybdates, 94 for mercury, 304
as reagent for cadmium, 78 for molybdates, 1 ^ , 304
Dinitraniline, identification, 326 Diphenylcarbazone as reagent for cop-
Dinitroacetanilide (1,3,4) solution as per, 74
reagent for reducing sugars, 409 for mercury, 48
Dinitroaminobenzoic acid, identifica- Diphenylcarbohydrazide, eonversion to,
tion, 326 as test for phosgene, 416
Dinitroarsanilic acid, detection of ar- Diphenylhydrazine, identification, 386-
senic in, 319 387
m-Dinitrobenzene, identification, 324, test for selenious acid, 264, 465
326 Diphenyline test for tungsten, 97
Dinitrochlorobenzoic acid, identifica- Diphenylsulfoiirea, identification, 356
tion, 326 Diphenylthiodarbazone, see Dithizone
m-Dinitro compounds, identification Diphenyl thiocarbonate, identification,
tests for, 326
potassium cyanide test for, 323 356
summary of tests for aromatic, 507 Dipicrylamine, reaction with ammo-
1,8-Dinitronaphthaline, identification, nium, ceshun, rubidium, and thal-
326 lium 3atls,-179
reaction with potassium cyanide^ 323- test for potassium, 178,441
324 for thallium, 121
Dinitro-a-naphthol, identification, 328 Dipropylamine, identification, 370
SUBJECT I^n>EX 537
a,a'-Dipyridyl, a,a'-phenanthroline as Egg albumen, detection, 413-414
substitute for, 123 Electrically heated aluminum block' 26
reaction with metallic ions, 123 Electrically heated furnaces, 28
with molybdates, 94 Electric hot plate, 40
as reagent for ferrous salts, 89 Electric ignition furnace, 40
solution, preparation, 123 Electric muffle furnace, 40
test for iron, 122, 438 Electrodes for electrolytic deposition of
Disintegration processes as prelijoinary traces of metal, 477
operation, 8 Electrographic methodCs), 39
Disodium-l, 2-dihydroxybenzene-3,5-di- for detecting metals, 461
sulfonate, reaction with copper and Electrolysis apparatus, portable, 40
titanium salts, 126 Electrolytic depositions, 1
tept for iron, 126 Electrolytic reduction of nitro to nitroso
Dissecting needles, 14 compounds, 322
Distillation apparatus, 40 Elements, detection by sfcpt reactions, 5
Distilled water, differentiation from tap free, summary of tests, 505
water, 478 tests for, 272
Dithiocarlsamate reaction for 1,2-di- Emich centrifuge tubes, 25
ketones, 369 Emich filter stick, 36
Dithiocarbamate test for aliphatic Emulsin, detection, 422-423
amines, 368 Enamel(s), detection of boron in, 471
Dithizone, identification, 356 of lead in, 427
test for copper, 72 Enols, bromine and potassium iodide
for lead, 57 test for, 332
for mercury, 49 summary of tests, 507
for silver, ^ Enzymes, summary of tests, 509
for zinc, 139 tests for, 421-422
Di-p-tolyl trithiocarbonate, identifica- Eosin, formation, 194-195, 276
tion, 356 halogen in, detection, 312
Dolomite, in caustic magnesite, 444 Epichlorhydrin, identification, 345
distinction from magnesite, 442 Erythritol, conversion to formaldehyde
Dropper pipet, 15,38 and formic acid, 326
cleaning, 38 identification, 328
Dropping bottle, 10, 15 Erythrosine, formation, 276
Drops, application, 8, 14-17 Essential requirements for application of
removal ,14 spot tests, 9
Drugs, adulterants in, detection, 486 Esters, of carboxylic acids, hydroxamic
spot reactions, as purity tests for, 3 acid test for, 358
Drying, 26 tests for, 360
apparatus, for, 40 in mixtures of hydrocarbons, test for
of filter paper, 21-22 486,
as preliminary operation, 8 of nitric acid in explosives, 488
of spots, 34-36 in threads of textiles, detection, 488
Drying oven, portable, 40 Etching test for detecting hydrofluoric
Dyes, adflorptive property of magnesium
hydroxide on organic, 173 acid, 207
distinction between acid and basic, 483 for sulfur segregations in iron and
fluorescein type of, formation, 360 steel, 469
rhodamine, formation, 371-375 Ether, sulfur in, detection, 480
sulfide sulfur in, test for, 481 Ethyl acetate, identification, 360
Dyestuff inks, composition, 463 Ethyl acetoacetate, identification, 390
Ethyl alcohol, detection, 326
test for methyl alcohol in presence of
& 396
Earth osddes, test lor, 448 Ethylamine, identification, 370
Edeatin, detection, 413-414 Ethylenediamine, detection of secondary
amines in, 371
35
538 SUBJECT INDEX
Ethylenediamine, as reagent for 1,2-di- Ferricyanic acid (hydroferricyanic acid),

ketones, 369 benzidine test for, 218 >
Ethylene glycol, identification, 328 induced oxidationlof tetrabase test for,
Ethyl formate, identification, 360 220
n-EthyW-hydroxytetrahydroquinoline, phenolphthalin test for, 219
see Kairine trithiourea cuprous chloride test for,
Ethyl orthoformate, identification, 360 221
Ethyl stearate, identification, 360 Ferricyanide (s), cyanides in presence of,
Ethylurethan, identification, 360 209
Evaporation, 26, 28 and diethylaniline test for zinc, 137
and ignition residues, testing, 479 ferrocyanides in presence of, 216
as preliminary operation, 8 oxidation of benzidine by, 135
Explosives, spot tests in examining, 488 and p-phenetidine test for zinc, 141
Extraction, apparatus, 40 in presence of ferrocyanide, 218-219
processes, 2 of other oxidizing materials, test for,
as special expedient, 8 219
reaction with benzidine, 242
with silver nitrate, 8 ^
Fats, rancidity in, detection, 487 Ferrooyanio acid (hydroferrocyanic
test for, 408 acid), iron chloride test for, 216
Ferric chloride, reaction with hy- thiocyaiiate in presence of, 212
droxamic acids, 358-359 uranyl acetate test for, 215
with thiooyanate, 279 Ferrocyanide (s), cyanides in presence
test for acetic acid, 399 of, 209
zinc in presence of, 141 ferricyanide in presence of, 218-219
Ferric ferricyanide, reduction to Turn- in mixtures, test for, 284
iûll's blue as teat for sulfurous acid, in presence of ferricyanides, 216
336 of halide ions, 216
test for free metals and alloys, 273 of thiocyanates and iodides, 217-218
for hydrogen peroxide, 269 Prussian blue test for, 216-217
Ferric ferrocyanide,, formation, 274 reaction with ferrous sulfate and sul-
Ferric hydroxide, effect on benzidine test furic acid, 243
for manganese, 135 titanium tetrachloride test for, 221
Ferric iron as contaminant of filter Ferrocyanide paper test for copper, iron,
papers, 18 and zinc in minerals, 463
Ferric oxide in insoluble residue, 303 Ferrous dipyridyl iodide as reagent for
Ferric salts, dimethylglyoxime test for cadmium, 74
ferrous salts in presence of, 126 Ferrous ferrocyanide, formation, 274
interference in 9-methyl-2,3,7-trihy- Ferrous salt of ferricyanicacid, see Turn-
droxy-6-fluorone test for antimony, bull's blue
85 Ferrous salts, identification by dimethyl-
quercetin or quercitrin test for, 128 glyoxime, 89
reaction with alkali fluorides, 113 identification by a,a'-dipyridyl, 89
with ammonium thiooyanate, 113 in presence of ferric salts, dimethyl-
with diphenylamine, 244 glyoxime test for, 126
with nitrosonaphthol, 110 reaction with dimethylglyoxime, 114
with potassium ferrocyanide, 157 with 2-nitro80-l-naphthol-4-sulfonic
with thiosulfates, 63 acid, 113
reduction as test for tin, 89 Ferrous sulfate and sulfuric acid test for
Ferric thiooyanate, decomposition by
mercuric chloride, sodium fluoride, nitric acid, 243 ^
or sodium thiosulfate, 217 Fibers, differentiation of animal from
solvate formation with, as test for oxy- vegetable, 484 '
gen, 319 Filter paper, contaminants, 18
test for thiocyanates in presence of drying, 21-22
iodides, 213 impregnated, 17, 19-20
SUBJECT INDEX 539
impregnation with insoluble reagents, Fluorides, boric acid in presence of 259
20 carbonates in presence of, 255
with soluble reagents, 21 etching test for, 207
increase of sensitivity of spot reaction insoluble, detection by zirconium-
by, 6 alizarin teat, 203, 307
mineral constituents, 18 tests for, 307
proper method of using, 1^ interference in alizarin test for zir-
as reaction medium, 1, 8 conium, 154
Schleicher and Sohiill, 19 in anunonium molybdate test for
spot reactions on, 17 phosphoric acid, 251
spraying of reagents on, 21 in chromyl chloride test for hydro-
storage, 19 chloric acid, 193
wanning, 32-33 in p-dimethylaminoazophenylarson- ^
Whatman, 19 ' ic acid test for zirconium, 155
Filter pipet, 35-36 in hydrogen peroxide test for tita-
Filter stick, Emich, 36 nium, 150
Fixing baths, 'qualitative analysis of, 101 in jS-nitroso-a-naphthol test 'for zir-
Flame color test for boric acid, 261 conium, 153
for tin, 88, 307-308 in potassium ferrocyanide test for
Flaws in iron, detection, 461 iron, 122
Flotation processes, 2 in potassium thiocyanate test for
Flour, test for adulteration with gypsum, iron, 124-125
447 in sodium carbonate-phenolphthal-
Fluoboric acid, formation, 203 ein test for carbonic acid, 255
Fluorapatite,. detection of fluorine in, in titanium-malachite green test for
204 tungsten, 96
Fluorescein chloride test for amines, 371 iron in, detection, 437
Fluorescein-potassium bromide paper in mixtures, test for, 283
test for free halogens, 276 in presence of nitrates, 207
Fluorescein test for bromides, 194 of oxalates, 204
for free halogens, 276 of phosphates, 204
for hydrobromic acid, 194 reaction with p-nitrobenzeneazochro-
Fluorescein type of dyes, formation, 360 motropic acid, 258
Fluorescence, 2 sulfates in, test for, 465
of acid amides, 379 zirconium azoarsenate test for, 204
of citrazinic acid, 407 Fluorine, conversion into alkali fluoride
of dialkyl rhodamines,_373 as test for, 312
of dicarboxylic acids, '364-365 in mineral waters, test for, 463
of glucoronic acid, 402 in organic compounds, summary of
of glycolic acid, 405 tests, 506
of lactic acid, 400 in rocks, test for, 463
of malic acid, 400, 402 in solid substances, detection, 203
in morin test for aluminum, 142,452 in water, test for, 477
of primary and secondary aliphatic zirconium-alizarin test for, 202
amines, 376 o-Fluorobenzoic acid, detection of fluo-
of pyrrole derivatives, 378-379 rine in, 313
of saccharin, 487 (3-Fluoronaphthalene, detection of fluo-
of sodium zinc uranyl acetate, 177 rine in, 313
of tartaric acid, 405 Fluorspar, detection of fluorine in, 204
test for aluminum with morin, 142, 452 Fluxes, in fusions, 29
for lactic acid, 401 Foods, copper in, detection, 427
for niobium, 159 formic acid in, detection, 486
for uranium, 159 impurities in, tests for, 486
of tetra-alkyl rhodamines, 374 spot reactions in analysis of, 425
Fluorescent reaction products, quartz spot reactions as purity tests for, 3
lamp for observing, 40 Forceps, 14
540 SUBJECT INDEX
Foreign materials, effect on reactions, 7 test for aldehydes, 348

Forensic investigations, spot reactions for hydrobromic acid, 196
to secure evidence for, 3 p-Puchsin, action 1 of sulfurous acid on,
Formaldehyde, chromotropio acid test 234 ,1
for, 395, 397 p-Puchsinleucosulfpnic acid, formation,
conversion of glycoeoU to, 384 234
fluorescence with o-hydroxydiphenyl, Fucbsite, chromium in, 439
401 Fuels, motor, lead tetraethyl in, test for,
identification, 334,340,342,345,347 483
and plumbite solution as test for car- Fumes, removal, 28
bon disulfide, 418 Furfural, hydrolysis to, as test for carbo-
reaction with alkali cyanides, 76 hydrates, 410
with fuchsin-sulfurous acid, 327 identification, 334, 340, 344-345, 360
with p-hydroxydiphenyl, 401 reaction with chromotropio acid, 395
with sulfites, 235 with formaldehyde, 396
with sulfuric and gallic acids, 405 as reagent for aromatic amines, 383
and silver nitrate test for ammonia, 185 Furfural bisulfite, identification, 348
summary of tests, 509 Furnaces, electrically heated, 28
test for formic acid, 397 Furs, detection of p-phenylenediamine
for methyl alcohol, 396 in, 416
Formic acid, conversion to formaldehyde Fu8ion(s), 26, 29
as test for, 397 apparatus for, 29
in foodstuffs, test for, 486 oxidizing, 29
in vinegar, detection, 486 G
Franckeite, tin in, 432
Free carbon, test by oxidation, 281 Galena, free sulfur in, detection, 483
FrSfe elements, tests for, 272 lead in, detection, 429
Free halogens, fluorescein test for, 276 Gallic acid and - sulfuric acid test for ,
starch-potassium iodide test for, 276 tartaric acid, 405
tests for, 276 Gallium, ferrocyanide and manganese
Free hydrochloric acid, test for, 239 salts test for, 164
Free metals and alloys, ferric ferri- summary of tests, 498
cyanide test for, 273 Gallium salts, reaction with anthra-
phosphomolybdic acid test for, 273 quinone-1-azo^-dimethylaniline hy-
tests-for, 272 drochloride, 89
Free phosphoric acid, test for, 239 reaction with morin, 142
Free selenium, reaction with thallous Gallocyanine, reaction with zirconium,
sulfide paper, 277, 279-280 157
test by addition to thallous sulfide, 279 as reagent for lead hydroxide, 58
by formation of silver aelenide, 280 Gaseous reagents, 22
Free sulfur, test by conversion to thio- Gases, action and liberation, 29^
cyanate, 278 apparatus for detection, 30-32
by conversion to thiosulfate, 279 as auxiliary reagents, 29
by formation of thallium polysulfide, reaction with reagent solution or rea-
277 gent paper, 8 '
Free sulfuric acid, test for, 239
Fructose, reaction with chromotropio Gas generator, 29
acid, 895 Gas-purifying masses, detection of free
with formaldehyde, 396 sulfur in, 482
Fruit juices, detection of ascorbic acid Gelatin gels as medium for spot tests,
in, 420 6,8 ^
Fuchsin, reaction with sulfites, 234 Gelatin paper fDr_imprinting procedure,
and sulfurous acid reaction with alde- 457
hydes, 339, 384 Germanic acid, reaction with hydroxy-
with formaldehyde, 327 anthraquinones, 91
SUBJECT INDIIX 641
reaction with molybdates in acid solu- reaction with |3,p'-dinaphthol, 406

