V O L U M E 27, NO.

8, A U G U S T 1 9 5 5
1293
1.0
-
k3
B
p
U
PARTS PER MILLION
Figure 6. Sensitivity curves for amine
determinations
Table 11. Degree of Interference of
Ethylenimine Testa
Solution Concn., P.P.X
Reagent blank
Ethyleniniine 1
Ethanolaniine 6
Ethanolamine 10
Ethanolamine 24
Ethylenimine-ethanolamine 1 to 6
Ethylenimine-ethanolamine 1 to 10
Ethylenimine-ethanolamine 1 to 24
Chloroform extraction method.
Ethanolaniine in
Absorbance
at 420 m&
(.4v.)
0 015
0 491
0 025
0 048
0 062
0 521
0 541
0 548
small errors in timing nould not introduce appreciable errors in
the absorbance readings.
The
sensitivities of the analyses are 0.40 for ethylenimine, 0.19 for
n-butylamine, and 0.048 for ethanolamine, n here sensitivity is
defined as
Sensitivity and Adherence to the Beer-Lambert Law.
Absorbance of sample - iibsorbance of reagent blank
.~
part. per million of amine
The determinations show excellent adherence to the Beer-
Lambert law over the measurable concentration ranges (Figure
6) as well as great sensitivity. Colorimeter readings were also
made, with t,he Klett-Summerson photoelectric colorimeter,
with S o . 12 or Xo. 44 filters. These readings were likewise
linear with concentration, and the measurable concentration
ranges were about t,he same as with the Fpectrophotometer.
Degree of I nterference of Ethanolamine in the Ethylenimine
Test. The presence of a relatively high concentration of ethanol-
amine in an aqueous solution containing ethylenimine has but
slight effect on the determination of the latter by the chloroform
extraction method. Table I1 shows that the sensitivity of this
method for ethanolamine is but 1/100th that of the test for
ethylenimine.
ACKNOWLEDGiCIENT
The authors wish t,o thank Reuben Proper of this branch for
carrying out the syntheses of S-but>-lethylenimine and potaspiurn
1,2-naphthoquinone-4-sulfonate.
LITERATURE CITED
(1) Danielson, I. S. . J . Bi d. Chem. , 101, 505-22 (1933).
(2) Drake, T. L., Organic Syntheses, 1-01, 21, p. 91, Wiley,
(3) Elderfield, R. C. , J . 0,s. Chem., 14, 605-37 (1949).
(4) Folin, O., J . Bi d. Chem. , 51, 377-91 (1922).
(5) Lange, -4. L., Handbook of Chemistry, 6th ed., p. 1102,
(6) Letonoff, T. V., and Reinhold, J . G., Am. J . Me d . Sci., 188, 142
(7) Schmidt, E. G., ISD. ENG. CHEY. , ASAL. ED., 11, 99--100
(8) Schmidt, E. G., J . Bi d. Chena., 122,757 (1938).
(9) Shirley, D. A, Preparation of Organic Intermediates, p. 153,
(10) Sullivan, hf. X., and Hess, W. C., Public Health Rept s . ( C7. S, ) ,
New York, 1941.
Handbook Publishers, Sandusky, Ohio, 1946.
(1934).
(1939).
-
Wiley, Sew York, 1951.
44,1421-8,1699-608 (1929).
RECEI VED for review Se~iteinber 2, 1934. .-iccepted .\pril 2, 195.5.
Col ori met ri c Determi nati on of the Perchl orat e Ion
WOLF BODENHEIMER and HANNAH WEILER
An al y t i c al Labor at or y, Sci ent i f i c Depar t ment , Mi n i s t r y o f Def enc e, Jer usal em, Isr ael
The perchlorate ion gives a precipitate with the cupric
tetrapyridine cation. The ensuing decrease in the color
intensity of solutions of cupric tetrapyridine ion can be
measured spectrophotometrically and used for the
quantitative determination of the perchlorate ion. The
method has also been applied to the determination of
the perchlorate ion in organic perchlorates.
