Fifth Edition

Revised by
VOGEL'S
G. Svehla, Ph.D., D.Sc., F.R.I.C.
Reader in Analytical Chemistry,
Queen's University, Belfast
TEXTBOOK OF
MACRO AND SEMI MI CRO
QUALITATIVE INORGANIC
ANALYSIS
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Longman London and New York
CHAPTER I THE THEORETICAL BASIS OF
QUALITATIVE ANALYSIS
A. Chemical formulae and equations
I. 1 Symbols of elements
1.2 Empirical formulae
1.3 Valency and oxidation number
I .4 Structural formulae
1.5 Chemical equations
B. Aqueous solutions of inorganic substances
1.6 Electrolytes and non-electrolytes
1.7 Electrolysis, the nature of electrolytic conductance, ions
1.8 Some properties of aqueous solutions
1.9 The theory of electrolytic dissociation
I. 10 Degree of dissociation. Strong and weak electrolytes
I. 1 1 The independent migration of ions. Calculation of
conductivities from ionic mobilities
I. 12 Modem theory of strong electrolytes
I. 13 Chemical equilibrium; the law of mass action
I. 14 Activity and activity coefficients
C. Classical theory of acid-base reactions
I. 15 Acids, bases, and salts
I. 16 Acid-base dissociation equilibria. Strength of acids and bases
I. 17 Experimental determination of the dissociation equilibrium
constant. Ostwald's dilution law
I. 18 The dissociation and ionic product of water
I. 19 The hydrogen-ion exponent (pH)
1.20 Hydrolysis
1.2 1 Buffer solutions
1.22 The experimental determination of pH
D. The Br9nsted-Lowry theory of acids and bases
1.23 Definition of acids and bases
FROM PREFACE TO THE FIRST EDITION
Experience of teaching qualitative analysis over a number of years to large
numbers of students has provided the nucleus around which this book has been
written. The ultimate object was to provide a text-book at moderate cost which
can be employed by the student continuously throughout his study of the subject.
It is the author's opinion that the theoretical basis of qualitative analysis, often
neglected or very sparsely dealt with in the smaller texts, merits equally detailed
treatment with the purely practical side; only in this way can the true spirit of
qualitative analysis be acquired. The book accordingly opens with a long
Chapter entitled 'The Theoretical Basis of Qualitative Analysis', in which most
of the theoretical principles which find application in the science are discussed.
The writer would be glad to hear from teachers and others of any errors which
may have escaped his notice: any suggestions whereby the book can be improved
will be welcomed.
A. I. Vogel
Woolwich Polytechnic London S.E.18
THE THEORETICAL BASIS OF
CHAPTER I QUALITATIVE ANALYSIS
A. CHEMICAL FORMULAE AND EQUATIONS
1.1 SYMBOLS OF THE ELEMENTS To express the composition of
substances and to describe the qualitative and quantitative changes, which occur
during chemical reactions in a precise, short, and straightforward way we use
chemical symbols and formulae. Following the recommendations of Berzelius
(181 l), the symbols of chemical elements are constructed by the first letter of
their international (Latin) names with, in most cases, a second letter which
occurs in the same name. The first letter is a capital one. Such symbols are:
0 (oxygen, oxygenium) H (hydrogen, hydrogenium), C (carbon, carbonium),
Ca (calcium), Cd (cadmium), C1 (chlorine, chlorinum), Cr (chromium), Cu
(copper, cuprum), N (nitrogen, nitrogenium), Na (sodium, natrium), K (potas-
sium, kalium), etc. As well as being a qualitative reference to the element, the
symbol is most useful in a quantitative context. It is generally accepted that the
symbol of the element represents 1 atom of the element, or, in some more specific
cases, 1 grammatom. Thus C represents 1 atom of the element carbon or may
represent 1 grammatom (12.01 1 g) of carbon. In a similar way, 0 represents
one atom of oxygen or one grammatom (15.9994 g) of oxygen, H represents
one atom of hydrogen or 1 grammatom (1.0080 g) of hydrogen etc. Names,
symbols, and relative atomic masses of the elements are given in Section IX.l.
1.2 EMPIRICAL FORMULAE To express the composition of materials
whose molecules are made up of more atoms, empirical formulae are used.