tion, 250 with sulfuric and gallic acids, 406
with p-nitrobenzeneazochromo- summary of tests, 509
tropic acid, 91-9^ Glycerides, test for, 408
Germanium, ammonium molybdate and Glycerol, catalysis of decomposition of
benzidine test for, 90 oxalic acid as test for, 409
in presence of arsenic, 90-91 combination of germanic acid with, 90
of iron and of tin, 90 conversion to acrolein as test for, 408,
of selenium, 90-91 486,486
summary of tests, 498 to formaldehyde and formic acid,
teat by formation of a complex with 3%
mannite, 89 identification, 328, 486
Germanomolybdic acid, formation, 90, reaction with formaldehyde, 396
Glass, alkali in, detection, 449 Glyceryl oleate, identification, 360
chemical resistance of, test for, 449 GlycocoU, conversion to formaldehyde,
containing bases, identification, 448 384
differentiation as to alkali resistance, identification, 358, 384
470 ' GlycocoU ester, identification and fluo-
equipment for blowing and working, rescence, 376
40 GlycocoU ethyl ester hydrochloride,
as medium for spot tests, 8 identification, 360, 370
orienting tests, 448 Glycol, conversion to formaldehyde and
rods for inixing powders, 13 formic acid, 326
for taking drops, 14 Glycolic acid, conversion to, as test for
sintered, tests on, 6 oxalic acid, 402-403
. spot plates, 23-24 2,7-dihydroxynaphthalene and sul-
stirrer, 24, 26 furic acid test for, 399, 403
tin in, detection, 308 fluorescence with 0-naphthol and sul-
titanium in, test for, 440 furic acid, 405
vessels, spot reactions in, 23 in presence of citric acid, 400
vulnerability to attack by alkalis, test reaction with /3,j3'^linaphthol, 406
for, 469 with sulfuric and gallic acids, 405
Gliadin, detection, 413 summary of tests, 509
Gluconic acid, reaction with p,/S'-dinaph- Glyoxal, identification, 342
thol, 406 Glyoxylic acid, conversion to glycolic
Glucosazone, identification, 388 acid, 403
Glucose, combination of germanic acid reaction with fl,/3'-dinaphthol, 406
with, 90 with sulfuric and gallic acids, 405
identification, 328, 334, 410^11 Gneiss, detection of phosphates in, 472
interference with formaldehyde test Gold, benzidine test for, 100
for formic acid, 397 copper in presence of, 426
/9-Glucosidases, detection, 423 p-dimethylaminobenzylidene rhoda-
Glucuronic acid, reaction with naphtho- nine reaction for, 43, 100
resorcinol, 402 distinction from copper, 101
with p,/5'-dinaphthol, 406 interference in dithizone test for
Glucuronic acid phenylhydrazone, iden- mercury, 60
tification, 388 palladium in presence of, test for, 104
Glutaconic aldehyde, conversion to, as reduction of gold salts to metallic, 100
test for pyridine, 414 silver in presence of, 45
test for primary aromatic amines, summary of tests, 498
378 test with reducing substance, 101
Glyceraldehyde, identification, 345, 347 Gold alloys, qualitative analysis of, 101
reaction with chromotrîc acid, 395 Gold chloride, reaction with rhodamine
Glyceric acid, naphthoresorcinol and B, 86
sulfuric acid test for, 401 test for arsenic hydride, 81
542 SUBJECT INDEX
Gold platinibromide, reaction with rubid- silver carbonate and phenolphthalein

ium salts, 182 preliminary test for, 193
test for cesium, 182 Halogen hydracids, detection of hydra-
Gold salts, interference in test for palla- zoic acid in presence of, 215
dium, 106 preliminary tesi for, 193
interference in o-tolidine test for cop- Halogens, free, tests for, 276
per, 67 summary, 505
reaction with cacotheline, 52 in organic compounds, 311
with p-dimethylaminoazophenylar- Beilstein test for, 311
sonic acid, 155 summary of tests, 506
with p-dimethylaminobenzylidine test by conversion into copper halide,
rhodanine, 107 311
reduction to gold by hypophosphorous Hardness, of metals and alloys, 272
acid, 266 of water, determination, 478
to metallic gold, 100 HCl-phenetidine and hydrogen peroxide
by stannous chloride, 104 test for copper, 74
Graduated cylinder, 11 Heatable spot plate, 40
Granite, phosphates in, detection, 472 Heating of small volumes of liquid, 33
Granitic gneiss, phosphates in, detection, of solutions, 32-33
472 Heliantbin, identification, 368
Graphite, carbon in, 308 Heliotropin, identification, 343, 350
Graphitic carbon, detection, 281 Heller and Krumholz method for analy-
Griess reaction of nitrites, 189, 247 sis of mixtures, 287
Grinding and mixing solids, 12 Heller method, for analysis of alloys, 291
Grooved magiiesia for ignitions, 28 of water, 476
Group arrangement of metals, 41 Hemin, oxidation of luminol in presence
Group separations, 3 of, as test for hydrogen peroxide, 271
of metals, 41 Hemipinic acid, identification, 364
Gum arable, identification, 328, 411 Hemipinic anhydride, identification, 361
Gutzeit procedure, in analysis of mix- Hemoglobin, detection, 413, 424
tures, 283 Hepar reaction for sulfate in hydrofluoric
test for arsenic, 80, 83 acid, 466
Gypsum, as adulterant of flour, test for, Heptyl aldehyde, reaction with p-hy-
447 droxydiphenyl, 401
distinction from anhydrite, 447 Heptylamine, identification, 370
in gas-detection apparatus, 30 Hexamethylene tetramine, identifica-
identification, 445 tion, 348
in a mixture of barium and calcium Hexanitrodiphenylamine, see Dipicryl-
sulfates, 446-447 amine
Hide powder, identification^ 414
H Holder for pipets and glass rods; 16
Hot air apparatus, 40
H-acid, identification, 368, 377 Hydrated metallic ions, reactions as
nitrogen in, detection, 316 basis for spot analysis, 41
sulfur in, detection, 313, 317 Hydrazine(s), aliphatic and aromatic,
sulfur and nitrogen in, detection, 317 test with soditun pentacyanoam-
Hair dyes, detection of p-phenyjene- mine ferroate^385
diamine in, 416 in presence of hydroxylamine, 187-190
Halide ions, ferrocyanides in presence reaction with benzaldehyde, 186
of, 216 salicylaldehyde test for, 186
Halides, interference in silver ion cataly- summary of tests, 498, 50J
sis of diphenylcarbazide test for tests for, 385-388
chromium, 129-130 Hydrazine sulfate, identification and
reaction with cobalt salts in presence fluorescence, 376
of acetone, 215 Hydrazobenzene, identification, 37S
with potassium permanganate, 214 Hydrazoic acid as reducing agent of
SUBJECT INDEX 543
permanganate in test for chromate, and sulfuric acid for decomposing sili-
262 cates, 29
removal of nitrites by, 246 summary of tests, 503
summary of tests, 602 test by conversion into silicomolybdic
test by formation of silver or iron acid, 206
azide, 215 zirconium-alizarin solution test for,
Hydrazones, formation with azo dye- 202
stuffs as'test for hydrazines, 385 zirconium azoarsenate test for, 204
sunmiary of tests, 607 Hydrogen, condensation, detection of
tests for, 388 platinum metals by, 101
Hydrindone (a), identification, 337 in organic compounds, presence, 311
Hydriodic acid, for converting insoluble Hydrogen chloride group, tests for cat-
compounds into water-soluble io- ions of, 287
dides, 300 Hydrogen-flame luminescence test for
palladous chloride test for, 197 antimony, 86
reaction with tellurous acid, 263 for bismuth, 62
summary of tests, 502 Hydrogen-ion concentration, determina-
test for selenious acid, 263 tion, 474
Hydrobromic acid, fluorescein test for, indicators for, 474, 476
194 Hydrogen peroxide, and ammonia test
fuchsin test for, 196 for cerium, 160
. permolybdate and a-naphthoflavone auric chloride test for, 271
test for, 196 discharge of chromate-diphenylcarba-
and phosphomolybdic acid test for zide reaction by, 271
. thallium, 120 ferric-ferricyanide test for, 269
potassium permanganate test for, 197 and HCl-phenetidine test for copper,
as reagent for copper, 74 74
summary of tests, 503 interference in ammonium molybdate
test by oxidiation to bromine, 194 test for phosphoric acid, 251
Hydrocarbons, esters in mixtures of, lead sulfide test for, 268
tests for, 485 and manganese sulfate test for am-
unsaturated, oxidation to a,0-unsat- monia, 185
urated ketones by selenious acid, 335 and nitric acid test for lead peroxide,
Hydrochloric acid, copper in presence of, 305
detection of, 66 for manganese dioxide, 305
formation of chromyl chloride as test reaction with alkali thiocyanates, 271
for, 191 with cerium salts, 150
free, test for, 239 with chromates, 150
summary of tests, 603 with iron salts, 160
volatilization test for, with formation with molybdates, 150
of silver chloride, 193 with o-tolidine solution, 271
Hydrocyanic acid, copper aeetate-bei^- with vanadates, 150
dine acetate test for, 208, 317 reduction of chromates by, 271
copper sulfide test for, 209 of nickel oxides as test for, 269
formation, 281 summary of tests, 503
of thiocyanate as test for, 209 test by catalyzed oxidation of phenol-
summary of tests, 503 phthalin, 270
Hydroferricyanic acid, see also Ferri- by oxidizing luminol in presence of
cyanic acid hemin, 271
summary of tests, 503 with potassium cerous carbonate,
Hydroferrocyanic acid, see also Ferro- 271
cyanic acid for titanium, 15(J, 304
summary of tests, 503 for vanadium, 97
Hydrofluoric acid, etching test for, 207 Hydrogen phosphide, reaction with sil-
sulfates in, detection, 465 ver nitrate, 81
544 SUBJECT INDBX
Hydrogen sulfide, carbon disulfide in Hydroxylamine hydrochloride, identifi-