UPRIC tetrapj-ridine perchlorate, studied aiid characterized
C by Weinland, Effinger, and Beck ( a) , had been suggested by
Shead and Bailey ( 1 ) as a means of identifying the perchlorate
ion. The object of the present investigation n-as to use the cu-
pric tetrapyridine complex for the quantitative estimation of the
same ion. The solubility of the cupric tetrapyridine perchlorate
in water, although slight. excludes a gravimetric method. How-
ever, the solutions of salts of the cupric tetrapyridine complex in
aqueous pyridine show an intense blue color, the intensity of
which decreases as part of the complex is precipitated as per-
1 Present address, Geological I nsti tute, I srael hlinistry of Development
and Hebrew University, J erusaleni, Israel.
chlorate. This fact makes the colorimetric determination of
perchlorate possible.
INORGi UIC PERCHLORiTES
Using the conditions described b - Shead and Bailel- ( 1 ) a solu-
tion of cupric tetrapyridine nitrate in a mixture of water and pvri-
dine IT as prepared; varying quantities of ammonium perchlo-
rate were added to equal volumes of this solution and after crys-
tallization of the cupric tetrapyridine perchlorate, the absorb-
ance of the solutions -A-as measured. -1 curve v-as thus obtained,
showing the absorbance of a solution of the complex as a function
of the amount of perchlorate added. The results obtained ni th
this curve, hom-ever. nere satisfactory only as long as no ions other
than perchlorate and nitrate were present. Quantities of chlo-
rate, chloride, or sulfate, of the same order of magnitude as the
amount of perchlorate present. affected the color or gave precipi-
tates. As i t is often necessary to determine the perchlorate in
the presence of these interfering ions, conditions rrere sought
under which their influence was suppressed.
The folloir-ing four points nere studied.
1294 A N A L Y T I C A L C H E M I S T R Y
Table I. Influence of \.arious Salts on Absorbance of Solutions of Cupric Tetrapyridine Sitrate
__-- ~~ Salts Added. l I g./l I l . ~~
XR?SO$ KCLo:i__ HSOa, XHICL. .\IqCI?. CaCl ?, BaCI ?.
Xone 8 20 8 20 20 20 2i) ' 0 20
Absorbance of solutions
Containing 0.2 mg. h l . of perchlorate 0 673 0 6i i i 0.040 0.642 0.672 0.682 0. 681
Containing 0.4 nig./nil. of perchlorate 0.481 . . . 0.498 o:& 0.501 0 . x ~ 0. 508 0.501 o:Si i o' i i i
Table IJ.
Temp..
Influence of Temperature on Absorbance of
Cupric Tetrapj-ridine Kitrate Solution
0 c. 11 71 25 30 35 40 45 50
Absorbanre 0. 279 0 2 G i 0.263 0.255 0. 243 0. 232 0 . 2 2 2 0.17:
Effect of Pyridine Concentration. The addition of more pyri-
dine to the solution prevented the formation of precipitates by
sulfates or cthlorides, and deepened the color of the cuprir tetra-
pyridine complex. Figure 1 shows the variation of the absorbance
of a solution of the coniples as a function of the quantity of
pyridine added. .it eqiial volumes of water and p>-ridine, the
maximum absorbance of the complex is practically reached.
Further additions of pyridine increase the soluhility of the rupric
tetrapJ -ridine perchlorate and must, therefore. be avoided.
Effect of Various Anions on Color of Complex. The absorbance
of solutions containing varying quantities of sodium chloride,
sodium sulfate. potnssium bromide, or potassium nitrate \Tar;
measured (Figure 2'1. Sodium chloride solutiom give the deepePt
color n-ith the cupric tetrapyridine complex, bromide has a
smaller influence. and sulfate and nitrate do not change the color
at all. J Ioreover. in the presence of a high concentration of
sodium chloride the effect of other anions (chlorates. phosphates,
nitrates, bromides, etc.) on the color of the solution was almost
entirely suppressed (Tables I and 111).
Effect of Various Cations. The presenre of sodium, potasi um,
ammonium ions, or of alkaline earth metals in concentrations up to
10 mg. per nil. has no influence. Higher concentrations affect
the extinction slightly (Table I ). Other metals (silver, manga-
nese, iron, aluminum. zinc). on the other hand, were found to form
either compleses Kith pyridine or precipitates of the hydroxides;
they have, therefore. to be removed before determination of the
perchlorate.