These are made up of the symbols of the elements of which the substance is
formed. The number of atoms of a particular element in the molecule is written
asa subscript after the symbol of the element (but 1 is never written as a subscript
as the symbol of the element on its own represents one atom).
Thus, the molecules of carbon dioxide is formed by one carbon atom and two
oxygen atoms, therefore its empirical formula is C02. In the molecule of water
two hydrogen atoms and one oxygen atom are present, therefore the empirical
formula of water is H20. In the molecule of hydrogen peroxide on the other hand
there are two hydrogen and two oxygen atoms present, its empirical formula is
therefore H202.
Although there are no strict rules as to the order of symbols appearing in a
formula, in the case of inorganic substances the symbol of the metal or that of
hydrogen is generally written first followed by non-metals and finishing with
oxygen. In the formulae of organic substances the generally accepted order is
C, H, 0 , N, S, P.
1
EXPERIMENTAL TECHNIQUES
QUALITATIVE
CHAPTER II INORGANIC ANALYSIS
11.1 INTRODUCTION Before the student attempts to carry out the analyti-
cal reactions of the various cations and anions detailed in Chapters 111 and IV,
he should be familiar with the operations commonly employed in qualitative
analysis, that is with the laboratory technique involved. It is assumed that the
student has had some training in elementary practical chemistry; he should be
familiar with such operations as solution, evaporation, crystallization, distil-
lation, precipitation, filtration, decantation, bending of glass tubes, preparation
of ignition tubes, boring of corks, and construction of a wash bottle. These will
therefore be either very briefly discussed or not described at all in the following
pages.
Qualitative analysis may be carried out on various scales. In macro analysis
the quantity of the substance employed is 0.5-1 gram and the volume of
solution taken for the analysis is about 20 ml. In what is usually termed semi-
micro analysis, the quantity used for analysis is reduced by a factor of 0.1-0.05,
i.e. to about 0.05 gram and the volume of solution to about 1 ml. For micro
analysis the factor is of the order of 0.01 or less. There is no sharp line of
demarcation between semimicro and micro analysis: the former has been called
centigram analysis and the latter milligram analysis, but these terms indicate
only very approximately the amounts used in the analysis. It will be noted that
only the scale of the operations has been reduced; the concentrations of the
ions remain unchanged. Special experimental techniques have been developed
for handling the smaller volumes and amounts of precipitate, and these will be
described in some detail. For routine analysis by students, the choice lies be-
tween macro and semimicro analysis. s here aremany advantages in adopting
the semimicro technique; these include :
(i) Reduced consumption of chemicals with a considerable saving in the
laboratory budget.
(ii) The greater speed of the analysis, due to working with smaller quantities
of materials and the saving of time in carrying out the various standard opera-
tions of filtration, washing, evaporation, saturation, with hydrogen sulphide,
etc.
(iii) Increased sharpness of separation, e.g. washing of precipitates can be
carried out rapidly and efficiently when a centrifuge replaces a filter.
(iv) The amount of hydrogen sulphide used is considerably reduced.
(v) Much space is saved both on the reagent shelves and more especially
in the lockers provided immediately below the bench for the housing of the
CHAPTER Ill REACTIONS OF THE CATIONS
111.1 CLASSIFICATION OF CATIONS (METAL IONS) INTO ANALYTI-
CAL GROUPS For the purpose of systematic qualitative analysis, cations
are classified into five groups on the basis of their behaviour against some
reagents. By the systematic use of these so-called group reagents we can decide
about the presence or absence of groups of cations, and can also separate these
groups for further examination. Systematic qualitative analysis by separations
will be dealt with extensively in Chapter V, but the reactions of cations will be
dealt with here according to the order defined by this group system. Apart from
being the traditional way of presenting the material, it makes the study of these
reactions easier because ions of analogous behaviour are dealt with within one
group.
The group reagents used for the classification of most common cations are
hydrochloric acid, hydrogen sulphide, ammonium sulphide, and ammonium
carbonate. Classification is based on whether a cation reacts with these reagents
by the formation of precipitates or not. It can therefore be said that classifi-
cation of the most common cations is based on the differences of solubilities of
their chlorides, sulphides, and carbonates.