presence of, 418-419, 484 cation and fluorescence, 376.
catalysis of the iodine-azide reaction 8-Hydroxynaphthylhydrazine-3,6-di8ul-
as test for, 227 fonic acid, identification, 386
group, tests for, 42 o-Hydroxyquinoline,| identification, 332
tests for cations of, 287 8-Hydroxyquinoline test for copper, 73
interference in silicomolybdic acid test for vanadium, 100
for fluorides, 206-207 8-Hydroxyquinoline-7-iodo-5-sulfonic
paper test for antimony and cadmium acid test for iron, 124
in minerals, 463 a-Hydroxysulfonic acids, formation, 333
for precipitating sulfides, 22 Hsrpohalogenites, reaction with benzi-
reaction with cacotheline, 87 dine, 242
with silver nitrate, 81 Hypophoaphorous acid, reduction of
sodiiun nitroprusside test for, 226 metallic salts by, 266
and sodium pentacyanoammine fer- test for iodic acid, 223
roate test for aldehydes, 349 for telluric and tellurous acida, 286
in spot test analysis, 29-30
in water, detection, 473, 478
Hydroquinone, identification, 331 Ignition, 26, 28
flydroxamic acid(s), conversion of car- apparatus for, 40
boxylic acids to, 356 and evaporation residues, testing, 479
identification tests for, 353 as preliminary operation, 8
and oximes, identification tests for, 353 Ignition tube, heating of sample in, 295
reaction with ferric chloride, 358-359 Imbibition qualities of filter paper, 18
summary of tests, 508 Impregnated filter paper, apparatus for
tests for, 352 drying, 40
Hydroxyanthraquinones, reaction with Impregnation, of filter papers, 21-22
boric and germanic acids, 91 homogeneous, 21
test for boric acid, 257 Imprinting procedure.for detecting he-
o-Hydroxybenzaldehyde, see Salicylalde- terogeneities in metals, minerals,
hyde etc., 457
0-, m-, p-Hydroxybenzaldehydes, iden- Indamine dye, oxidation to, as test for
tification, 331, 334, 340, 350 p-phenylenediamine, 415
p-Hydroxybenzoic acid, identification, Indicator papera, stability, 23
331 Indicators, for measuring hydrogen-ion
a-Hydroxybutyric acid, reaction with p- concentration, 474, 476
hydroxydiphenyl, ^ 1 "protein error" of, 413
m-Hydroxycinnamic acid, identification, Indigo, conversion into, as test for
332 methyl ketones, 351^ ^ ^ ..^
Hydroxydiphenyl and sulfuric acid tests formation, as test for acetic acid,~398
for lactic acid, 4 0 0 ^ 1 Indium, alizarin test for, 162-163
o-Hydroxydiphenyl and sulfuric acid test in presence of aluminum, 163
for pyruvic acid, 402 of anmionium' sulfide group of me-
Hydroxylamine, ammonia test for, 190 tals, 163 ~
diacetylinonoxime and nickel salts, of cesium, 163 ,
test for, 186 of chromium, 164
in presence of hydrazine, 187-190 of cobalt, iron, manganese, nickel,
as reagent for carboxylic acid esters and zinc, 163-1^
and anhydrides, 358-359 quinalizarin test for, .162-163
salicylaldehyde and copper salts, tebt - summary of testa, 498 /
for, 187 Indole, fluoresceiy!e7379
summary of tests, 498 identification, 379, 391
test by conversion to nitrous acid, 189 Induced reactions, 2
for oximes, 352 Inks, classification, 452
SUBJECT INDEX 54
Ink writing, chemical identification, 452 with cobalt salts, in presence of
detennination of age, 452, 454 acetone, 215
Inorganic materials, and organic (basic) ^ with potassium permanganate, 214
reaction with mineral acids, detec- reduction of iodine to, 82
tion, 479 silver nitrate test for, 201
reaction with organic reagents, 2 test by oxidation to free iodine, 198
solid products, detection of free sulfur for small amounts of, 199, 201
in, 482 thallium nitrate test for, 202
Insecticides, detection of free sulfur in, thiocyanate in presence of, 212, 214-
482 215
"Insoluble residue,'' detection of mer- in water, test for, 477
cury in, 228 Iodine, adsorption on magnesitim hy-
detection of sulfides in, 228-2^ droxide, 173
identification of constituents, 300 and lanthanum nitrate test for acetic
Insoluble sulfates, identification, 301 acid, 397
Insoluble sulfides, identification, 301 oxidation of pyrogallol by, 224
Intermetallic mercury compounds, de- reaction with arsenious acid, 82
tection, 275 reduction to iodide, 82
Inulase, detection, 422 release on starch filter paper as test for
Invertase, detection, 422 nitrous acid, 249
lodates, oxidation of pyrogallol by, 224 test for iodides by oxidation to, 198
reaction with alkali thiocyanates, 223 lodine-azide reaction, catalysis of, B&
with diphenylamine, 244 test for alkaline earth sulfates, 238
with ferrous sulfate and sulfuric for carbon disulfide, 417
acid, 243 for detecting sulfide corrosion in
starch-iodine reaction for detecting, machinery metal, 469
223 for explosives, 488
test for iodides by conversion to, 199 for hydrogen sulfide, 227
Iodic acid, hypophosphorous acid test for insbluble sulfates, 238
for, 223 for insoluble sulfides, 228-229
potassium thiocyanate test for, 223 for lead sulfate, 238-239
pyrogallol test for, 224 for soluble sulfides, 228
summary of tests, 803 for sulfates, 301
Iodide (s), bromides in, detection, 196 for sulfides, 227, ^ 7 , 301, 313, 466
bromides in presence of, 195 for sulfide sulfur in charcoal and dyes,
catalytic reduction of cerium salts as 481
test for, 200 ^ in rooks, 464
conversion intQ iodates as test for, kw for sulfur in carbon disulfide, ether,
cyanidesHn presence of, 209 and organic solvents, 480
ferrocyanides in presence of, 217-218 for thiocyanates, 227-228
interference in chromyl chloride test for thiocyanic acid, 212
for hydrochloric acid, 192 for thioketones and mercaptans, 353
in ferrous sulfate-sulfuric acid test for thiosulfates, 227-228, 279
for nitric acid, 243 for thiosulfuric acid, 240
in hydrogen peroxide test for vana- Iodine compounds, reaction with copper
dium, 98 oxide, 311
in oxidation test for manganese, 133 lodoeoein, formation, 19S
in silieomolybdic acid test for halogen in, detection, 312
fluorides, 207 test for basic oxides in glass, 448
in mixtures, test for, 283 Ions containing cyanogen radical, capil-
palladous chloride as reagent for, 197, lary detection, 221
Iridium, detection by condensation of
202 hydrogen on, 101-102
in presence of bromides, 202 Iridium saltb, reaction with anthra-
of chlorides, 201-202 quinone-l-azo-4-dimethylaniUae hy-
reaction with arsenic acid, 82 drochloride, 89
546 SUBJECT INDEX
Iron in alloys, test for, 292-293 Iron azide, formation, as test for hydra-
in alumina, detection, 303^ 438 zoic acid, 215!
aluminum in presence of, 145-146 Iron chloride test for ferrocyanic acid,
beryllium in presence of aluminum 216 j
and, 148 Iron and cobalt salts, nickel in presence
cerium in presence of, 161 of, 114, 116
cobalt in presence of, 110-111, 113 Iron (II) dimethylglyoxime test for
detection by zinc ferrocyanide paper, vanadium, 98
20 Iron gallate inks, composition, 452
dimethylglyoxime test for, 125 Iron hydroxamate formation as test for
a,Q:'-dipyridyl test for, 122, 438 carboxylic acids, 355
disodium-1,2-dihy droxy benzene-3,5- Iron periodate complex test for lithium,
disulfonate test for, 126 180
dithizone test for zinc in presence of, Iron salts, (II) in presence of (III), de-
140 tection, 123
in fluorides, test for, 437 interference in ammonium, mercury
germanium in presence of, 90 thiocyanate test for copper, 73
8-hydroxyquinoline-7-iodo-5-sulfomc in cacotheline test for vanadium, 99
acid test for, 124 in test for palladium, 106
indium in presence of, 163-164 in o-tolidine test for copper, 67
in ink writing, test for, 453 reaction with alizarin, 144
interference in cerium salt reduction with ammoniacal silver nitrate, 160
test for iodides, 201 with chromotropic acid, 152
in fluorescence test for uranium, 159 with hydrogen peroxide, 150
in phosphomolybdic acid test for 'with pyrocatechol, 151
vanadium, 100 with 1,2,7-trihydroxyanthraqui-
lake formation with alizarin, 144 none, 89
magnesium in presence of, 175 reduction of phosphomolybdates by,
manganese in presence of, 135 120
in mercury salts, test for, 438 as solvent for calcium fluoride, 203
in minerals, test with ferrocyanide Iron sulfate as reagent for tellurites and
paper, 463 tellurates, 268
in mixtures, test for, 286, 289-290 Iron sulfinate, precipitation, as test for
nickel in presence of, 115, 118 sulfinate, 363
2-nitroso-l-naphthol-4-sulfonic acid Isatin potassium sulfonate, detection of
test for, 74, 128 sulfur in, 313
phosphorus segregations in, detection, Isoamyl alcohol, detection, 326
460 Isobutyl a,lcohol, detection, 326
potassium ferrocyanide test for, 122 Isobutylamine, identification, 370
potassium thiocyanate test for, 124 Isonitrosoacetophenone, identification,
in potassium thiocyanate test for 322, 353
molybdenum, 92 Isonitrosoacetylacetone, identification,
in presence of chromium, cobalt, cop- 322
per, and nickel, detection, 126 Isonitrosomethyl ethyl ketone, identifi-
in pyrolusite, test for, 438 cation,. 353
reaction with curcumin, 256
with potassium ferrocyanide, 138
solubility in nonoxidizing acids, 272
sulfur segregations in, detection, 458 Jena glass, alkali in, 449
in tanned leather, test for, 452 K
thiocyanate reaction for, 212
thioglycolic acid test for, 127-128 K-acid, identification, 382
titanium in presence of, 153 Kairine test-foFarsenic, 83
uranium in presence of, 157-158 Kaolin, detection of titanium in, 440
in water, test for, 477 Kavalier glass, alkali in, 449
SUBJECT INDEX 547
Ketohexoses, test for, with stannous in pharmaceutical preparations, detec-
chloride, sulfuric acid, and urea, 410 tion, 432
Ketones, interference in o-dianisidine in presence of other metals, detection,
test for aldehydes, 340 57
Ketoximes, detection, 352 reaction with potassium iodide, 119
Kjeldahl method, 311 sodium rhodizonate test for, 56, 306,
Kolthoff's method of water'analysis, 476 428
Krumholz method of analysis of mix- solubility in nonoxidizing acids, 272
tures, 289 in sulfuric acid, detection, 430-431
thallium in presence of, test for, 119
in tin platings and enamels, 427
Labeling of bottles, 10 in water, detection, 430
Lactic acid, fluorescence test with -hy- in zinc dross or zinc oxide, detection,
droxy diphenyl, 401 429
hydroxydiphenyl and sulfuric acid zinc in presence of, 142
tests for, 400-401 Lead chloride, silver in a mixture of
reaction with 2,7-dihydroxynaphtha- mercurous and silver chlorides and,
lene, 400 44
summary of tests, 509 Lead chromate in insoluble residue, 305
Lactones, reaction with hydroxylamine, Lead glass, alkali in, 449
358 Lead hydroxide, detection by gallo-
Lactose, identification, 328, 334, 411 cyanine, 58
reaction with formaldehyde, 396. Lead nitrate, zinc in presence of, 141
Lactosyl fluoride, detection of fluorine Lead oxides, detection of free metal in,
in, 313 450
Lanthanum nitrate and iodine test for Lead peroxide, conversion of lead salts
acetic acid, 397 ^ to, 55
Lanthanum salts, lake formation with formation of benzidine blue by, 55
quinalizarin, 148 hydrogen peroxide-nitric acid test for,
reaction with quinalizarin, 172 305
Lassaigne's test for nitrogen, 316 in insoluble residue, 305
for sulfur, 313 and manganese dioxide, distinction,
Lateral spotting, 36 306 ^
Lead, in alkali salts, detection, 430-431 Lead salts, in alkaline stannite test for
in alloys, test for, 292-293, 428. bismuth, 60
benzidine test for, 55 ammonia in presence of, 185
in bismuth compounds, test for, 432 cadmium in presence of, detection, 75
bismuth in presence of, detection, 59- carminic acid as reagent for, 59
60 conversion to lead peroxide, 65
cadmium stannoiodide test for, 58 formation of benzidine blue by, 131
copper in presence of, detection, 68 interference in kairine test for arsenic,
dithizone test for, 57 83
for zinc in presence of, 140 reaction with benzidine, 131, 305
magnesium in presence of, 175 with potassium chromium thio-
in metals, detection, 428 cyanate, 62
in minerals, ores, and pigments, detec- Lead sulfate, induced precipitation of,
tion, 429 as test for barium, 167
in minerals, test with potassium chro- in insoluble residue, sodium rhodi-
mate paper, 463 zonate test for, 301-302
in mixtures, tests for, 285, 288, 291 iodine-azide reaction for, 238-239
in neutral solution, detection by gallo- in presence of alkaline earth sulfates,
cyanine, 58 301
in oils, pigments, and varniahea, detec- reduction to sulfide, 238
tion, 429 Lead sulfide paper, production, 22-23
548 SUBJECT INDEX
Lead sulfide test for hydrogen peroxide, Magnesia spoon, heating of sample on,
268 295 i
Lead tetraethyl in motor fuel, test for, Magnesite, caustic, calcite and dolomite
484 in, 444 j
Leather, oxalic acid in, test for, 485 distinction from ibraunerite, 442
test of, for tanning minerals, 451 from dolomite, 442
Leucylglycine, identification, 370 lime in, detection, 444
Leucylglycylglycine, identification, 370 Magnesium, alkali hypoiodite test for,
Levulinic acid phenylhydrazone, identi- 171
fication, 388 aluminum in presence of, quinalizarin
Levulose, identification, 328, 334, 410-411 test tor, 147
Liberation of gases (vapors), 29 in asbestos and talc, 440
Liebermann reaction for phenols, 329 beryllium in presence of, 148-149
Liebermann's reagent, 331-332 in chalk, detection, 443
Lime, ignition with, as test for phos- as contaminant of filter paper, 18
phorus, 317 fluorescence of sodium zinc uranyl ace-
in magnesite, detection, 444 tate as test for, 177
test for arsenic in organic compounds, in mixtures, test for, 287
318 p-nitrobenzeneazo-ot-naphthol test for,
for nitrogen in organic compounds,, 173,440
315 p-nitrobenzeneazoresorcinol test for,
Limit of identification, defined, 4 173
Lipase, detection, 422-423 phenolphthalein paper test for, 176
Liquid and solid phases, separation, 34 in presence of other metals, tests for,
Liquors, glycerol in, detection, 486 175-176
Litharge, detection of free metal in, 450 quinalizarin test for, 148-149, 172
Lithium, complex iron periodate test in silicate rocks, detection, 440
for, 180 summary of tests, 499
in presence of cesium, potassium, in tap water, detection, 174
rubidium, and sodium, 181 Titan yellow test for, 173,176
of other alkali chlorides, 181 zinc uranyl acetate test for, 176
summary of tests, 499 Magnesium compounds, reaction with
Lithium salts, interference in zinc diphenylcarbazide, 442
uranyl acetate test for sodium, 176 Magnesium hydroxide, adsorption of
reaction with sodium cobaltinitrite, iodine on, 173
178 Magnesium hypoiodite as reagent for re-
Litmus, as indicator of hydrogen-ion ducing sugars, 409
concentration, 474 Magnesium salts, interference in di-
paper test for ammonia, 184 picrylamine test for thallium, 121
Logwood inks, composition, 453 interference in zinc uranyl acetate test
Luminescence test for antimony, 62,86 for sodium, 176 ^ * _
for bismuth, 62 reaction with ammonimn^ ferrocy-
for manganese, 62 anide, 170
for tin, 307-308 with p-nitrobenzeneazoorcinol, 149
Luminol, oxidation in presence of hemin, Magnesium ^sulfate, interference in
starch-iodine reaction, 198
as test for hydrogen peroxide, 271 interference in titanium-malachite
Luster of metals and alloys, 272 green test for tungsten, 96
Magnetic properties of metals and alloys,
M 272
Magnifying glass, 14, 40
Macrobalance, analytical, 40 Malachite green, decolorization of, as
Macrochemical tests, choice of, 41 test for sulfurous acid, 234
Macrodistillation apparatus, 40 reaction witlralfiehydes, 339
Magnesia, in gas-detection apparatus, 30 with cobaltous hydroxide, 162
as medium for spot tests, 6,25,28-29 with numganese hydroxide, 182
SUBJECT INDEX 549
with silver oxide, 162 in insoluble residue, 305
with thallium hydroxide, 162 and lead peroxide, distinction, 306
test for cerium, 162 reduction of, as test for ascorbic acid,
Malachite green-titanium reaction, ca 420
talysis of, as test for tungsten, 95-96 Manganese hydroxide, conversion into
Malic acid, in fruit vinegar, test'for, hydrated manganese dioxide, 135'
486 reaction with malachite green, 162
identification, 364 Manganese nitrate and alkali test for
0-naphthol and sulfuric acid test for, silver, 42
405 Manganese salts, catalytic reduction of,
reaction with 2.7-dihydroxynaphtha- as test for silver, 47
iene, 400 cerium in presence of, 161
with /3,/?'-dinaphthol, 406 and ferroeyanide test for galliimi, 164
with naphthoresorcinol, 402 interference in benzidine test for lead,
Malonic acid semialdehydes, formation, in cerium salt reduction test for
362 iodides, 201
Malonic ester, identification, 332, 390 in fluorescence test for uranium, 169
Maltose, identification, 328 in o-tolidine test for copper, 67
Mandelonitrile, identification, 348 in zinc uranyl acetate test for so-
Manganese, in alloys, test for, 137, 292- dium, 176
293 oxidation to permanganates, 130
aluminum in presence of, 145 presence in 1,2-diaminoan thraquinone-
benzidine test for, 134, 222, 305 3-sulfonic acid test for copper, 70
chromium in preaenc^&f, 128, 131 reaction with alkali hypobromites, 133
dithizone test for zinc in presence of, with ammoniacal silver salts, 160
140 with benzidine, 120, 161
hydrogen-flame luminescence test for, with diphenylcarbazide, 128
62 with persuifates, 225
indium in presence of, 163-164 and tetrabase test for periodic acid,
lake formation with alizarin, 144 224
magnesium in presence of, 175 Manganese sulfate, and hydrogen perox-
in mixtures, tests for, K6, 289-290, 292 ide test for ammonia, 185
nickel in presence of, 115-116 reaction with chlorates, 221
periodate and tetrabase test for, 134 and silver nitrate test for ammonia,
in presence of cerium, test for, 136 184
of cobalt, 133-135 cine in presence of, 141
of copper, test for, 136 ManganouB salts, reaction with alkali
of iron, test for, 135 periodates, 134, 224
of nickel, 133-134 Manganous sulfate, and phosphoric acid
of silver, test for, 136 test for chloric acid, 221
of small amounts of silver salts, 132 for periodic acid, 224
of thallium, test for, 136 reaction with chlorates, periodates,
reaction with potassium ferroeyanide, and persuifates, 224 ^
138 and sulfuric acid test for bromic acid,
silver ammine salts test for, 137 222
in special steels, test for, 137 Mannite, combination with s^rmanic
summary of tests, ^ 9 acid, 90
test by catalytic oxidation to perman- test for germanium, 89
ganate, 132-133 Mannitol, conversion to formaldehyde
titanium in presence of, 153 and formic acid, 326
in water, test for, 477 identification, 328
Manganese dioxide, in boric acid, detec- Mannose, identification, 328
tion, 260 Marcasite, detection of free sulfur in, 483
hydrogen peroxide-nitric acid test for, Melting-point apparatus, 40
305
560 SUBJECT INDEX
Mercaptans, iodine-azide reaction test dropper, 17

for, 353 drops of uniform size, delivery, 17
summary of tests, SOS electrolytic precipitation, 63
and thioketonea, identification tests in "insoluble residue," detection, 228
for, 356-357 in mixtures, tests for, 285, 288, 290
Mercuric chloride, decomposition of in organic compounds, 311
ferric thiocyanate by, 217 precipitation by antimony sulfide
diphenylcarbazone test for, 49 paper, 20
interference in tests for free metals and in presence of chlorides, detection, 51
alloys, 273 of copper, detection, 52
in wood preservatives, detection, 450 of free acids, detection, 51
Mercuric cyanide, and diphenylcar- of silver, dithizone test for, 50
bazide test for palladium, 107 reaction with diphenylcarbazide, 304
starch-iodine test for, 211 with potassium iodide, 119
summary of tests, 504 . with thiourea, 265
test by conversion into mercuric iodide silver in presence of, detection, 44
and cyanide ion, 211 solubility in nonoxidizing acids, 272
by formation of cyanogen iodide, 211 stannous chloride and aniline as rea-
by precipitation with silver nitrate gents for, 60
in alkaline solution, 210 summary of tests, 499
Mercuric iodide and cyanide ion con- test by activation of aluminum, 53
version test for mercuric cyanide, by reduction of palladium chloride,
211 274
Mercuric nitrate and nitrous acid test thallium in presence of, test for, 119
for phenols, 330 Vapor, selenium sulfide as reagent for,
Mercuric nitrate test for calcium sulfate, 275
445 test by reduction of palladium chlo-
Mercuric salts, cuprous iodide test for, 55 ride, 274
detection by chromotropic acid, 55 Mercury chloride, reaction with rhoda-
interference in cerium salt reduction mine B, 86
test for iodides, 201 Mercury salts, ammonia in presence of,
reaction with alkali and manganese 185
salts, 42 cadmium in presence of, 75
Mercurous chloride, silver in a mixture interference in dithizone test for zinc,
of lead and silver fehlorides and, 44 139
test for gold, 101 in kairine test for arsenic, 83
Mercurous salts, detection by chromo- in potassium thiocyanate test for
tropic acid, 55 iron, 125
reaction with alkalis, 42 for molybdenum, 92
reduction of phosphomolybdates by, in silver nitrate test for arsenic
120 hydride, 81
Mercury, arsenic in presence of, detec- in test for palladium, 106
tion, 79 in o-tolidine test for copper, 67
bismuth in presence of, detection, in zinc uranyl acetate test for so-
59-61 dium, 176
catalytic acceleration of the reduction iron in, detection, 438
of tin salts as test for, 52 reaction with anthraquinone-l-azo-4-
chromium in presence of, detection, 130 dimethylaniline hydrochloride, 89
copper in presence of, detection, 68 with chromotropic acid, 162
derivatives, organic, 274 i with p-dimethylaminobenzylidene
detection in acid solution, 64 rhodanine, 107
in neutral solution, 54 with diphenylcarbifzide, 130
p-dimethylaminobenzylidene ,rhoda- with potassium chromium thiocya-
nine testfor, 43, 51, 100 nate, 62
diphenylcarbazone test for, 48 reduction by stannites, 266
dithizone test for, 49 by stannous chloride, 79
SUBJECT INDEX 551
Mercury sulfides, detection by sodium flame test for boric acid, 261
azide, 229 in presence of ethyl alcohol, test for,
Mesoxalic acid, reaction with |3,|3'-di- 396
naphthol, 406 summary of tests, 509
Metaldehyde, fluorescence with o-hy- Methylamine hydrochloride, identifica-
droxydiphenyl, 401 tion and fluorescence, 376
reaction with p-hydroxydiphenyl, 400 Methyl borate and alkali fluoride test for
Metallic ions, interference in titanium- boric acid, 259
malachite green test for tungsten, 96 Methylene blue, solution as reagent for
reaction with a,a'-dipyridyl, 123 reducing sugars, 409
Metallic objects, tin in, detection, 432 test for sulfides, 230
Metallic oxides, heavy, test for, 448 and zinc test for titanium, 152
Metallic salts, detection by spot reac- Methyl ether of salicylaldoxime, identi-
tions, 5 fication, 353
interference in hydrogen peroxide test Methyl ethyl ketone, identification, 334,
for vanadium, 98 336, 352
Metals, ammonium carbonate group, Methylheptanone, identification, 337,
tests for, 165 351-352
ammonium sulfide group, aluminum in Methyl p-hydroxybenzoate, identifica-
presence of, 1 4 3 - ^ tion, 331
indium in presence of, 163 Methyl iodide and sodium 1,2-naphtha-
tests for, 109 quinone-4-sulfonate test for tertiary
apparatus for electrolytic deposition, ring bases, 392
40 Methyl ketone, identification, 351
copper in, developing process for de- summary of tests, 507
tection, 461 test by conversion into indigo, 351
electrodes for electrolytic deposition test with sodium nitroprusside, 349
of traces of, 477 Methyl a-naphthylcarbodithionate, iden-
electrographic test for, 39, 461 tification, 356
free, in oxides, detection, 449 Methyl orange as indicator of hydrogen-
in printed paper, detection, 449-450 ion concentration, 474
reaction with phosphomolybdic acid, Methylphenylhydrazine, identification,
449 386-387
summary of tests, 505 Methyl red as indicator of hydrogen-ion
tests for, 272 concentration, 474, 476
group arrangement, 41 Methyl salicylate, identification, 331,360
group separations, 41 Methyl stearyl ketone, identification, 351
hydrogen sulfide group, acid sulfide 9-Methyl-2,3,7-trihydroxy-6-fluorone as
group, tests for, 79 reagent for antimony, 85
basic sulfide group, tests for, 42 Methylxanthic methyl ester, identifica-
imprinting and developing procedure tion, 357
for detecting heterogeneities in, 457 Michler's ketone, identification, 378
lead in, detection, 428 Microanalysis, 4-5
phosphorus segregations in, test for, Microbalance, 40
460 Microbeakers, support for, 33
plated, test for zinc in, 437 Microburets, 17, 40
solution of, 39 Microbumer, 28, 40
sulfur segregations in, test for, 458-469 Microcentrifuge, 37, 40
tests for, 41 tubes, 25, 32, 37-38
Metafltannic acid, detection of antimony support for, 33
oxide or antimonic acid in, 84 Microchemical tests, choice of, 41
in insoluble residue, 307 Microcrucibles, spot reactions in, 25, 32
Methods of spot test analysis, 1 support for, 33
Methyl alcohol, conversion to formalde- Microdesiccator, 26
hyde, as test for, 396 Microdistillation apparatus, 32, 40
detection, 328 Microextraction apparatus, 40
552 SUBJECT INDEX
Microfiltration apparatus, 38-37 Molybdenum, chromium in presence of,