Effect of Temperature. The effect of changcs of temperature
on the color of the solution is shown in Table 11.
I n the range between 10" and 25' C. there is very little change
in the absorbance of the solution.
PROCEDURE
As a result of these studies the following method waq adopted.
Thrce stock solutions are required.
Solution A. Ai solution prepared by dissolving about 25 grams
of cupric nitrate trlhydrate in water, adding 540 ml. of pyridine,
and making up xi th nxter to 1 liter. (Kept in a brown bottle,
this solution did not change its optical properties for at least 2
years.)
Solution B. -i n aqueouc solution of 20 grams of sodium chloride
per 100 ml.
Solution C. -1 solu-
tion containing 58.75
mg. of ammonium per-
chlorate per nil. (50 nig.
of perchlorate anion per
ml.).
Preparation of Cali-
bration Curve. &%dozen
solutions are prepared
containing: 2 nil. of solu-
tion A; 20 ml. of solu-
tion B; varying quanti-
ties of solution C (in-
creasing gradually the
perchlorate cmtent i n
the final Polutions from
zero to 1.6 nig. per nil.);
and watcr to 2.5 nil.
These solutions are left for 48 hours to crystallize (for con-
centrations up to 0.5 mg. per ml. 24 hours are sufficient). The
solutions are filtered and the absorbances of the filtrates are
measured in a Beckman DC spectrophotometer at 6350 A. The
results are plotted against the concentrations of perchlorate ion,
as shown in Figure 3.
A solution is prepared from the sample
as described in the preparation of the calibration curve ( 2 ml. of
solution A, 20 ml. of solution B, a weighed quantity of the un-
knom sample, and water to 25 ml.). After 48 hours, the ahsorb-
ance of the supernatnnt solution is measured, and the concentra-
tion of perchlorate is rei d from the cslibration curve. (For tech-
, results can be obtained after a few hours if
the solution is shaken mechanically. The calibration curve has
then to be prepared under the changed conditions. The accuracy
of the method n-ill be reduced, but n-ill still suffice in many cases.)
RESCLTS
Analysis of Sample.
I n Table I11 results are given of determinations carried out
both in the absence and in the presence of other salts. The ac-
curacy of the method is within 0.01 mg. per ml. At concentrations
of 0.5 to 1.2 mg. of perchlorate per nil.. the error lies between 1 and
2%.
If the concentration of other ions in the soliltion rises above 10
0 5 10
Pyr i di ne Ad d ed , ML/5 MI. Sol uti on
Absor bance
Figure 1. Change in color intensity of cupric
tetraprridine nitrate solution on addition of
pyridine
0 9.0 4.0 6.0 8. 0 10.0 19.0
Figure 2. Change in color intensity of cupric tetrapyidine nitrate solution on
addition of anions
A. NaCladded C. Na2SOI added
B. KBradded D. KNOa added
V O L U M E 27, NO. 8, A U G U S T 1 9 5 5 1295
1 .o or more, \%hich is not sufficient
for organic analyses. For solu-
tions saturated with sodium chlo-
ride the calibration curve is
:"0.5 practicallv a straight line for
4 much lo\ver concentrations. I t is
thus possible to determine quan-
2
tities of perchlorate even helon-
100 y per ml. with an accuracj-
within &5 -1.
Y
2
0
0 0.5 1 .o 1. 5 2.0 2.5 PROCEDURE
Perchlorate Added, Mg./MI.
Preparation of Calibration
Curve. Solutions of potassium per-
Figure 3. Calibration curve for inorganic perchlorates
0.400
0.300
W U
Z
Q
p 0.200
0
2
Q
0.100
0
0 0.2 0.4 0.6 0.8 1 .o
Calibration curie for organic perchlorates
Perchlorate Added, Ms./MI.
Figure 4.
mg. per ml.. in some cases slight deviations occur nhich, however.
do not cause an erior gretater than 0.03 mg. per ml. If very high
concentrations of another ion are prespnt, it is advisable to pre-
pare a calibration ciirve cor1 cspondirig to these conditions.