The five groups of cations and the characteristics of these groups are as
follows :
Group Z Cations of this group form precipitates with dilute hydrochloric acid.
Ions of this group are lead, mercury(I), and silver.
Group ZZ The cations of this group do not react with hydrochloric acid, but
form precipitates with hydrogen sulphide in dilute mineral acid medium. Ions
of this group are mercury(II), copper, bismuth, cadmium, arsenic(III), arsenicv),
antimony(III), antimony(V), tin(II), and tin(III)(IV). The first four form the sub-
group IIa and the last six the sub-group IIb. While sulphides of cations in
Group IIa are insoluble in ammonium polysulphide, those of cations in Group
IIb are soluble.
Group ZZZ Cations of this group do not react either with dilute hydrochloric
acid, or with hydrogen sulphide in dilute mineral acid medium. However they
form precipitates with ammonium sulphide in neutral or ammoniacal medium.
Cations of this group are cobalt(II), nickel(II), iron(II), iron(III), chromium(III),
aluminium, zinc, and manganese(I1).
CHAPTER I V REACTIONS OF THE ANIONS
IV.l SCHEME OF CLASSIFICATION The methods available for the
detection of anions are not as systematic as those which have been described in
the previous chapter for cations. No really satisfactory scheme has yet been
proposed which permits of the separation of the common anions into major
groups, and the subsequent unequivocal separation of each group into its
independent constituents. It must, however, be mentioned that it is possible to
separate the anions into major groups dependent upon the solubilities of their
silver salts, of their calcium or barium salts, and of their zinc salts; these how-
ever, can only be regarded as useful in giving an indication of the limitations of
the method and for the confirmation of the results obtained by the simpler
procedures to be described below.
The following scheme of classification has been found to work well in practice;
it is not a rigid one since some of the anions belong to more than one of the
subdivisions, and, furthermore, it has no theoretical basis. Essentially the
processes employed may be divided into (A) those involving the identification
by volatile products obtained on treatment with acids, and (B) those dependent
upon reactions in solution. Class (A) is subdivided into (i) gases evolved with
dilute hydrochloric acid or dilute sulphuric acid, and (ii) gases or vapours
evolved with concentrated sulphuric acid. Class (B) is subdivided into (i) pre-
cipitation reactions, and (ii) oxidation and reduction in solution.
CLASS A
(i) Gases evolved with dilute hydrochloric acid or dilute sulphuric acid :
Carbonate, hydrogen carbonate, sulphite, thiosulphate, sulphide,
nitrite, hypochlorite, cyanide, and cyanate.
(ii) Gases or acid vapours evolved with concentrated sulphuric acid.
These include those of (i) with the addition of the following: fluoride,
hexafluorosilicate,* chloride, bromide, iodide, nitrate, chlorate (DANGER),
perchlorate, permanganate (DANGER), bromate, borate? hexacyanoferrate(II),
hexacyanoferrate(III), thiocyanate, formate, acetate, oxalate, tartrate, and
citrate.
* This is often included in Class B(i).
SYSTEMATIC QUALITATIVE
CHAPTER V
V.l INTRODUCTION In the scheme of analysis to be described in the
following pages, it is assumed that the student is already familiar with the tests
and operations described in the preceding chapters. It will be shown how these
isolated facts are incorporated in the systematic methods of qualitative analysis,
applicable not only to simple solid substances, but also to mixtures of solid
substances, to liquids, to alloys, and to 'insoluble' substances, i.e. substances
which are insoluble in aqua regia and acid solvents.
It must be emphasized that the object of qualitative analysis is not simply to
detect the constituents of a given mixture; an equally important aim is to
ascertain the approximate relative amounts of each component. For this
purpose 0.5-1 g of the substance is usually employed for the analysis; the
relative magnitudes of the various precipitates will provide a rough guide as to
the proportions of the constituents present.
Every analysis is divided into three parts:
1. The preliminary examination. This includes preliminary examination by dry
tests, examination of the volatile products with sodium hydroxide solution
(for ammonium), and with dilute and concentrated sulphuric acid (for acid
radicals or anions).