Mjcromortar, 12-13 130 (
Microscope, 40 cochineal fluorescence test for, 94
Microsieve, 13 di-P-naphthylcarbazone test for, 94
Microspatula, 13-14 diphenylcarbazide test for, 94
Microsublimation apparatus, 40 in insoluble residue, 306
Micro test tubes, 25-26 interference in di8odium-l,2-dihy-
cleaning, 26 droxybenzener3,5-disulfonate test
sling for holding, 33 for iron, 126
Millon's reagent for phenols, 330-332 phenylhydrazine test for, 94
Mineral acids, detection of inorganic and potassium thiocyanate and stannous
organic (basic) materials-that react chloride test for, 92
with, 479 potassium xanthate test for, 93, 306,
detection of selenites in solutions of, 433
265 reaction with curcumin, 256
Mineral constituents of filter paper, 18 in steel, detection, 433
Mineral oils, detection of waxes and summary of tests, 500
resine in, 485 in technical materials, detection, 432
Minerals, calcium sulfate in, 447 in titanium-malachite green test for
electrographic test for, 39 tungsten, 96
imprinting and developing procedure in tungsten ores, detection, 433
for detecting heterogeneities in, 467 tungsten in presence of, 95
lead in, detection, 429 zirconium in presence of, 156
phosphates in, detection, 471 Molybdenum blue, constituents, 273
selenium in, test for, 465 formation, 105, 130, 207, 273, 306,
silicic acid in, detection, 470 421, 449
spot reactions in studies of, 3, 425 by antimony salts, 84
tin in, detection, 432 by germanium molybdic acid, 90
titanium in, detection, 440 by phosphomolybdic acid, 260
uranium in, detection, 439 by potassium cuprocyanide, 68
used for leather tanning, test for, 461 by silicomolybdic acid, 206,252
Mineral waters, fluorine in, tests for, 463 by stannous chloride, 87
Minute quantities of gas, apparatus for, by thallium salts, 120
30-31 by vanadium salts, 99
Mixing of reagent and test solution, 24 Molybdenum oxalic acid, formation, 130
Mixtures, analysis of anions in, 298 Molybdenum oxides, interference in
of common metals, detection, 41 cacotheline test for tin, 88
systematic analysis by spot tests, 282 Molybdenimi salts, reaction with anthra-
Molybdates, interference in alizarin test quinone l-azo-4-dimethylaniline hy-
for zirconium, 154 drochloride, 89
interference in cacotheline test for Molybdenum trioxideT'reaction with di-
vanadium, 99 .phenylcarbazide, 306
in diphenylcarbazone test for mer- Monazite, detection of titanium in, 440
ciry, 49 Monochloroacetic acid, identification,
in tests for vanadium, 97-98 358
reaction with p-dimethylaminoazo- Monoethylamine, detection in commer-
phenylarsonic acid, 156 cial triethancdamine, 371
with diphenylamine, 244 Montan wax, reaction with hydroxamic
with diphenylcarbazide, 130, 304 acid, 485
with a,a'-dipyridyl, 94 Morin, reaction with beryllium, gallium,
with ferrous sulfate, 243 scandium, and zinc salts, 142
with hydrogen peroxide, 150 test for aluminum, 142 /
with rhodamine B, 86 in tanned leather, 462
with 1,2,7-trihydroxyanthraqui- Mortars, 12- "^ - -
none, 89 Motor fuels, corrosive sulfur in, 480
reduction by stannous chloride, 86 lead tetraetbyl in, 484
SUBJECT INDEX 553
Mucic acid, identification, 328 indium in presence of, 163-164
Murano glass, alkali in, 449 interference in dimethylglyoxime test
for iron, 125
in ferric-thiosulfate test for copper,
N 64
a-Naphthalenesulfinic acid, identifica- in stannous chloride test for arsenic,
tion, 367 79
Naphthalene-/3-sulfonic acid, identifica- iron in presence of, 125
tion, 368 magnesium in presence of, 175
Naphthalene-4-sulfonic acid-l-azo-5-orin minerals, test with dimethyl-
tho-8-hydroxyquinoline test for pal- glyoxime, 463
ladium, 107 J in mixtures, test for, 286, 289-290
Naphthalic acid, identification, 365 plating, detection, 434
j8-Naphthaquinoline iodomethylate, iden- in presence of cobalt, 114-116, 118, 435
tification, 390 of cobalt and iron salts, 114, 116
a-Naphthoiflavone and permolybdate of copper, 115-116, 118
test for hydrobromic acid, 196 of cyanides, 117
a-Naphthol, identification, 330, 332 of iron, 115, 118
/S-Naphthol, identification, 332 of manganese, 115-116
and sulfuric acid test for malic acid, reaction with potassium ferrocyanide,
405 138
Naphthoresorcinol and sulfuric acid test rubeanic acid test for, 70,112,117
for glyceric acid, 401 summary of tests, 600
tt-Naphthylamine, identification, 377, test for manganese in presence of, 133-
382 134
as reagent for arylhydrazines, arylhy- Nickel carbonyl in benzene solutions, de-
drazones and osazones, 387,389 tection of traces, 484
and selenious acid test for arylhy- Nickel dimethylglyoxime, formation, 186
drazines, 387 precipitation from alkaline cyanide
and sulfanilic acid test for nitrous solutions in presence of formalde-
acid, 248 hyde, 435
/8-Naphthylamine, identification, 377, as reagent for acid-consuming mate-
382, 391 rials, 479
1,8-Naphthylamine, identification, 382 test for alkalis and alkaline earths, 456
a-Naphthyldithiocarboxylic acid methyl for palladium, 106
ester, identification, 360 Nickel dioxime salts, test for aliphatic
1,8-Naphthylenediamine, reaction with 1,2-dioxo compounds by conversion
selenites, 266 to, 334
test for nitrites, 249 Nickel hydroxide, induced oxidation of,
Naphthylhydrazine, identification, 388 as test for sulfurous acid, 233
Neodymium salts, lake formation with reaction with p-nitrobenzeneazoresor-
quinalizarin, 148 cinol, 174
reaction with quinalizarin, 172 Nickel oxides, reduction of, as test for
Nessler reaction, 183-184 hydrogen peroxide, 269
as spot test for ammonia, 185, 283 Nickel salt and diacetylmonoxime test
Neutral red as indicator of hydrogen-ion for hydroxylamine, 186
concentration, 474 Nickel salts,- as catalyst- in oxidation test
Nickel, in alloys, test for, 292-293, 434 for manganese, 133
aluminum in presence of, 146 cobalt in, test for, 112-113
chromium in presence of, 128 induced reduction of, as test for plati-
in cobalt salts, detection, 434 num metals, 103
copper in presence of, 71-72, 426 interference in ammonium mercuri-
crucible for air bath, 27 thiocyanate test for copper, 73
' dimethylglyoxime test for, 114, 434 in benzidine test for lead, 55
in presence of oxidizing agents, 117 in cerium salt reduction test for
-free cobalt salts, preparation, 436 iodides, 201
35
554 SUBJECT INDEX
Nickel salts, interference in potassium Griess reaction of, 189

thiocyanate tSst for iron, 126 hydroxylamine 'in presence of, 189
in zinc uranyl acetate test for interference in chromyl chloride test
sodium, 176 for hydrochloric acid, 193
presence in 1,2-diaminoanthraqui- in cobalt salt' test for thiocyanates,
none-3-sulfonic acid test for cop- 215
per, 70 in potassium thiocyanate test for
reaction with ammonium thiocyanate, molybdenum, 92
113 in test for hydroxylamine, 190
with 1,2-diaminoanthraquinone-3- in thiourea test for selenious acid,
sulfonic acid, 69 265
with diphenylcarbazide, 128 in mixtures, test for, 284
with rubeanic acid, 109, 118 1,8-naphthylenediamine test for, 249
with sodium hypophosphite, 103 nitrates in, test for, 245
zinc in presence of, 139 reaction with aminosulfonic acid, 246
Niobium, fluorescence test for, 159 with brucine, 245
reaction with curcumin, 256 with chrysean, 260
Niobium salts, interference in cacothel- with diphenylamine, 244
ine test for tin, 87 with potassium thiocyanate, 125
m-Nitraniline, identification, 325,382 reduction of nitrates to, 246
o-Nitraniline, identification, 325, 382 removal by hydrazoic acid, 246
p-Nitraniline, identification, 325,377,382 by sodium azide or aminosulfonic
Nitrates, in black powder, test for, 488 acid, 246-247
fluorides in presence of, 207 sulfanilic acid test fpr, 248
interference in cerium salt reduction test by release of iodine on starch filter
test for iodides, 201 paper, 249
in chromyl chloride test for hydro-
chloric acid, 193 m-Nitroaniline, identification, 390
in hydrogen peroxide test for vana- OT-Nitrobenzaldehyde, identification,
dium, 150 325,334,340,350
in silicomolybdic acid test for fluor- o-Nitrobenzaldehyde, detection of nitro-
ides, 207 gen in, 316
in sodium carbonate-phenolphthal- identification, 325, 334, 340, 343, 345,
347, 350
ein test for carbonic acid, 255 p-Nitrobenzaldehyde, identification, 325,
in titanium-malachite green test for
tungsten, 96 340, 343, 346, 347, 350
in mixtures, test for, 284 Nitrobenzene,-identification, 324
in nitrites, test for, 245 p-Nitrobenzeneazochromotropic acid, re-
reaction with pyrogallol, 224 action with germanic acid, 91-92
reduction to ammonia, 247 test for boric acid, 258
to nitrites, 246 p-Nitrobenzeneazo-a-naphthol, prepara-
Nitric acid, brucine test for, 245 tion, 174
diphenylamine or diphenylbenzidine reaction with calcium carbonate, 174
test for, 244 with calcium hydroxide, 174,176
extract, Gutzeit test in, 284 test for magnesium, 173, 440
ferrous sulfate and sulfuric acid test- p-Nitrobenzeneazoresorcinol, reaction
for, 243 with cadmium, cobalt, and nickel
summary of tests, 504 hydroxides, 174
test by reduction to ammonia, 247 reaction with magnesium salts, 149
in water, test for, 478 test for beryllium, 149
Nitriles, detection of acid, 375 test for magnesium, 173
identification, 346 p-Nitrobenzenediazonium chloride test
summary of tests, 506 for ammonia, 182-183
Nitrites, acetic acid "ring test" for, 250 m-, p-Nitrob"enzoic acid, identification,
benzidine test for, 260 325
carbonates in presence of, 255 Nitrocellulose in explosives, test for, 488
SUBJECT INDEX 555
0-, m-, p-Nitrocinnamic acid, identifica- 5-Nitroso-8-hydroxyquinoline, as rea-
tion, 326 ^ gent for aromatic amines, 383
Nitro compounds, electrolytic reduction test for phenols, 329
to nitroso compounds, 322 Nitrosonaphthol reaction with ferric and
identification tests for, 324-325 palladium salts, 110
summary of tests, 507 a-Nitroso-fi-Qaphtbol, 2
test with sodium pentacyanoammine detection of nitrogen in, 315-316
ferroate, 322 A identification, 322, 353
p-Nitrodiazoaminoazobenzene as rea- reaction with copper and uranyl salts,
gent for cadmium, 79 110-111
Nitrogen, fusion'with alkali metals as reagent for cobalt, preparation, 110
test for, 316 test for cobalt, 109
Lassaigne's test for, 316 for tyrosine, 411
in organic compounds, 311 (S-Nitroso-a-naphthol, identification, 322
lime test for, 315 test for zirconium, 153
summary of tests, 506 2-Nitroso-l-naphthol-4-sulfonic acid, re-
and sulfur in the same sample, test action with copper salts, 113,128
for, 317 with ferrous salts, 113
test by heating with calcium oxide, 315 test for cobalt, 74,113
Nitroglycerin in explosives, test for, 488 for cobalt salts, 128
1,5-Nitronaphthylamine, identification, for copper, 74
325 for iron, 74, 128
o-Nitrophenol,'identification, 325,330 p-Nitrosophenyl, detection of nitrogen
p-Nitrophenol, detection of nitrogen in, in, 315-316
316 identification, 322
identification, 325, 331 5-NitrososaIicylaldehyde bisulfite, iden-
aa indicator of hydrogen-ion concen- tification, 348
tration, 474 Nitrosylthiocyanate, formation, 125
OT-Nitrophenylhydrazine, identification, 0-, p-Nitrotoluene, identification, 325
325, 38&-388 Nitrous acid, conversion of hydroxyl-
o-Nitrophenylhydrazine, identification, amine to, 189
325, 386-387 and mercuric nitrate test for phenols,
p-Nitrophenylhydrazine, identification, 330
325, 386, 388 1,8-naphthylenediamine test for, 249
p-Nitrophenylnitrosamine ammonium sulfanilic acid and a-naphthylamine
salt, formation of, 183 test for, 248
3-Nitrophthalic acid, identification, 364 summary of tests, 504
m-Nitrophthalic anhydride, identifica- test for phenols, 329
tion, 361 test by release of iodine on starch filter
6-Nitroquinoline, identification, 325 paper, 249
3-Nitrosalicylaldehyde, identification, in water, test for, 478
346 Noble metal (s), reaction with alkali and
5-Nitrosalicylaldehyde, identification, manganese salts, 42
345 Noble metal salts, reduction by stannous
Nitroso compounds, identification tests chloride, 79
for, 322 Nylander's solution as reagent for re-
reaction with sodium pentacyanoaquo ducing sugars, 409
ferroate, 321
sodium pentacyanoammine ferroate O
test for, 321
summary of tests, 507 Oenanthal, identification, 334, 340, 342,
test with phenol and sulfuric acid, 321 345, 347
Nitroaodimethylaniline as reagent for Oils, lead in, detection, 429
aromatic amines, 383 Oleic acid, identification, 358
p-Nitroodimethylaniline, identification, Olivinic tesinite, chromium in, 439
322 Opianic acid, identification, 343
656 SUBJECT INDEX
Optical glasses, alkali in, 449 Osmium salts,, aiud catalytic action of
Orcinol, identification, 331 mercury, 52-53
Ores, lead in, detection, 429 interference in; cerium salt reduction
solution of, 39 test for iodides, 201
Organic acids, interference in p-di- reduction by stannous chloride, 104
methylaminoazophenylarsonic acid Osmium tetroxide, action on potassium
test for zirconium, 155 iodide, 108
in stannous chloride test for tung- Oxalates, fluorides in presence of, 204
sten, 95 interference in ammonium molybdate
reaction with molybdates, 92-93 test for phosphoric acid, 251
Organic analysis, spot reactions in, 309 in potassium ferrocyanide test for
Organic components, decomposition by iron, 122
copper oxide, 274 in potassium thiocyanate test for
Organic compounds, detection of atomic iron, 124-125
groups in, 309 in zirconium-alizarin test for fluo-
detection of characteristic groups, 320 rides, 202
of elements in, 310 Oxalic acid, formation of aniline blue as
of sulfur in, 313-314 test for, 403, 485
identification of specific, 393 in leather, aniline blue test for, 485
identification by spot reactions, 5 summary of tests, 509
Organic groups, sunamary of tests, 506 test by conversion to glycolic acid,
Organic hydroxy acids, interference in 402-403
alizarin test for zirconium, 154 thiocyanate in presence of, 212
Organic and inorganic (basic) materials Oxazine dyes, conversion to, as test for
that react with mineral acids, detec- aromatic o-dioxo compounds, 338
tion, 479 Oxidation, as preliminary operation, 8
Organic li(iuids, detection of free sulfur test for free carbon, 281
in, 483 Oxides, basic, in glass, detection, 448
Organic materials, charring, 239-240 free metals in, detection, 449
reaction with inorganic reagents, 2 precipitation by ammonia, 22
Organic reagents, use in spot tests, 2 Oxidizing agent(s), boric acid in presence
Organic solid products, detection of free of, 259
sulfur in, 482 chloramine-T as, 194
Organic solvents, detection of sulfur dimethylglyoxime test for nickel in
in, 480 presence of, 117
Organic substances, tests for added formation of benzidine blue by, 242
materials and undesirable admix- interference in 8-hydroxyquinoline-7-
tures in, 486 iodo-5-sulfonic acid test for iron, 124
Original substance, Gutzeit test on, 283 reaction with p-nitrobenzeneazochro-
Orthoperoxyvanadic acid, formation of, motropic acid, 258, ^
98 Oximes, summary of tests, 508
Osazones, -naphthylamine test for, 387, tests for, 352-353
389 Oxine test for vanadium, 99
summary of tests, 507 Oxobenzalbutanone oxime, identifica-
test for, 388 tion, 353
Osmium, activation of chlorate solutions Oxomethylene compounds, identifica-
as test for, 107 tion, 336 '
detection by induced reduction of summary of tests, 507
nickel salts, 104 test by conversion to l,2-diketone8,
detection of palladium in presence of, 335
106 tests for, 334
interference in test for palladium, 105 Oxonium compounds, test for, 392
reaction with benzidine acetate, 109 m-Oxybenzjildehyde, identification, 343,
with potassium ferrocyanide, 109. 345, 347
ruthenium in presence of, detection, o-Oxybenzaldehyde, identification, 343,
109 347
summary of tests, 500 p-Oxybenzaldehyde, identification, 343
SUBJECT INDEX 657
a-Oxy-n-butyric aldehyde, identification, Paper as reaction medium, 8
342 '' Paraffin, use in storage bottles for alka-
Oxydimercuriamido iodide, formation of, line solutions, 10
183 Paraldehyde, fluorescence with o-hy-
Oxygen, in organic compounds, presence, droxydiphenyl, 401
311 identification, 342, 345
summary of tests, 506 reaction with p-hydroxydipfaenyi, 400
test through solvate formation with Parallel tests recommended, 9
ferric thioc^jsiate, 319 Pepsin, identification, 414
Oxygen-containing organic solvents, ex- Peptone, dried, identification, 414
traction of ferric thiocyanate from Peridotite, chromium in, 439
solution by, 319 Periodate(s), oxidation with, and detec-
2-Oxy-l-naphthaldehyde, identification, tion of formaldehyde and formic
"344-^345 acid, as tests for polyhydroxy alco-
Oxyquinoline in the Beilstein reaction, hols, 327, 328
311 reaction with manganous sulfate, 224
and phosphoric acid, 222
and tetrabase test for manganese, 134
Palladium, detection by condensation of Periodic acid, formation of complex cop-
hydrogen on, 101-102 per salts as test for, 225
detection by induced reduction of formation of stable copper salts by,
nickel salts, 103-104 133, 225
by mercuric cyanide and diphenyl- manganese salts and tetrabase test for,
carbazide, ^107 224
in presence of osmium, 106 manganous sulfate and phosphoric acid
p-dimethylaminobenzylidine rhoda- test for, 224
nine reaction for, 43, 100, 107 as preventive of copper catalysis, 133
distinction from platinum foil, 434 summary of tests, 604
naphthalene-4-sulfonic acid-1 -azo-5- test for polyhydrio alcohols by oxida-
ortho-8-hydroxyquinoline test for, tion with, 326
107 Permanganate (s), chromates in presence
nickel dimethylglyoxime test for, 106 of, 262
in platinum salts, test for, 106 interference in tetrabase oxidation test
in presence of gold and platinum, stan- for ferricyanic acid, 220
nous chloride test for, 104 oxidation of manganese salts to, 130
reaction with dimethylglyoxime, 114 in presence of chromate, 261
silver in presence of, 45 cellulose test for, 261
summary of tests, 500 reaction with benzidine, 242
test by catalysis of the carbon mon- with dip.lenylamine, 244
oxide reduction of phosphomolyb- with sodium azide, 130
dates, 105 Permanganic acid, summary of tests, 504
Palladium chloride, and auric chloride, test for, 261
reaction with rubidium and thallium Permolybdate and a-naphthoflavone test
salts, 182 for hydrobromic acid, 196
test for cesium, 182 Peroxidase, detection, 424
reaction with silver iodide, 303 Peroxides, discharge of chromate-di-
reduction, as test for mercury, 274 phenylcarbazide reaction by, 271
Palladium salts, reaction with cacothe- in fats, detection, 487
line, 52 reaction with diphenylamine, 244
reaction with nitrosonaphthol, 110 Peroxodisulfatotitanio acid, formation,
with rubeanic acid, 109 150
reduction by stannous chloride, 104 Persulfates, reaction with dimethyl-
Palladous chloride test, for hydriodic glyoxime, 117
acid, 197 reaction with manganese salts, 225
for iodides, 202 with manganous sulfate, 224
Pancreatin, identification, 414 and phosphoric acid, 222
Paper ash, detection of alkali in, 456 with pyrogallol, 224
558 SUBJECT INDEX
Persulfuric acid, beuzidine test for, 242 m-Phenylenediamine hydrochloride as

