THE COLORIMETRIC DETERMINATION OF PLATINUM WITH

5- (p-DIMETHYLAMINOBENZYL1DENE)-RHODANINE'

E. PIERCY
FRANCES AND D. E. RYAN
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Department of Chemistry, Dalhousie University, Halifax, Nova Scotia

Received October 17. 1962

ABSTRACT
5-(p-Dimethylaminobenzy1idene)-rhodanineis used to determine 0.5 to 6 p.p.m. of platinum
calorimetrically, after reduction of platinum IV with ascorbic acid. Platinum can be deter-
mined in the presence of a 10-fold excess of palladium; low concentrations of the other
platinum metals, except rhodium, do not seriously interfere.

INTRODUCTION
The colorimetric methods that have proved successful for the determination of platinum
involve the use of valences lower than the usual quadrivalent state. The widely used
stannous chloride method (I) contains tin, platinum, and chloride in a complex in which
the platinum has a valence of zero (2). Both the p-nitrosodimethylaniline (3), and the
N,iVr-bis(3-dimethylaminopropyl)-dithiooxamide (4) procedures make use of the bivalent
state, reduction of quadrivalent platinum occurring either through the action of excess
reagent or by deliberate addition of a reducing agent. The colorimetric method described
herein constitutes part of the results of an investigation into the use of the bivalent
For personal use only.

state in the determination of platinum.

EXPERIMENTAL
Preliminary
In preliminary studies, a large number of compounds were investigated as possible reagents for reducing
platinum, a t rooni temperature and in dilute acid solution, from the quadrivalent to the bivalent state.
Since 9-nitrosodimethylaniline gave immediate color development with bivalent platinum a t room tem-
perature, but not with quadrivalent platinum, the compound being investigated was added to platinum
IV solutions containing p-nitrosodimethylaniline and the development of coIor taken as evidence of re-
duction. Only sodium sulphite, chromous chloride, and ascorbk acid, of the following compounds investi-
gated, were effective for this purpose: resorcinol, hydrazine, hydroxylamine, ascorbic acid, d-glucose,
hydrogen peroxide, chromous chloride, formic acid, methyl alcohol, sodium sulphite. Ascorbic acid, which
is itself colorless and gives a colorless oxidation product, has been used by Maksimyuk (5) to reduce platinum
IV to platinum I1 quantitatively, and was therefore used throughout the remainder of the experimental
work.
5-(9-Dimethylaminobenzy1idene)-rhodanine,of a number of reagents investigated for the determination
of platinum in the bivalent state, appeared most promising. This reagent, which has been used for the
colorimetric determination of palladium ( 6 ) , reacted immediately with platinum I1 to give a dark red
precipitate in aqueous solution b u t very slowly with platinum IV. T h e problem in using this reaction for
the colorimetric determination of platinum was to find a suitable solvent or a suitable extractant for the
precipitate. Difficulties in obtaining complete extraction with chloroform, petroleum ether, benzene, and
carbon tetrachloride discouraged further investigation into extraction possibilities. Although water-mis-
cible solvents, such as alcohols, acetone, and dioxane, dissolved the precipitate, the resulting solutions
were unstable, with solid separating from solutioil or the color fading on standing. Propionic acid, however,
used b y Ayres and Narang in the determination of palladium, dissolved the platinum complex to give
stable, red-colored solutions and proved a satisfactory solvent in the colorimetric determination.
Reagents
Standard platinum solutions.-These solutions were prepared by dissolving a known weight of Johnson
Matthey, "Specpure" ammonium chloroplatinate in water containing a few drops of dilute hydrochloric
acid, and diluting to volume.
'This work received$nancial assistance from the National Research Council, and i s abstracted from the M.Sc.
Thesis of Frances E. Piercy.
Canadian Journal of Chemistry. Volume 41 (1963)
 668 CANADIAN JOURNAL OF CHEMISTRY. VOL. 41, 1963