ORG.41UIC PERCHLO RriTES
Owing to their l o ~ eoluhility in \Tater. organic perchlorates are
often used for the separation and purification of organic bases.
R7hilr the comblistion :insl>-sis of thrse perchlorates is not prac-
tical, bemuse of their tentietic>. to explosive decomposition. the
colorimetric method desrrihctl above ni:dies i t possible to deter-
mine the perchlornte ion tlirec>tlj-. even in wry dilute solutions
of the salts.
Under the conditions tlrwrihed. optimal accuracy is ohtnined
only with quantities of ahout 0.12 mg. of perchlorate ion per nil.
chlorate are prepared containing
0.0, 1.0, 2.5, 5.0, 7. 5, 10.0, 12.5.
15.0, 20.0, and 50.0 mg. of perchlorate ion, respectively, 2 ml. of
stock solution A. and water to 25 ml. These solutions are satu-
rated with an eicess of dry sodium chloride of analytical grade.
They are t,hen shaken vigorously, left to crystallize overnight,
and filtered through dry filter paper. The absorbance of the fil-
trates is measured in a Klett-Summerson colorimeter with filter
66 (hnsmi ttance range from 6400 to 7000 L4,), and is plotted
against the concentration of the perchlorate ion (Figure 4).
Analysis of Sample. The sample is dissolved in water to a con-
centration of betn-een 50 and 600 y of perchlorate ion per ml. A
volume of 2 ml. of stock solution A is added, and the solution is
made up to 25 ml. If only very small quantities of sample are
available, this volume can be correspondingly smaller, the only
limit being that required for the colorimetric measurement. This
solution is shaken with an escess of dry sodium chloride, kept
overnight, and filtered. The absorbance of the filtrate is measured
and the perchlorate ion content is read from the calibration curve.
RESUL TS
The percentage of perchlorate ion contained in the organic per-
chlorate is readily obtained from the perchlorate contrnt of the
solution. The molecular weight of the organic compound can
be derived from this drtermination. Table I V shone results oh-
tained b\ this method.
ACKY OWL EnGME\T
The autbo1.s \\.ish to thank Felix Bergmann for the suggestion
to extend their method to organic perchlorates, and E. D. Berg-
mann for the interest shomn in this Tvork.
This investigation has hen carried out under the auspices of
the Israel Mi ~~i stry of Defence.
LI TERATURE CI TED
(1) Shead, d. C., and Bailey, P. S., Mi kr ochemi e, 33, 1 (1947).
( 2) Weinland, R., Effinger, K., and Beck, V., Arch. Pharm., 265, 352
RECEI VED for review September 16, 1954.
(1927).
Accepted April 12, 1955.
Table 111. Results Obtained Using Calibration Curve (Figure 3)
.______
Salt Present Besides NaC1, Mg./l I I .
KBr, SaZSOA, KCIOZ, KSOa, PiHaCI, BaCI ?, CaClz, BImClr, KBr,
8 Sone 8 8 8 8 8 8 "8 8 None
Added 0.48 0 . d2 0 56 0.60 0.68 0.72 0.76 0.84 0.88 0.92 1 .oo
Found 0.47 0.52 0.57 0.60 0.69 0.73 0.76 0.85 0.89 0 90 0 98
Perchlorate, mg./nil.
Table IV. Determination of Perchlorate Ion in Various Organic Perchlorates
hIolecular Weight
Substance Found Theoretical Found Theoretical
70 of Perchlorate I on
Benzoylcholine perchlorate 32.2, 32.4,31.9, 32.4, 32.3 32.4 308, 307. 312, 307, 308 307
Quinaldine perchlorate 42.4, 41.5, 42.0 40.4 236. 240, 217 243,7
Trirnethylbutylammoniuni perchlorate 45.8, 46.6 46.2 217, 214 213 5
Trirnethyloctylainrnoniuni perchlorate 36.1, 37.4. 37.3 36 6 276, 266, 267 271.5
Trirnethyldodecylanimoniuin perchlorate 30.9, 30.6 30.4 322, 325 328
Brucine perchlorate 19.7, 20.3 20.1 502, 490 495
Trimethylheptylarninonium perchlorate 39.3, 38.1, 38.6 38.8 254, 262. 258 257.5