Pertitanic reaction for titanium, 150, 304 reagent for reducing sugars, 409
Pharmaceutical materials, free sulfur in, Phenyl ethyl alcohol, detection, 326
detection, 482 Phenylhydrazine, identification, 370,
lead in, detection, 432 386-388
spot reactions in examination of, 425 test for molybdenum, 94
test for copper in, 427 l-Phenyl-2-methylamino propane, iden-
Phenanthraquinone, identification, 339, tification, 372
371 Phenyl mustard oil, identification, 357
a,a'-Phenanthroline as substitute for Phenyl salicylate, identification, 360
a,a'-dipyridyl, 123 Phloroglucinol, identification, 331
p-Phenetidine and ferricyanide test for pH meter, 40
zinc, 141 values, adjustment to, aa preliminary
Phenetidine-HCl and hydrogen peroxide operation, 8
test for copper, 74 Phosgene, in commercial chloroform and
Phenols), identification, 330-332 carbon tetrachloride, 417
5-nitroso-8-hydroxyquinoline test for, conversion to diphenylcarbohydrazide
329 as test for, 416
nitrous acid test for, 329 summary of tests, 509
and mercuric nitrate test for, 330 Phosphate(s), as contaminant of filter
reaction with chloranil, 383 paper, 18
p-substituted, reaction with a-nitroso- conversion to ammonium phospho-
/3-naphthol, 412 molybdate, 317
and sulfuric acid test for nitroso com- conversion to, as test for phosphorus,
pounds, 321 317
summary of tests, 508 fertilizers, distinction from super-
Phenolase, detection, 422 phosphate, 447
Phenolphthalein, and barium carbonate fluorides in presence of, 204
test for sulfuric acid, 237 interference in alizarin test for zir-
as indicator of hydrogen-ion concen- conium, 154
tration, 474 in p-dimethylaminoazophenylarson-
paper test for magnesium, 176 ic acid test for zirconium, 155
reduction to phenolphthalin, 219 in potassium thiocyanate test for
and silver carbonate preliminary test iron, 124-125
for halides, 193 in zirconium-alizann test for fluo-
and sodium carbonate test for carbonic rides, 202
acid, 254 in zirconium azoarsenate test for
Phenolphthalin, catalyzed oxidation of, fluorides, 205
as test for hydrogen peroxide, 270 in minerals, detection, 471
reduction of phenolphthalein to, 219 in mixtures, test for, 284
solution, preparation of, 220 in presence of arsenic and silicic acids,
test for ferricyanio acid, 219 261
Phenol red aa indicator of hydrogen-ion reaction with molybdates, 92
concentration, 476 in acid solution, 250
Phenylacetaldehyde, identification, 337, in rocks, detection, 471
344-345, 347 Phosphomolybdates, catalytic carbon
Phenyl acetate, identification, 360 monoxide reduction of, as test for
Phenylacetic acid, identification, 358 palladium, 105
1 -Phenyl-1 -chloroethylene-2-phosphoric platinum B catalyst in reduction of,
acid, detection of phosphorus in, 318 105 '
p-Phenylenediamine, identification, 377, reduction by antimony, copper, iron,
382 mercurous, and tin salts, 120
oxidation to indamine dye aa test for, by antimony trichloride, 87
415 by staimous chloride, 87
oxidation test for aldehydes, 345 Phosphomolybdio acid, formation, 250
summary of tests, 5C9 formatfon of benzidine blue by, 250
SUBJECT IITOEX 559
of molybQnum blue by, 250 Piperidine, fluorescence, 376
and hydrobromic acid test for thal- identification, 370, 372, 376, 391
lium, 120 and sodium nitroprusside test for ace-
reaction with free metals, 449 tic acid, 399
with stannous chloride, 87 for acrolein, 408
test for antimony, 84 Piperonal, identification, 343, 345
for cerium, 161 Pipet(s), 11, 14, 15
for copper, 67 bottles, 10
for free metals and alloys, 273 dropper, 14,38
for vanadium, 99 filter, 35-36
Phosphoric acid, ammonium molybdate holder, 16
and benzidine test for, 250 rinser, automatic, 40
effect on quinalizarin test for magne- transfer capillary, 38
sium, 172 use, 35
free, test for, 239 Piterite, chromium in, 439
interference in molybdate-benzidine Platinic chloride solution for treatment
test for germanium, 91 of platinum wire, 16
in stannous chloride test tor tung- Platinum, as catalyst in reduction of
sten, 96 phosphomolybdates, 105
and manganous sulfate test for chloric crucibles for ignitions, 28
acid, 221 detection by condensation of hydrogen
for periodic acid, 224 on, 101-102
in presence of arsenic acid, 251 p-dimethylaminobenzylidene rhoda-
of silicic acid, 252 nine reaction for, 43
reaction with benzidine, 253 foil, distinction from palladium, 434
with molybdates, 92 loops for obtaining drops, 16
silicic acid in presence of, 253 metallic, ferric ferricyanide test for,
thioeyanate in presence of, 212 palladium in presence of, 104
in water, test for, 478 in presence of arsenic, detection, 103
Phosphorus, in organic compounds, 311 of other noble metals, stannous chlo-
fusion with lime as test for, 317 ride test for, 104
summary of tests, 506 reaction with dimethylglyoxime, 114
in l-phenyl-l-chloroethylene-2-phos- silver in presence of, 45
phinic acid, detection, 318 spoon, for fusions, 29
segregations in iron and stee.l, detec- summary of tests, 500
tion, 460 wires for mixing powders, 13
Photochemical reactions, apparatus for Platinum metals, catalytic tests for, 101
observing, 40 detection by induced reduction of
o-Phthalaldehyde, identification, 344-345, nickel salts, 103-104
350 . interference in dithizone test for mer-
Phthalic acid, identification, 364 cury, 50
Phthalic acid dialdehyde, identification, summary of tests, 500
347 Platinum salts, reaction with p-di-
Phthalic anhydride, identification, 361 methylaminobenzylidene rhodanine,
Phthalimide, identification and fluores- 107
cence, 379 reaction with rubeanic acid, 109
a-PicoIine, test for, 394 reduction to platinum by hypophos-
Picramine, identification, 326 phorous acid, 266
Picric acid, in explosives, test for, 488 by stannous chloride, 104
identification, 325-326 Plumbite solution and formaldehyde test
and sodium carbonate, reaction with for carbon disulfide, 418
sulfides, 212 Polyhydroxy alcohols, test by oxidation
test for cyanide, 212 with periodate and detection of
P*icryl chloride, identification, 326 formaldehyde, 328
Figments, lead in, detection, 429 test by oxidation with periodate and
detection of formic acid, 327
560 SUBJECT INDEX
Pontachrome blue-black R test for alu- and manganese salts test for gallium,
minum, 147 164
Porcelain, beakers for holding glass rods paper, 20
and pipets, 15 reaction with aluminum, 145
crucibles for ignitions, 28 with calcium, 169
dish, heating of sample in, 295 with cobalt, copper, iron (II), man-
as medium for spot tests, 6-8 ganese, and nickel, 138
spoon, spot reactions in, 25 with copper and ferric salts, 157
spot plates, 23-24 with osmium, 109
vessels, spot reactions in, 23 with silver chloride, 193
Porous threads as medium for spot test for iron, 122
tests, 6 for uranium, 157, 439
Portable drying oven, 40 Potassium fluoride, detection by zir-
Portable electrolysis apparatus, 40 conium alizarinate, 202, 312
Potassium, as contaminant of filter iron in, detection, 437
paper, 18 Potassium hydrogen benzene disul-
dipicrylamine test for, 178, 441 fonate, identification, 367
in glass, test for, 448 Potassium hydrogen p-benzene sul-
lithium in presence of, 181 fonate, identification, 368
in mixtures, test for, 287 Potassium iodide, action of osmium
in presence of sodium, 179-180 tetroxide on, 108
in silicate rocks, detection, 441 and bromine test for enols, 332
sodium cobaltinitrite and silver nitrate as catalytic reducing agent for arsenic
test for, 177 acid, 80
summary of tests, 500 paper test.for bismuth in minerals, 463
Potassium bichromate, detection of po- potassium thiocyanate in, test for, 213
tassium chromate in, 479 reaction with lead, mercury,, and
Potassium bismuth iodide, reaction with Sliver, 119
thallium, 182 test for antimony pentoxide, 307
test for cesium, 182 for thallium, 119
Potassium bromide-cuprous bromide Potassium isatin sulfonate, detection of
test for bromides, 197 sulfur and nitrogen in, 317
Potassium cerous carbonate test for hy- Potassium manganocyanide as reagent
drogen peroxide, 271 i for bismuth, 63'
Potassium chlorate decrepitation test Potassium methionate, identification,
for carbon in coal, 308 367
Potassium chloride, in electroip-aphic Potassium nitrite and potassium thio-
method, 39 cyanate paper test for cobalt in
lithium in presence of, 181 minerals, 463 ^
Potassium chromate, in potassium bi- Potassium percerio carbonate, forma-
chromate, detection, 479 tion, 271
test for lead in minerals, 463 Potassium permanganate, formation of
for. silver, 48 benzidine blue by, 214
Potassium chromium thiocyanate as rea- precipitation of barium sulfate in pres-
gent for bismuth, 62 ence of, as test for barium, 167
Potassium cobalticyanide test for zinc, test for hydrobromic acid, 197
141 Potassium persultate, detection by ben-
Potassium cuprocyanide, reduction of zidine, 242-243
molybdenum in phosphomolybdates Potassium salts, interferencejin dipicryl-
by, 68 amine test for thallium, 121
Potassium, cyanide, formation, 281 in zinc uranyl acetate test for sodium,
176 . ^ -
test for m-dinitro compounds, 323 Potassium sulfate,' in electrographic
Potassium ferricyanide as oxidizing method, 39
agent, 335 zinc in presence of, 141
Potassium ferrocyanide; interference in Potassium thiocyanate, in potassium
iodine-azide test for thiocyanate, iodide; test for, 213
213 . in presence of sodium thiosulfate, 214
SUBJECT INDEX 661
and stannous chloride test for molyb- test for ferrocyanide, 216-217
denum, 92 Prussic acid, benzidine reaction for, 214
for testing filter papers, 18 copper acetate-benzidine acetate reac-
test for iodic acid, 223 tion tor, 208
for iron, 124 and starch-iodine test for cyanides, 212
a,Q;'-dipyridyl test as alternative test for thiocyanates by conversion
for, 123 into, 214
Potassium xanthate, identification, 357, Purity, of filter papers, 18
360 spot reactions in tests of, 425
test for molybdenum, 93, 306,433 Purpurin, as reagent for boric acid, 267
Potato starch, identification, 411 Purpurogallin, formation, 224
Powder, spot tests in examining, 488 Pyrex glass, alkali in, 449
testing hardness and streak of, 14 Pyridine, conversion to glutaconic alde-
Praseodymium salts, lake formation -with hyde as test for, 414
quinalizarin, 148 in denatured alcohol, test for, 487
reaction with quinalizarin, 172 irradiated, reaction with primary aro^
Precipitations in conical microcentrifuge matic amines, 378, 380
tubes, 37 as solvent, 278, 281
Preliminary operations, 8 substituted, in the Beilstein reaction,
special appliances and devices for, 39 311
Preliminary tests, 320 summary of tests, 509
for acid radicals, 191 test for, 394
for halogen hydracids, 193 a-Pyridylbenzoylphenylhydrazone iden-
of sample, 41 tification, JS8
spot reactions in, 41, 282, 294 Pyrite, detection of free sulfur in, 483
Preparation and storing of solutions, 9 Pyrocatechol, identification, 330-331
Primuline yellow, censtitution, 482 iron salts of, 126.
Printed paper, free metals in, detection, reaction with antimony salts, 85
449-450 with iron salts, 151
^-Proline, identification, 372 test for titanium, 150
Propionaldehyde, identification, 342, 347 Pyrogallol, identification, 330-331
reaction with p-hydroxydiphenyl, 400 oxidation by chromate and iodine, 224
Propionaldehyde cyanhydrin, 348 reaction with antimony salts, 85
Propionaldehyde phenylhydrazone, iden- with bromate, nitrate, and persul-
tification, 388 fate, 224
Propionates, reaction with lanthanum test for gold, 101
salts and iodine, 397 for iodic acid, 224
Propyl alcohol, detection, 326 Pyrolusite, test for, 305
Propylfimine, identification, 370 test for iron in, ^
Propyl benzoate, identification, 360 Pyrope, chromiimi in, 439
Proteins, hydrolysis to amino acids, as Pyrrole, fluorescence, 379
test for, 414 identification, 379, 391
prevention of starch-iodine reaction test for selenious acid, 264
by, 198 Pyrrole blue, formation, 264
reaction with p-dimethylaminobenzal- Pyrrole derivatives, fluorescence, 379
dehyde, 383 identification, 378-379
with a-nitroso-/S-naphthol, 412 summary of tests, 508
summary of tests, 509 Pyrrolidine, identification, 372
tetrabromophenolphthalein ethyl ester Pyruvic acid, o-hydroxydiphenyl and
test for, 412 sulfuric acid test for, 402
in urine, detection, 414 identification, 351
Protocatechuic aldehyde, identification, reaction with p-hydroxydiphenyl, 401
331, 344-345, 348, 350 summary of tests, 509
Prussian blue, distinction from Turn-
bull's blue, 218 Q
formation, 122, 212, 216, 221, 269, Qualitative inorganic analysis, 3
273-274 Qualitative organic analysis, 3
562 SUBJECT INDEX
Quartz analytical lamp, 40 Residue, "insoluble," detection of sub-