6-(9-Dinzethylaminobenzy1idene)-rhodanie-The reagent was obtained from Eastman Kodak, and

reagent solutions contained 0.04% reagent in 98% formic acid. Ninety percent formic acid was also satis-
factory.
L-Ascorbic acid.-These solutions were prepared fresh daily t o avoid possible deterioration. The solutions
mere 0.1 M ascorbic acid in water, adjusted t o pH 2 with dilute hydrochloric acid.
Propionic acid.-Reagent grade was used.
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Spectral Curves
The absorption curves for reagent and for a solution containing 2 p.p.m. of platinum are shown in Fig. 1.
These curves were obtained using a Bausch and Lomb spectronic recording Spectrophotometer. Maximum
absorption occurs a t 545 mp but, since the reagent absorbs strongly a t ;hat wavilength, all colorimetric
results recorded were carried out a t 590 mp, where the reagent shows 100% transmittance.
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FIG. 1. -Absorption spectra: A, 1ml reagent solution (1.51 X10-8 mole reagent) +
2 ml water + 3 drops
ascorbic acid diluted to 10 ml with propionic acid; B, as A plus 2 p.p.m. of platinum.
Effect of Heating
Although immediate color development is obtained-on adding reagent t o platinum solutions reduced
with ascorbic acid, maximum color is not attained for several hours. However, by heating the sample
solutions a t 65-75' C for 5 minutes, stable maximum color is obtained. For example, the optical density
of a solution containing 2 p.p.m. of platinum changed from 0.158, without heating, to 0.233, after heating
for 5 minutes a t 70' C. In a number of experiments in which the heating was carried out by immersing
t h e 1 0 - n ~ volumetric
l flasks in a water bath a t the desired temperature, consistent results were obtained
in solutions heated for 5 t o 10 minutes a t temperatures between 65 and 75" C. There was some decrease
in optical density if solutions were heated for a longer period; thus a reading of 0.219 was obtained after
heating for 15 minutes a t 70' C.
Effect of p H
For the reagent blank alone, the p H of the water solution may be varied between 2 and 6 without sig-
nificant changes in the resulting spectra, and with 10070 transmittance a t 590 mp; a t p H 1, the reagent
color is considerably faded. In samples containing 1.6 p.p.m. platinum, the optical density a t 590 mp was
found to be 0.185, between pH 2 and 4. At p H I , this falls off to 0.156; a t pH 5, the reading is 0.174. From
these experiments it was obvious t h a t between p H 2 and 4, consistent results may be obtained.
Effect of Water, Ascorbic Acid, and Reagent
When optical density measurements are made a t 590 mp, the sample solution may contain from 5 %
t o 25Yo water solution; if more than 2.5 ml of water per 10 ml final solution is present, the precipitate
may be difficultly soluble in the propionic acid. Since the reagent does not absorb a t 590 mp, the con-
centration of reagent has no effect on the optical density; however, a large excess must be avoided due to
the limit of its solubility in propionic acid. The volume of 0.1 M ascorbic acid solution added can be varied
from 2 drops to 1 ml, with no effect on the resulting optical density.
Procedure
T h e platinum solution was adjusted to pH 2 t o 4 with dilute hydrochloric acid, and a 0.5- to 2.5-ml
aliquot (containing 5 to 60 pg platinum) was taken for analysis. T o this aliquot, in a 10-ml volumetric
 PIERCY AND RYAN: COLORIMETRIC DETERMINATION O F Pt 669
flask, was added three drops of 0.1 M ascorbic acid and the solution mixed. One milliliter of reagent was
added and the flask placed i11 a water bath a t 65-78' C for 5 minutes. The solution was then cooled t o
room temperature under cold water. Propionic acid was added, almost t o volume, and the solution allowed
t o come to room temperature (about 15 minutes). T h e volume was then adjusted to 10 ml with propionic
acid and the optical density read a t 590 mp against a reagent blank.
Optical densities obtained on a series of platinum samples are given in Table I. These results show t h a t
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Beer's law is obeyed between 0.5 and 6 p.p.m. T h e color was stable for 1 hour, after which time i t faded
very slowly; a sample containing 2.0 p.p.m. platinum gave a constant optical density of 0.236 for 1 hour,
falling t o 0.233 after 90 minutes and to 0.226 after 2 hours.