2. The examination for metal ions (cations) in solution.
3. The examination for anions in solution.
The substance to be analysed may be: (A) solid and non-metallic, (B) a liquid
(solution), ( C) a metal or an alloy, and (D) an 'insoluble' substance. Each of
these will be discussed separately.
V.2 PRELIMINARY TESTS ON NON-METALLIC SOLID SAMPLES
1. Appearance The appearance of the substance should be carefully noted;
a lens or microscope should be used ifnecessary. Observe whether it is crystalline'
or amorphous, whether it is magnetic and whether it possesses any characteristic
odour or colour.
Some of the commonly occurring coloured coinpounds are listed below:
Red: Pb304, As,S,, HgO, HgI,, HgS, Sb,S,, CrO,, Cu,O, K,[Fe(CN),];
dichromates are orange-red; permanganates and chrome alum are reddish-
purple.
Pink: hydrated salts of manganese and of cobalt.
Yellow: CdS, As,S,, SnS,, PbI,, HgO (precipitated), K,[Fe(CN),] . 3H20;
chromates; iron(II1) chloride and nitrate.
Green: Cr203, Hg,I,, Cr(OH),; iron(I1) salts, e.g. FeSO4.7H2O,
SEMIMICRO QUALITATIVE
CHAPTER VI
VI.1 INTRODUCTION It is assumed that the student is already familiar
with the operations (ignition tests, blowpipe tests, flame tests, borax bead tests,
precipitation, filtration, evaporation, etc.) described in Sections 11.1 to 11.3.
A detailed description of semimicro apparatus and of semimicro analytical
operations is given in Section 11.4. The student should read this carefully and
thus acquire a general knowledge of semimicro technique. To secure the intro-
ductory practical experience the following course of instruction may be followed.
Reactions are normally carried out in 4 ml test-tubes or in 3 ml centrifuge tubes,
unless otherwise stated. The solutions employed in testing for cations or anions
contain 10 mg of cation or anion per ml. For purposes of calculation a drop of
solution may be assumed to have a volume of 0.05 ml; this will help in rough
computations as to volumes required in adding excess of reagents, etc.
For the cations, a limited number of preliminary reactions should be studied
first, followed by an analysis of a mixture or solution containing a member or
members of each group. This will give practical experience in the routine
operations of semimicro analysis and also provide practice from the very outset
in the use of Group Separation Tables. Particular attention should be paid to:
(i) the exact experimental conditions of the reaction;
(ii) the colour and physical characteristics (e.g. whether crystalline,
amorphous or gelatinous) of each precipitate; and
(iii) the solubility of each precipitate in excess of precipitant, or in solutions
of other reagents.
VI.2 THE STUDY OF REACTIONS OF CATIONS AND ANIONS ON
THE SEMIMICRO SCALE Before attempting to analyse unknown samples
with semimicro techniques, it is worth while to study, in semimicro scale, some
of the reactions of cations and anions described in Chapters I11 and IV. To
illustrate the manner In which the simple reactions should be carried out, a few
selected examples will be given.
Reactions of lead ions, Pb +
1. Dilute hydrochloric acid Place 2 drops of the test solution in a 3 ml centri-
fuge tube, and add 2-3 drops of dilute HCl. Note the colour and characteristics
of the precipitate. Centrifuge the mixture, balancing the tube with another
similar tube containing an approximately equal volume of water. Remove the
supernatant liquid, termed the centrifugate, by means of a capillary dropper to
REACTIONS OF SOME
CHAPTER VII
VI1.l INTRODUCTION In the previous chapters the discussions were
restricted to those cations and anions which occur most often in ordinary
samples. Having studied the reactions, separation, and identification of those
ions, the student should now concentrate on the so-called 'rarer' elements.
Many of these, like tungsten, molybdenum, titanium, vanadium, and beryllium,
have important industrial applications.
The term 'rarer' elements as originally employed in the sense of their com-
parative rare occurrence and limited availability must now, in a number of cases,
be regarded as a misnomer. Large quantities of some of these elements are
utilized annually, and the range of their application is slowly but surely widening.