watch glasses, 25 stances in, 300
Quercetin or quercitrin, reaction with Resins in mineral pils, detection, 485
uranium salts, 128 Resorcinol, identification, 330-331
test for ferric salts, 128 prevention of starch-iodine reaction
for uranium, 159 by, 198 I
Quinaldine, test for, 394 as reagent for aromatic amines, 383
Quinalizarin, reaction with beryllium test for 1,2-dicarboxylic acids, 360
salts, 172 for zinc, 141
reaction with cerium, lanthanum, neo- Rhodamine(s), dialkyl, fluorescence, 373
dymium, praseodymium, thorium, formation of dyestuffs, 371-375
and zirconium salts, 148, 172 tetra-alkyl, fluorescence, 374
with magnesium, 148-149 Rhodamino B test for antimony, 86
test for aluminum, 146 Rhodanine, identification, 357, 390
for beryllium, 147-148 Rhodium, detection by condensation of
for boric acid, 257 hydrogen on, 101-102
for indium, 162-163 Rhodium salts, interference in cacothe-
for magnesium, 172 line test for tin, 87
Quinic acid, reaction with naphthoresor- Rhodizonic acid, reaction with barium
cinol, 402 salts, 236
Quinoline, and potassium iodide as rea- test for barium, 165
gents for bismuth, 63 Riegler's reagent, preparation, 183
test for, 394 "Ring'test" for nitrites, 250
Quiaoneanildiphenylhydrazone, forma- Rinmann's green, formation, 141
tion, 264 Rocks, basic, detection, 479
boron in, detection, 471
R chromium in, detection, 438
Rancidity in fats, detection, 487 fluorine in, detection, 463
Rare earths, cerium in mixture of, 160, phosphates in, detection, 471
162 spot reactions in studies of, 3
Reactions, choice of, 6 sulfide sulfur in, iodine-azide reaction
increase of sensitivity on filter paper, 6 for, 464
Rosocyanine, conversion of curcumin to,
use of sensitive and characteristic, 3
Reactive CHj and NHj groups, summary 256
of tests, 508 Rubber, vulcanized, detection of free
tests for, 390-391 sulfur in, 482
Rubeanic acid, identification, 356
test with sodium 1,2-naphthaquinone- reaction with copper, cobalt, and
4-suIfonate, 389 nickel salts, 108-109, 118
Reagent paper, impregnated with insolu- with copper and nickel, 112
ble compound, 20 test for cobalt, 70,112' -
spot reactions on, 17 for copper, 70, 426
stability, 23 for nickel, 70, 117
Reagents, arrangement, 11 for ruthenium, 108
gaseous, 22 Rubidium, lithium in presence of, 181
for use in preliminary examination of a Rubidium chloride, lithium in presence
mixture, 296-298 of, 181
Redistillation of water, apparatus for, 40 Rubidium salts, reaction with auric chlo-
Red lead, detection of free metal in, 450 ride and palladium chloride, 182
Redox reactions, 272 reaction with dipicrylamihe, 179
Reducing agents, interference in alkali with gold platinibromide, 182
hypoiodite test for magnesiimi, 172 Ruthenium, activation of chlorate solu-
Reducing sugarg, test for, 409 tions as test-for, 107
test by reduction of silver oxide, 410 detection' b y induced reduction of
Reduction, as preliminary operationi, 8 nickel salts, 104
test for antimony, 83 interference in test for palladium, 105
SUBJECT INDEX 563
in presence of osmium, test for, 109 reaction with 1,8-naphthylenediamine,
rubeanic acid test for, 108 266
summary of tests, 600 with thiourea, 266
Ruthenium salts, reaction with rubeanic reduction by iron sulfate, 268
acid, 109 Selenium, free, reaction with thallous
Rutile, titanium in, detection, 440 sulfide paper, 277, 279-280
stmunary of tests, 605
S test by addition to thallous sulfide,
279
Sacchareins, formation, 360 by formation of silver selenide, 280
Saccharin, fluorescence, 379, 487 germanium in presence of, 90
identification, 365, 379, 487 in minerals, test for, 465
Saccharose, identification, 328, 410-411 in presence of sulfur, detection, 280
Sago starch, identification, 411 of tellurium, test for, 263
Salicylaldazine, formation, 186,188 reaction with silver, 280
Salicylaldehyde bisulfite, identification,
reduction of selenious acid to, 263, 266
348
Salicylaldehyde, and copper salts test in sulfur, detection, 465
for hydroxylamine, 187 in tellurium, detection, 465
identification, 343, 345-346, 350 tellurium in presence of, test for, 266-
reaction with 2,7-dihydroxynaph- 267
thalene, 400 Selenium dioxide, as oxidizing agent, 335
test for hydrazine, 186 in tellurium dioxide, detection, 265
Salicylaldoxime, methyl ether of, iden- Selenium sulfide as reagent for mercury
tification, 353 vapor, 275
as reagent for copper, 66,188 Semicarbazide, fluorescence, 379
Saimin, detection, 413 identification, 379, 386-387, 390
Salol, identification, 331 Semimicroanalysis, 5
Salts of organic bases, detection, 480 Semimicrochemical tests, choice of, 41
Samarskite, uranium in, detection, 439 Sensitivity data, validity, 41
Samples, apparatus for comparison, 40 Sensitivity of reactions, 1
preliminary tests, 41 Separation, as preliminary operation, 8
Sand bath, 27-28 of solid and liquid phases, 34
Scandium salts, reaction with morin, 142 by shaking with organic solvent, 39
Scheelite, molybdenum in, 433 Serpentine, chromium in, 439
Schiff's base, 340, 380, 383, 408, 411, 414 Serum, detection of tyrosine in, 412
Schleicher and Schtill filter paper, 19 Serum albumin, detection, 413
Sedimentation of insoluble materials by Silica, in caustic alkalis and alkaline
centrifuging, 36 solutions, 469
Selective reagents, 3 as contaminant of filter paper, 18
Selenates, reduction by iron sulfate, 268 in insoluble residue, 306
Selenic acid, distinction from selenious watch glass for ignitions, 28
acid, 264 in water, test for, 477
summary of tests, 504 Silicate rocks, potassium in, detection,
Selenious acid, diphenylhydrazine test 441
for, 264, 465 test for magnesium in, 440
distinction from selenic acid, 264 Silicates, alkali metals in, test for, 441
hydriodic acid test for, 263 conversion of silicon and silicides to,
interference in tellurium test, 267 307
and Q-naphthylamine test for aryl- decomposition, 29
hydraiines, 387 in insoluble residue, 306
pyrrole test for, 264
reduction to selenium, 263, 266 in mixtures, test for, 284
summary of tests, 604 titanium in, 446
Selenites, in mineral acid solutions, de- Siliceous products, vulnerability to at-
tection. 265 tack by alkalis, test for, 469
564 SUBJEJCT INDEX
Silicic acid, ammonium molybdate and potassium chromate test for, 48

benzidine test for, 252 precipitation by antimony sulfide
interference in etching test for fluo- paper, 20 j
rides, 207 in presence of gold, palladium, and
in molybdate-benzidine test for ger- platinum, detection, 45
manium, 91 of mercury, detection, 44
in minerals, test for, 470 of thallium, catalytic test, 47
phosphates in presence of, 251 reaction with potassiiutt iodide, 119
phosphoric acid in presence of, 252 with selenium, 280
in phosphoric acid, test for, 253 with sodium rhodizonate, 57
reaction with molybdates in acid solu- in silver plating, detection,.425
tion, 250 stannous chloride test for, 48
silioo-molybdate reaction for, 307 summary of tests, 600
simimary of tests, 504 test for, by deposition, 45
Silicides, conversion to silicate, 307 thallium in presence of, 119
in insoluble residue, 306 Silver ammine salts, test for manganese,
Silicofluorides, etching test for, 207 137
Silico-molybdate reaction for silicic Silver azide, formation, as test for hy-
acid, 307 drazoic acid, 215
Silicomolybdic acid, formation, 250, 252 Silver carbonate and phenolphthalein
formation of benzidine blue by, 251- preliminary test for halides, 193
252, 306 Silver chloride, identification, 193
of molybdenum blue by, 252 reaction with potassiufii ferrocyanide,
test for hydrofluoric acid by conver- y 193
sion into, 206 silver in a mixture of lead and mercur-
Silicon, conversion to silicate, 307 ous chlorides and, 44
in insoluble residue, 306 Silver ferrocyanide conversion to silver
Silicon dioxide, interference in fluores- ferricyanide, 193-194
cence test foruraaium, 159 Silver halides in insoluble residue, 302-
Silicon tetrafluoride, conversion intQ, as 303
test foj silicic acid in minerals, 470 Silver iodide, reaction with palladium
formation, 206 chloride, 303
Silk cloth for bolting powdered speci- Silver nitrate, and formaldehyde test for
mens, 12 ammonia, 185
Silk threads as medium for spot tests, 6 and manganese sulfate test for am-
Silver, in alloys, test for, 292-293, 425 monia, 184
catalytic reduction of manganese and paper test for arsenic in minerals, 463
cerium salts as test for, 47 precipitation in alkaline solution as
chromotropic acid and stannous chlo- test for mercuric cyanide, 210
ride test for, 48 as reagent for arsenic-hydride, 80
copper-in presence of, 426 and sodium cobaltinitrite test for
copper thiocyanate test for, 48 potassium, 177 ,
p-dimethylaminobenzylidene rhoda- -tannin test for ammonia, 185
nine test for, 43, 51, 71, 42S test for arsenates, 82
dithizone test for, 48 for iodides, 201
for mercury in presence of, 50 Silver oxide, reaction with malachite
for zinc in presence of, 140 green, 162,
manganese in presence of, 136 reduction test for aldehydes, 346
manganese nitrate and alkali test for reducing sugars, 410
for, 42 Silver salts, ammonia in presence of,
metallic, ferric ferricyamde test for, , 185 /
274 cadmium in presence of, 75
in minerals, test vrith chromate and and catalyticâction of mercury, 62-53
potassium iodide paper, 463 cerium in presence of, 161
in a mixture of lead, mercurous and formation of benzidine blue by, 131
silver chlorides, detection, 44 interference in benzidine test for lead,
in oiixtures, test for^ 284, 287 55
SUBJECT INDEX 565
in cerium salt reduction test for Sodium fluoride, decomposition of ferric
iodides, 201 thiocyanate by, 217
in o-tolidine test tor copper, 67 in wood preservatives, test for, 450-451
manganese in presence of, 132 Sodium hydrogen hydroxyquinoline di-
in manganese sulfate test for am- sulfonic acid, identification, 367
monia, 184 Sodium hydrogen j3-naphthalene disul-
oxidation of benzidine by, 135 fonate, identification, 367
in oxidation of chromium salts to Sodium p-hydroxyphenylarsenilate, de-
chromates, 129 tection of arsenic in, 319
reaction with benzidine, 120,131,161 Sodium hypophosphite, reaction with
with chromotropic acid, 152 nickel salts, 103
witli p-dimethylaminobenzylidene Sodium 1,2-naphthaquinone-4-sulfonate,
rhodanine, 107 and methyl iodide test for tertiary
with potassium chromium thiocy- ring bases, 392 ,
anate, 62 test for reactive CH2 and NHj groups,
reduction to silver by hypophospho- 389
rous acid, 266 Sodium nitroprusside, and acetaldehyde
by stannites, 266 test for aliphatic amines, 371
in sodium cobaltinitrite test for po- and piperidihe test for acetic acid, 399
tassium, 178 for acrolein, 408
Silver selenide formation as test for free reaction with sulfides, 226
selenium, 280 test for hydrogen sulfide, 226
Sintered glass as inedium for spot tests, 6 for methyl ketones, 349
Small volumes of liquid, heating, 33 for sulfide, 239
Smaragdite, chromium in, 439 for sulfurous acid, 231
Sodium, in glass, test for,,448 Sodium pentacyanoammine ferroate test
lithium in presence of, 181 for aldehydes, 349
in mixtures, test for, 287 for aliphatic and aromatic hydrazines,
potassium in presence of, 179-180 385
summary of tests, 501 for nitro compounds, 322 '
Sodium acetate, identification, 358 for nitroso compounds, 321
Sodium acetylarsenilate, detection of Sodium pentacyanoaquoferriate test for
arsenic in, 319 primary aromatic amines, 381
Sodium azide, and iodine test for carbon Sodium pentacyanoaqub ferroate reac-
disulfide, 417 tion with nitroso compounds, 321
reaction with metallic sulfides, 228-229 Sodium phosphate, interference in io-
with permanganates and chromates, dine-azide test for thiocyanate, 213
130 Sodium plumbite test for sulfides, 231
with sulfo salts, 228 Sodium-potassium carbonate, as flux, 29
removal of nitrites by, 246-247 fusion with, as test for silicic acid in
test for mercury sulfide, 229 minerals, 470
Sodium bisulfate as flux, 29 Sodium rhodizonate, reaction with bari-
Sodium carbonate, extracts in tests for um, cadmium, silver, tellurium, and
acid radicals, 191 tin, 57
and phenolphthalein test for carbonic reaction with barium salts, 169, 236
acid, 254 with strontium salts, 165-166
as solvent for thallium, 121-122 test for barium, 165
Sodium chloride, lithium in presence of, for lead, 56, 306, 428
181 for lead sulfate in insoluble residue,
solution, detection of iodine and bro-
mine in, 197 301-302
Sodium cobaltinitrite, reaction with am- for strontium, 169
monium, lithium, and thallium salts, Sodium salts, interference in dipicryl-
178 amine test for thallium, 121
and silver nitrate test for potassium, sulfate in "pure," detection, 467
177 Sodium sulfide, detection, 226, 228
566 SUBJECT INDEX
Sodium sulfite in presence of sodium Standard solutions, 10