TABLE I
Optical densities for varying platinum concentrations

P t (p.p.m.) density
Optical I/ P t (p.p.m.)
Optical
density

Effect of Va'ali o z ~ sIons

No interference mas noted when 2000 p.p.m. of the sodium, potassium, or ammonium salts of the followiug
ions was added to 2 p.p.m. of platinum, as the chloride, and the usual colorimetric procedure carried out:
C1-, So4-', NO3-, B02-, C03-2. Acetate ion, in excess of 500 p.p.m , and fluoride or bromide, beyond
100 p.p.m., interfere. Thiosulphate, sulphite, sulphide, oxalate, and iodide ions interfere b y producing
turbid solutions. Although sulphate in large amounts does not interfere in the determinations, the colored
complex does not form in solutions t h a t have been fumed with sulphuric acid.
For personal use only.

Studies of the reactions of various ions, when 200 p.p.m, of the metal ions as chlorides or nitrates was
added t o 2 p.p.111. of platinum, showed no interference from the following ions: K f , Naf, NHpf, Ni+2,
C O + ~€d+2,
, Mg+2, Ca+2,S F , B d 2 , A1+3, Asf3. Zinc and manganese interfered beyond 50 p.p.m. Antimony,
tin, iron, and chromium ions interfere through precipitate formation or b y giving low optical density
readings.
Silver, mercury, copper, gold, palladium, and rhodium react with the reagent to give precipitates similar
t o that obtained with platinum. Of these, only interferences from palladium can be eliminated in the
determination of platinum; 25 p.p.m. of palladium in the presence of 2 p.p.m. of platinum does not interfere
if a small amount of dimethylgloxime is added. Some results obtained in the presence of other platinum
group metals are given in Table 11.

TABLE I1
Platinum determinations in the presence of other platinum group metals
--
P t taken P t found P t metal present
(pa) (pa) (pa) Remarks
Added as ammonium chloroiridate

Two drops 0.1 M dimethylglyoxime

added
0.5 ml dimethylgloxime added in excess
Added as ammonium chlororuthenate;
ruthenium absorbs itself a t 590 mp
Added as ammonium chloroosmate

A color is developed with Rh alone

21.5 Ir, 20 Ru, Two drops 0.1 M dimethylglyoxime added
20 Os, 25 P d
2 1 . 5 Ir, 20 Ru,
20 0 s . 25 P d
 6'70 CANADIAN JOURNAL O F CHEMISTRY. VOL. 41, 1963

Rhodium interferes seriously and gives a color nearly as intense as t h a t of platinum. The results show
t h a t iridium, ruthenium, and osmium, in low concentration, do not interfere and t h a t platitlu~ncat1 be
determined (provided dimethylglyoxime is added) in the presence of a 10-fold excess of palladium.
Stoichiometry of the Reaction
The stoichiometr~of the reaction was investigated spectrophototnetrically by both the mole ratio
method (7) and the method of continuous variations (8); both studies showed t h a t three molecules of
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reagent reacted with one atom of platinum. Attempts to support this somewhat surprising result by analysis
of the precipitated product were unsuccessful because of the inability to obtain a pure product.

REFERENCES
1. E. B. SAXDELL. Colorimetric determination of traces of metals. Interscience Publishers, Inc., New
York, N.Y. 1944.
2. G. H. AYRESand A. S. MEYER. J. Am. Chem. Soc. 77, 2671 (1955).
3. J. J. KIRKLANDand J. H. YOE. Anal. Chem. 26, 1340 (1954).
4. W. D. JACOBS. Anal. Chem. 33, 1279 (1961).
5. E . A. MAKSIMYUK.ILV.Sektora Platiny i Drug. Blagorod11. Metal., Inst. Obshch. i Seorgan. Khim.,
Akad. Nauk SSSR, 30, 180 (1955).
6. G. H. AYRESand B. D. NARANG. Anal. Chim. Acta, 24, 241 (1961).
7. J. H. YOE and A. L. JOKES. Ind. Eng. Chem., Anal. Ed. 16, 111 (1944).
8. P. JOB. Ann. Chim. Ser. 10, 9, 113 (1928).
For personal use only.