A few examples may be mentioned : the use of molybdenum, tungsten, titanium,
and beryllium in the steel industry, of tungsten in the manufacture of in-
candescent lamps, and of titanium and uranium in the paint industry. The
interpretation of the term 'rarer' elements, as applied to the elements described
in this chapter, is perhaps best accepted in the sense of their comparatively rare
occurrence in routine qualitative analysis.
No attempt has been made to give more than a short introduction to the
subject; to economize in space, most of the simple equations have been omitted.
The elements have been classified, in so far as is possible, in the simple groups
with which the student is already familiar, and methods of separation have been
briefly indicated. Thus thallium and tungsten are in Group I; molybdenum,
gold, platinum, selenium, tellurium, and vanadium in Group I1 ; and beryllium,
titanium, uranium, thorium, and cerium in Group 111. The presence ofvanadium
will be revealed by the blue colour and absence of precipitate produced by
hydrogen sulphide in acid solution; its actual isolation as sulphide is effected by
the addition of acid to the ammonium sulphide solution in Group IIIB. It is
hoped that the subject- matter of this chapter will suffice to enable the student to
detect the presence of one or two of the less common ions.
VII.2 THALLIUM, TI (A,: 204.34) - THALLIUM(1) Thallium is a heavy
metal with characteristics reminiscent of lead. It melts at 302.3OC. Thallium
metal can be dissolved readily in nitric acid; it is insoluble in hydrochloric acid.
Thallium forms the monovalent thallium(1) and trivalent thallium(II1) ions,
the former being of greater analytical importance. Thallium(II1) ions are less
frequently encountered in solutions, as they tend to hydrolyse in aqueous
solution, forming thallium(II1) hydroxide precipitate. Thallium(1) ions can be
AN ABBREVIATED COURSE
OF QUALITATIVE
CHAPTER Vlll INORGANIC ANALYSIS
VIII.l INTRODUCTION In many universities and colleges there is not
enough time allocated in the curriculum to carry out a full study of qualitative
inorganic analysis. For such institutions the abbreviated course, described in
the present chapter can be recommended. With good preparation and organ-
ization such a course can be completed within 24 to 48 hours net laboratory time.
It can also be recommended as a course to those whose main interests lie outside
chemistry, but who wish to acquire some knowledge of qualitative inorganic
analysis.
It is assumed that the student is familiar with the laboratory operations
described in Chapter 11. First, most important reactions of a limited number of
cations and anions should be studied, followed by preliminary tests, testing for
anions in mixtures and separation of cations.
V111.2 REACTIONS OF CATIONS AND ANIONS For the abbreviated
study, a selected number of cations and anions only should be studied, and only
the most important reactions should be carried out.
The following reactions should be tried in the laboratory:
CATIONS
Pb2 +
Hg? +
Ag+
Hg2 +
Bi3+
c u2 +
Cd2+
As3+
As5 + (As0:-)
Sb3+
Sn2 +
Sn4 +
Fe2+
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
Section
m.4, reactions 1, 5, 6, 7, 16a.
[IS, reactions 1, 3, 10.
M.6, reactions 1, 5, 6, 12.
M.8, reactions 1, 3, 6, 1 1.
E.9, reactions 1, 2, 6, 7, 11.
E.10, reactions 1, 2, 3, 5, 6, 8, 14.
m.11, reactions 1, 2, 4, 9.
E.12, reactions 1, 2, 3.
M.13, reactions 1, 2, 3, 4.
l.15, reactions 1, 2, 8.
1.18, reactions 1, 2, 3.
1.19, reactions 1, 3,4.
1.21, reactions 1, 2, 3,4, 6, 7, 8, 9.
APPEN DlX
M.1 RELATIVE ATOMIC MASSES OF THE ELEMENTS
Element
- --
Symbol Atomic Relative Log of
number atomic mass relative
(1971) atomic mass
Actinium
Aluminium
Americium
Antimony
Argon
Arsenic
Astatine
Barium
Berkelium
Beryllium
Bismuth
Boron
Bromine
Cadmium
Calcium
Californium
Carbon
Cerium
Cesium
Chlorine
Chromium
Cobalt
Copper
Curium
Dysprosium
Einsteinium
Erbium
Europium
Fermium
Fluorine
Francium
Gadolinium
Gallium
Germanium
Gold
Hafnium
Helium
Holmium