thioBulf ate, detection, 236 Stannite, reduction of metallic salts by,
Sodium thiosulfate, decomposition of 266 \
ferric thiocyanate by, 217 test for bismuth, 60, 63
potassium thiocyanate in presence of, tin in, 432
214 Stannous chloride, and aniline test for
in ptesence of sodivun sulfide, 242 mercury, 50
as reagent for molybdenum, 92 reaction with 2-benzylpyridine, 236
sodium sulfite in presence of, 236 with cacotheline, 308
Sodium zinc uranyl acetate, formation, with phosphomolybdic acid, 86-87
176 reduction of gold, osmium, palladium,
Solid (s), apparatus for extraction with and platinimi salts, 104
organic solvents, 40 of mercuric salts, 50
choice of solvent for, 39 of molyjadates, 86
extraction with organic solvents, 12 of phosphomolybdates, 87
fusion with disintegating agents, 12 test for arsenic, 79, 318
grinding and mixing, 12 for gold, 101
metal sulfides, reaction with sodium for ketohexoses, 410
azide, 228-229 for palladium in presence of gold and
preparation of solutions of, 11, 12 platinum, 104
reaction with reagent solution, 8 for platinum in presence of other
testing by spot reactions, 35 noble metals, 104
volatilization of components, 12 for silver, 48
Solid and liquid phases, separation, 34 for tungsten, 94, 306
Solid reagents, use in spot analysis, 9 Stannous salts, reaction with alkali and
Solubility, determination, 35 manganese salts, 42
of metals in nonoxidizing acids, 272 Starch, as contaminant of filter paper, 18
Solution, of alloys, metals, and ores, 39 identification, 328, 410-411
as preliminary operation, 8 Starch-iodine reaction, detection of
Solution dish, 11, 15 iodates by, 223
Solutions, heating, 32-33 sensitivity, 198
preparation, 9 test for mercuric cyanide, 211
storage,9 Starch-potassium iodide test for free
"Soromin," reaction with hydroxamic halogens, 276
acid, 485 Stearic acid, identification, 358
Soxhlet apparatus, 40 Steel, chromium in, detection, 438-439
Special aids in spot test analysis, 8, 39 manganese in, detection, 137
Specificity of reactions, 1 molybdenum in, detection, 433
Specific reactions, 3 phosphorus segregations in, detection,
Spermidine, identification, 372 460
Spermin, identification, 372 sulfur segregations in, detection, 458
Spoons, horn, for transferring powders, Stirrer, glass, 24, 26
13 Stock solutions, 9
Spot(s), drying, 19, 34-35 Stolzite, lead in, detection, 429
Spot analysis, applications, 3 Stop watch, 40
Spot colorimetry, 7, 17 Storage bottle for solutions, 16-17
use for preliminary examination, 7 Storing and preparation of solutions, 9
Spot nephelometry, 7 Streak plates, 14
Spotplate(s),.ll, 23, 24 Strontium, barium in presence of, 165-
glass, 23 166, 168 ^
beatable, 40 magnesium in presence of, 176
porcelain, 23-24 in mixliuresr test for, 287
Spotting, 8 in presence of barium, 166, 169
lateral, 35 sodium rhodizonate test for, 169
Spraying of reagents on filter paper, 21 summary of tests, 501
Stability, of indicator papers, 23 Strontium salts, interference in cerium
of reagent papers, 23 salt reduction test for iodides, 201
SUBJECT INBEX 567
interference in zinc uranyl acetate test in explosives, test for, 488

for sodium, 176 insoluble, identification, 301
reaction with sodium rhodizonate, in "insoluble residue," detection, 228
165-166 interference in sodium carbonate-
Sublimation apparatus, 40 phenolphthalein test for carbonic
Succinic acid, identification, 300, 358, 364 acid, 255
Succinic anhydride, identification, 361, in tests for free metals and alloys,
364 273
Succinimide, identification, 364 iodine-azide test for, 237
Sucrose, reaction with chromotropic methylene blue test for, 230
acid, 395 in mixtures, test for, 283
with formaldehyde, 396 ores, detection of free sulfur in, 482
Sugars, reducing, test for, 409 precipitation by hydrogen sulfide, 22
Sulfamic acid, see Aminosulfonic acid apparatus for, 30
Sulfanilic acid, detection of nitrogen in, presence of, in iodine-azide test for
316-317 thiocyanic acid, 212
identification, 304, 367-368 reaction with picric acid ,and sodium
and a-naphthylamine test for nitrous carbonate, 212
acid, 248 with sodium nitroprusside, 226, 231
of sulfur in, 313, 317 with triphenylmethane dyestuffs, 234
Sulfates, barium rhodizonate test for, 237 reduction of insoluble sulfates to, 238
catalysis of iodine-azide reaction as reduction to, in alcohol flame, as test
test for, 301 for sulfur, 314
in fluorides, detection, 465 selenium in, test for, 465
in hydrofluoric acid, test for, 465 sodium nitroprusside test for, 239
in ink writing, test for, 454 sodium plumbite test for, 231
in inorganic fine chemicals, test for, solid, test for, 228-229
466 soluble, test by catalysis of iodine-
insoluble, identification, 301 azide reaction, 228
reduction to sulfides, 238-239 sulfites in presence of, 232
summary of tests, 504 sulfur in animal charcoal and in dyes,
tests for, 238-239 test for, 481
interference in alizarin test for zir- in rocks, iodine-azide reaction for,
conium, 154 464
in cerium salt reduction test for thiocyanates in presence of, 213
iodides, 201 thiosulfates in presence of, 241
in fluorescence test for uranium, 159 Sulfinate test by precipitation of iron
in ^-nitroso-a-naphthol test for zir- sulfinate, 363
conium, 153 Sulfinic acids, autoxidation to sulfonic
in zirconium-alizarin test for fluo- acids, 363
rides, 202 conversion to sulfite, 363
in zirconium azoarsenate test for identification tests for, 367
fluorides, 205 summary of tests, 508
in mixtures, test for, 284 Sulfite(s), bisulfites in presence of, 236
soluble, summary of tests, 504 carbonate in detection, 468
test with barium sulfate, 237 carbonates in presence of, 255
Sulfide(s), apparatus for detection, 30-31 conversion to aldehyde bisulfite, 419
carbonate in, detection, 468 conversion of sulfinic acids and sul-
carbonates in presence of, 256 fones to, 363
catalysis of iodine-azide reaction as
conversion of sulfonic acids to, 363
test for, 227, 301 cyanide in presence of, 209
as catalyst of iodine-azide reaction, interference in sodium carbonate-
240 phenolphthalein test for carbonic
corrosion of machinery metal, detec- acid, 255
tion, 459 in thioglycolic acid test for iron, 128
cyanide in presence of, 209 in mixtures, test for, 283
568 SUBJECT INDEX
Sulfite(s), nickel hydroxide test for, and nitrogen in Ihe same sample, test
233 for, 317 I
in presence of sulfides and thiosulf ates, in organic compounds, 311
reaction with 2-benzylpyridine, 236 in organic solvents, detection of traces,
with cacotheline, 87 480
with ferrous sulfate and sulfuric reaction with thallous sulfide paper,
acid, 243 277
with fuchsin, 234 segregations in iron and steel, tests for,.
with triphenylmethane dyestufEs, 458
234 selenium in, detection, 465
sodium nitroprusside test for, 231 selenium in presence of, detection, 280
in thiosulfate solutions, tests for, 235 summary of tests, 505
4-Sulfo-2,2'-dihydroxyazonaphthalene, test by reduction to sulfide in alcohol
zinc salt of, see Pontachrome blue- flame, 314
black R Sulfur dioxide, benzidine blue test for,
Sulfohydroxamic acid, reaction with 233
acetaldehyde, 366 interference in silicomolybdic acid test
Sulfonal, identification, 367 for fluorides, 206-207
Sulfones, conversion to sulfite, 363 reaction with 2-benzylpyridine, 236
identification tests for, 367 . with zinc nitroprusside, 231
summary of tests, 508 Sulfuric acid, barium carbonate and
Sulfonic acids, alkali hydroxide test for, phenolphthalein test for, 237
363 barium rhodizonate test for, 236
conversion into iron salt of acethy- in copper sulfate solution, detection,
droxamic acid as test for, 366 473
identification tests for, 367 and 2,7-dihydroxynaphthalene test for
summary of tests, 508 glycolic acid, 399, 403
Sulfo salts, reaction with sodium azide, and ferrous sulfate test for nitric acid,
.228 243
Sulfur, in carbon disulfide, detection of free, summary of tests, 504
traces, 480 . test for, 239
conversion to alkali sulfide, 314 lead in, detection, 430-431
corrosive, in motor fuels, test for, 480 and manganous sulfate test for bromic
in difficultly soluble organic com- acid_, 222
pounds, detection, 314 and phenol test for nitroso compounds,
in easily volatile organic compounds, 321
detection, 314 summary of tests, 504
in ether, detection of traces, 480 test by precipitation of_barium sulfate
free, in explosives, detection, 488 in presence of permanganate, 238
in gas-purifying masses, detection, Sulfurous acid, action on p-fuchsin, 234
482 decolorization of malachite green as
in organic liquids, detection, 483 test for, 234
in solid inorganic and organic prod- detection by reduction of ferric ferri-
ucts, detection, 482 cyanide to Turnbull's blue, 236
in sulfide ores, detection, 482 induced oxidation of nickel hydroxide
test by conversion to thiocyanate, as test for, 233
278 sodium nitroprusside test for, 231
by conversion to thiosulfate, 279 sununary of tests, 505
by formation of thallium polysul- Supernatant liquid, removal from centri-
fide, 277 fuge tube,. 32-38^
in vulcanized rubber, detection, 482 Superphosphate, distinction from phos-
fusion with alkali metals as test for', phate fertilizers, 447
313 Suspension of reagent paper in gas-detec-
in insoluble sulfides, detection, 314 tion iapparatus, 30-31
Lassaigne's test for, 313 Syntheses i& preliminary operation, 8
<7
SUBJECT INDEX 569

Tellurium dioxide, detection of selenium
dioxide in, 265
Talc, magnesium in, detection, 440 Tellurium salts, detection of cadmium in
as reagent-purifying adsorbent, 64 presence of, 75
Tannin-antipyrine test for titanium, 152 reaction with anthraquinone-l-azo-4-
Tannin-silver nitrate test for ammonia, dimethylaniline hydrochloride, 89
185 Tellurous acid, alkali stannate test for,
Tanning minerals, testing of leather for, 266
451 complex copper salt formation as test
Tantalum, reaction with curcumin, 256 for, 267
Tap water, differentiation from distilled hypophosphorus acid test for, 266
water, 478 reaction with hydriodic acid, 263
Tartaric acid, p^/3'-dinaphthol and sul- summary of tests, 505
furic acid test for, 406 Tertiary cyclic bases, siunmary of tests,
fluorescence with /S-naphthol and sul- 508
furic acid, 405 Tertiary ring bases, test with methyl
identification, 328, 364 iodide and sodium 1,2-naphtha-
reaction with 2,7-dihydroxynaphtha- quinone-4-sulfonate, 392
lene, 400. tests for, 394
with naphthoresorcinol, 402 Test tubes, micro, 25-26
sulfuric acid and gallic acid test for, Tetra-alkyl rhodamines, formation, 374
405 Tetrabase, induced oxidation as test for
summary of tests, 509 ferricyanio acid, 220
thiocyanate in presence of, 212 and manganese salts test for periodic
Tartrates, interference in potassium acid, 224
thiocyanate test for iron, 124-125 Tetrabromofluorescein (II), see Eosin
Tartrazine, identification, 367 Tetrabromophenolphthalein ethyl ester
Tartronic acid, reaction with j3,/3'- test for protein, 412
dinaphthol, 406 Tetraethyl rhodamine, see also Rhod-
with naphthoresorcinol, 402 amine B
with sulfuric and gallic acids, 405 test for antimony, 86
Teallite, tin in, 432 Tetrahydro-^-nitroso-a-naphthol, iden-
Technical materials, molybdenum in, tification, 322
detection, 433 1,2,5,8-Tetrahydroxyanthraquinone, see
spot reactions for examination of, 3, Quinalizarin
425 Tetrahy droxy dinaphthy Imethane, forma-
Tellurates, reduction to tellurium, 266, tion, 399
268 Tetrahydroxyquinone test for barium,
Telluric acid, alkali stannite test for, 266 168
complex copper salt formation as test Tetraiodofluorescein, see Erythrosine
for, 267 o-Tetralone, identification, 337
formation of stable copper salts by, Tetramethyldiaminodiphenylmethane,
133, 225 see Arnold's base
hypophosphorus acid test for, 266 p-Tetramethyldiaminodiphenylmethane,
as preventive of copper catalysis, 133 see Tetrabase
summary of tests, 505 Tetranitropentaerythrite in explosives,
Tellurites, reduction to tellurium, 266,
test for, 488
268 Textiles, detection of esters of nitric acid
Tellurium, in presence of selenium, test in threads of, 488
for, 266-267 Thallium, benzidine test for, 119
reaction with sodium rhodizonate, 57
with thiourea, 265 catalytic test for silver in presence of,
reduction of tellurites and tellurates 47
to, 266, 268 dipicrylamine as reagent for, 121
selenium in, test for, 465 manganese in presence of, 136
selenium in presence of, test for, 263 phosphomolybdic acid and hydro-
Tellurium compounds, reaction with bromic acid test for, 120
cacotheline, 88 potassium iodide test for, 119
37
570 SUBJECT INDEX
I
Thallium, in presence of lead, test for, of ferrocyanic, oxalic, phosphoric
119 and tartaric acid, 212
of mercury, potassium iodide test of halides, detection, 214
for, 119 of iodides, 212
of silver, test for, 119 of sulfides and thiosulfates, test for,
reaction with potassium bismuth io- 213
dide, 182 reaction with ferric chloride, 279
sodium carbonate as solvent for, 121- with ferrous sulfate and sulfuric
122 acid, 243
summary of tests, 501 for iron, 212
Thallium carbonate, solubility, 191 test for free sulfur by conversion to,
Thallium chloride, reaction with rhod- 278
amine B, 86 Thiocyanic acid, catalysis of the iodine-
Thallium hydroxide, reaction with mala- azide reaction as test for, 212
chite green, 162 cobalt salts test for, 214
Thallium nitrate, as reagent for alkali, in presence of sulfides and thiosulfates,
230 212
test for iodides, 202 summary of tests, 505
Thallium polysulfide formation as test Thiocyanide group, reaction with copper
for free sulfur, 277 ojcide, 311
Thallium salts, cerium in presence of, 161 Thiocyanoacetic acid, identification, 390
interference in benzidine test for lead, Thioglycolic acid, identification, 356
55 test for iron, 127-128
in o-tolidine test for copper, 67 Thioketones, iodine-azide reaction test
oxidation of benzidine by, 135 for, 353
reaction with auric chloride and palla- and mercaptans, identification tests
dium chloride, 182 for, 35&-357
with benzidine, 161 summary of tests, 508
with dipicrylamine, 179 4-Thio-a-naphthofiavone, identification,
with . potassium chromium thio- 356
cyanate, 62 Thiosulfates, carbonates in presence of,
with sodium cobaltinitrite, 178 255
Thallous selenide, formation, 280 catalysis of iodine-azide reaction as
Thallous sulfide, test for free selenium by test for, 227-228
addition to, 279 in explosives, test for, 488
Thallous sulfide paper, reaction with free interference in sodium carbonate-
selenium, 277, 279-280 phenolphthalein test for carbonic
with sulfur, 277 acid, 255
Thapsiac anhydride, identification, 361 in zirconium-alizarin test for fluo-
Thioacetamide test for bismuth, 63 rides, 202
Thioacetic acid, identification, 357-368 in zirconium azoarsenate test for
Thiocyanates, catalysis of iodine-azide fluorides, 205
reaction as test for, 227-228 iodine-azide reaction for, 279
as catalyst of iodine-azide reaction, in mixtures, test for, 284
213, 240 presence of, in iodine-azide test for
conversion into prussic acid as test thiocyanic acid, 212
for, 214 in presence of sulfides, test for, 241
cyanides in presence of, 209 reaction with cacotheline, 87
in explosives, test for, 488 with cobalt salts, 215
ferric thiocyanate test for, in presence with ferric salts, 63 _,
of iodides, 213 with ferrous sulfate and sulfuric
ferrocyanides in presence of, 217-218 acid, 243";^
formation as test for hydrocyanic acid, sulfites in presence of, 232
209 test for free sulfur by conversion to, 279
in mixtures, test for, 284 thiocyanates in presence of ,213,215,
in presence of acetate, bromide, chlo- Thiosulfate solutions, test for sulfites in,
ride, iodide, and thiosulfate, 215 235 ^
SUBJTBCT INDSZ 571
Thiomilfurio acid, summuy of tests, zirconium in presence of, 166
505 Tin compounds in antimony reduction
tiest by oatalyais of iodine-aside reac- test, 83
tion, 240 Tin phosphate in inaoluble residue, 307
Thiourea, in the Beilstein reaction, 311 Tin-plated metals, tin in, detection, 433
detection of sulfur in, 313 Tin platings, lead in, detection, 427
of sulfur and nitrogen in, 317 Tin salts, detection of cadmium in pres-
identification, 356 encO'of, 76
reaction with bismuth, mercury and detection by reduction of ferric salts,
tellurium, 265 89
with selenite, 265 identification by cacotheline reaction,
Thorium, interference in alizarin or quin- 52
alizarin test for indium, 163 interference in cacotheline test for
sirconium in presence Of, 155 ranadium, 99
Thorium fluoride in insoluble residue, 307 reaction with p-dimethylaminoazo-
Thorium salts, cerium in a mixture of phenylarsonic acid, 156
zirconium salts and, 162 reduction by hypophosphites accel-
interference in fluorescence test for erated by mercury salts, 52
uranium, 159 of phosphomolybdates by, 120
lake formation with quinalizarin, 148 Titanium, chromotropic acid test for,
reaction with p-dimethylaminoao-
phenylarsonic acid, 155 151-152, 440
with quinalizarin, 172 hydrogen peroxide test for, 150, 304
zitoonium in presence of, 154 methylene blue and zinc test for, 153
Thymol, identification, 331 in minerals, detection, 440
Thymol blue as indicator of hydrogen- in presence of chromium, iron, man-
ion concentration, 476 ganese, and uranium, 153
H a , in alloys, test for, 292-293, 428 of other elements, test for, 152
ammonium phosphomolybdate teist pyrocatechol test for, 150
for, 86 reaction with curcumin, 256
anthraquiB0ne-l-azO:4-dimethyI- in silicates, test for, 440
aniline hydrochloride teat for, 89 summary of tests, 501
antimony in presence of large sbmounts tannin-antipyrine test for, 152
of, 86 uranium in presence of, 439
in antimony salts, detection, 87 lirconium in presence of, 156
2-benzylpyridine test for, 89 Titanium dioxide, interference in fluores-
cacotheline test for, 87 cence ^ t for uranium, 159
diazine green S(K) test for^ 89 Tfitaniiun-malachite green reaction, ca-
flame color test for, 88 talysis of, as test for tungsten, 95-96
germanium in presence of, 90 Titanium oxide in insoluble residue, 304
interference in dithizone test for Titanium salts, conversion to titanium
mercury, 60 fluoride, 98
in phosphomolybdic acid test for interference in cacotheline test for tin,
vanadium, 100
luminescence reaction for, 307-308 87
magnesium in presence of, 175 reaction with p-dimethylaminoazo-
mercuric chloride and aniline test for, phenylarsonic acid, 156
89 with di8odium-l,2-dihydroxyben-
in metallic objects, detection, 432 zene-3,5-disulfonate, 126
in minerals, detection, 432 with 1,2,7-trihydroxyanthraqui-
in mixtures, testa for, 286, 288, 290 none, 89
in presence of antimony, detection, 87
reaction with sodium rhodizonate, 57 zirconium in presence of, 154
summary of tests, 501 Titanium tetrachloride test for ferro-
1,2,7-trihydroxyanthxaquinone test cyanide, 221
for, 89 Titan yellow test for magnesium, 173,176
zinc in presence of, 142 Titrimetric ajialysis, 1
572 SUBJECT nn)EX
o-Tolidine, and ammonium thiocyanate summary of tests, 501

test for copper, 67 test by catalysis of titanium-malachite
solution as reagent for liydrogen perox- green reaction, 95-96
ide, 271 zirconium in presence of, 166
Toluene as solvent, 281 Tungsten oxide, i n insoluble residue, 306
Tolylaldehyde, identification, 344 interference' in cacotheline test for
Toning baths, qualitative analysis of, tin, 88
101 properties, 94-95
Tragacanth,. identification, 411 Turbidities of spot tests as basis for
Transfer capillary pipet, 38 quantitative ana,lysis, 7
cleaning, 38 Turmeric, see Curcuma, tincture of
Transparent paper as medium for spot Tumbull's blue, distinction from Prus-
tests, 6 sian blue, 218
Tribromophenylhydrazine, identifica- formation, 221, 269, 273-274
tion, 3 ^ reduction to ferro-ferrocyanide, 122
Tricarballylio acid, identification, 358, unsuitability for spot test, 218
364 Tyrosinase, detectibn, 422
Triethanolamine, detection of mono- and Tyrosine, detection, 384
diethylamine in, 371 -nitroso-(3-naphthol test for, 411
1,2,4-Trihydroxyanthraquinone, gee Pur- summary of tests, 509
purin in urine or serum, detection, 412
1,2,7-Trihydroxyanthraquinone, as re-
agent for aluminum, chromium, iron, U
titanium, and zirconium salts, 89
as reagent for bismuth, 89 Ultraviolet light, fluorescence of dialkyl
for molybdates, 89 rhodamines in, 373
test for tin, 89 Umbelliferone, formation, 362
Trimellitic acid trimethyl ester, identifi- Uranium, aluminum in presence of, 145-
cation, 364 146
Trional, identification, 367 cobalt in presence of, 110-111
Triphenylmethane dyestufis, reaction fluorescence test for, 159
with sulfites, mono- and polysulfides, lake formation with alizarin, 144
234 in minerals, detection, 439
test for aldehydes with, 339 potassium ferrocyanide test for, 157,
Trithiourea cuprous chloride test for 439 ;
ferricyanic acid, 221 in preseiice of iron, 157
Tropaelin OO as indicator of hydrogen- of iron and copper, test for, 158
ion concentration, 474 of titanium, 439
Trotyl in explosives, test for, 488 quercetin or quercitrin test for, 159
Tschugaeff reaction for nickel, 434 sanunary of tests, 50L __
Tungstates, interference in alizarin test titanium in presence of, 163
for zirconium, 154 Uranium oxide, interference in cerium
interference in cacotheline test for salt reduction test for iodides, 201
vanadium, 99 Uranium salts, interference in cacothe-
in dipyridyl test for molybdenum, 94 line test for tin, 87
in minerals, detection, 306 reaction with alizarin, 146
reaction with p-dimethylaminoazo- with anthraquinone-l-azo-4-dimeth-
phenylarsonic acid, 156 ylaniline' hydrochloride, 89
with ferrous sulfate, 243 with quercetin or quercitrin, 128
with rhodamine B, 86 Uranyl acetate test for ferrocyanic acid,
Tungsten, diphenyline test for, 97 215 ,
in insoluble residue, 306 Uranyl ferrocyanide tesf for zinc, 142
interference in the potassium thiocy- Uranyl salts, reaction with chromotropic
anate test for molybdenum, 92 ,^ acid, 152
ores, molybdenum in, detection, 433 reaction with nitrosonaphthol, 110-111
in presence of molybdenum, test for, 95 Urea in the Beilstein reaction, 311
stannous chloride test-for, 94, 306 Urease, detection, 422
SUBJECT INDEX 573
1Jreates,j"eaction with ammonium phos- Weighing bottles, Ji4
phomolybdate, 421 ' Whatman filter paper, 19
Uric acid, reaction with ammonium phos- Wines, glycerol in, detection, 486
phomolybdate, 421 Wire sling for holding micro test tubes,
Urine, ascorbic acid in, detection, 421 33
blood in, detection, 424 Wood, spot tests for chemicals used in
protein in, detection, 414 preserving, 450
tyrosine in, detection, 412 Wool, differentiation from cotton, 485
Working methods in spot test analysis, 8
Wringer for soaked filter paper, 40
Vanadates, reaction with benzidine, 131
reaction with diphenylamine, 244 X
with diphenylcarbazide, 130
with hydrogen peroxide, 160 Xanthate test for molybdenum, 93, 306,
Vanadic acid as catalyst for alkali chlo- 433
rate solutions, 108 Xanthone dyestuffs, reaction with anti-
Vanadium, cacotheline test for, 99 mony salts, 86
hydrogen peroxide test for, 97 Xylenoi, ideutification,'330
8-hydroxyquinoline test for, 100
iron (II) dimethylglyoxime test for, 98
oxine test for, 99
phosphomolybdic acid test for, 99 Zinc, in alloys, test for, 292-293
summary of tests, 501 aluminimi in presence of, 145
Vanadium salts, catalytic oxidation of cadmium in presence of, 76
aniline to aniline black by, 99 dithizone test for, 139
Vanadyl salts as catalysts for alkali ferricyanide and diethylaniline test
chlorate solutions, 108 for, 137
Vanillin, identification, 331,334,344-346, and p-phenetidine test for, 141
indium in presence of, 163-164
348, 350 interference in ferric thiosulfate test
Vapors, action and liberation, 29 for copper, 64
as auxiliary reagents, 29 magnesium in presence of, 175
Varnishes, lead in, detection, 429 metallic, copper in test for, 426
Vegetable and animal fibers, differentia- and methylene blue test for titanium,
tion, 484
Vinegar, citric and malic acids in, 486 153
formic acid in, test for, 486 in minerals, test with ferrocyanide
Vinyl acetate, identification, 360 paper, 463
Vitamin C, see Ascorbic acid in mixtures, tests for, 286, 289, 291
Volatilization test for hydrochloric acid, in plated metals, detection, 437
potassium cobalticyanide test for, 141
193 in presence of alkali and alkaline earth
Volumetric flask, 11 metals, 142
W of aluminum, test for, 137
of aluminum salts, 139
Warming of filter paper, 32-33 of bismuth, test for, 142
Watch glasses, spot reactions on, 25 of chromium,' test for, 137
Water, copper in, detection, 427 of lead, test for, 142
differentiation between tap and dis- of nickel salts, 139
tilled, 170, 478 of tin, test for, 142
hardness, determination, 478 reduction of nitrates to ammonia by,
hydrogen sulfide in, detection, 473, 478 247
lead in, detection, 430 resorcinol test for, 141
magnesium in, 174, 477 solubility in nonoxidizing acids, 272
spot methods for judging samples of, summary of tests, 502
476 test by coprecipitation with cobalt
Wavellite, chromium in, 439 mercury thiocyanate, 140
Waxes in mineral oils, detection, 485 uranyl ferrocyanide test for, 142
574 SUBJBCT INDEX
Zinc blende, free sulfur in, detection 483 of antimony, test for, 156
lead in, detection, 429 of molybdenum, tungsten, and ti-
Zincchloride in wood preservatives, teat tanium, test for, 156
for, 450 of thorium, 155
Zinc dross, lead in, detection, 429 of tin, test for, 166
Zinc ierrocyanide paper, detection of
reaction with carminic acid, 157
iron by, 20
Zinc nitroprusside, reaction with sulfur with chlorobromoamine acid, 157
dioxide, 231 with curcumin, 256
Zinc oxide, free metal in, detection, 449 with gallocyanin, 157
lead in, detection, 429 summary of tests, 502
Zinc salts, interference in thioglyoolic Zirconium alizarinate test for fluorides,
acid test for iron, 128 307
interference in zinc uranyl acetate test Zirconium-alizarin paper, preparation,
for sodium, 176 202
reaction with alkali mercury thiocy- Zirconium-alizarin solution as reagent
anates, 140 for fluorine, 202, 312, 463
with anthraquinone-l-azo-4-dimeth- Zirconium-alizarin test for hydrofluoric
ylaniline hydrochloride, 89 acid, 202
with morin, 142 Zirconium azoarsenate paper, prepara-
Zinc sulfide paper, 20 tion, 205
Zinc Uranyl acetate test for magnesium, test for fluorides, 204
176 Zirconium salts, cerium in a mixture of
Zirconium, alizarin test for, 154 thorium salts and, 162
p-dimethylaminoazophenylarsonic lake formation with quinalizarin, 148
acid test for, 155, ^
interference in alizarin or quinalizarin reaelion with quinalizarin, 172
test for indium, 163 with 1,2,7-trihydroxyanthraqur-
/J-nitroso-a-naphthol test for, 153 none, 89
in presence of aluminum, beryllium, Zorgite, selenium in, 465
thorium, and titanium salts, 154 Zymase, detection, 423
,9 3 ^ ^"^
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Qualitative Analysis by

by FRITZ FEIGL, Eng., Dr. Sc.

Third, completely revised, English edition

ELSEVIER PUBLISHING COMPANY, Inc.

Dr. Janet W. Matthews ^ of London translated the two previous

1,2-Dicarboxylic Acids /CCOOH GroupX 360

Efforts to detect, if not all, at least a large number of cations and

experimental investigations were necessary to discover possible new sen-

II to V) that the description and recommendation of many spot reactions

' F. Feigl, Mikrochemie, 1, 4 (1923).

and relatively (with respect to dilution) small quantities of material, spot

The detection of individual metal salts in solution can almost always

accompanying materials on the certainty and sensitivity of spot tests

course, always on an appropriately diminished scale, and, so far as is feasible,

volume and the actual concentration then determined gravimetrically or

auxiliary reagents, solvents, and spot reagents in racks or blocks on the

pending on the desired accuracy,' 1

ceeding. This point requires special consideration. As a rule, it is unwise

Mere grinding of hard materials in mortars usually produces a mixture

Fig. 4. Microiaortar Fig. 5. Microsieve

Fig. 6. Microspatula (nickel) (actual size)

3. Taking and Application of Drops

Taking drops from a test solution or reagent can be done in vari-

accomplished by a very slight, partial raising of the finger. A little prac-

Fig. 8. Support for pipets, rods, etc. <i actual size)

Eigure 11 shows a small apparatus for delivering uniform drops of

Fig. 9, Fig. 10 Fig. 11

- Burets can also be used to deliver drops. In qualitative spot test

must therefore be considered in every case. The purity of the paper is an

Filter papers intended for spot reactions should be stored in vessels

It is easy to impregnate filter paper with reagents that are soluble in

5. Spot Reactions in Porcelain and Glass Vessels

The drops of test solution and reagent brought together on a spot

opinion of the characteristic reaction picture and the range of application

liquid to be evaporated. Details of the apparatus for this operation are

If water bath temperatures are not sufficient to remove volatile com-

can be heated directly by a burner or placed on a hot plate. The tempera-

ing fumes away (i actual size)

Fig. 2.3. Grooved magnesia for ignitions (actual size)

A silica watch glass can be used when evaporating small volumes of

Fig. 27 Fig. 28 Fig. 29

Sometimes it is advantageous to heat spots on paper with avoidance of

9. Separation of Solid and Liquid Phases

of rubber tubing D is fitted over the top of B. i A disk of filter paper of

Fig. 36. Filtering pipet (actual size)

minute quantities of precipitate or of small volumes of filtrate can be

operated centrifuges. The centrifuge should be provided with a metal

Fig. 39. Removing supernatant liquid from a centrifuge tube by suction

the detection of the fomuition of minimal quantities of precipitate, that can

10. Other Special Aids

Microcentrifuge: For collecting precipitates in microcentrifuge tubes

In spot analysis, as in qualitative macro- and semimicroanalysis, the

chloric acid is repeated 3 to 5 times. Finally the manganese nitrate and

(I) ' (11)

it forms OH or SH groups in such quantity that a precipitation reaction

Detection in the presence of gold, platinum, and palladium.^ Gold, plati-

Limit of Identification: 0.(H)5 y silver

The sensitivity of the mercury test with diphenylcarbazone depends

^[ProcedveA drop of the test solution is mixed with 2 drops of the

IfProcednreA drop of the test solution is placed on test paper

2Hg++ + HjPOr + 2H2O = 2Hg + POr"" + 6*H+ {2)

reduce the catalytic action of mercury.'^ Cu(II) salts are reduced by

flVocednreWhea mercmy is to be detected in neutral solution, a

alkali. BiO(OH) is formed, which is not converted by hypobromite into