Spectrographic Determination of Platinum

by the Constant-Pair Method

JAMES J. MANNING AND JAMES COULL, Cooper Union Institute of Technology, New YorIr, N. Y.

W HILE investigating minute impurities in dental alloys

by means of the spectrograph, the authors were able to
develop a rapid method for the determination of platinum.
as a comparison standard in estimating the percentages’ of
the constituent to be determined. Using a microphotometer,
the intensity of the added element was compared with that
The present method of cupellation and subsequent chemical of the element being estimated, and from known amounts of
analysis, although more precise, is long and tedious, besides the latter, in standards, a calibration chart was constructed.
being expensive. The spectrographic method is not only This calibration chart could then be used in future analyses.
simple of execution but the most rapid by which the platinum
content of precious metal alloys, jeweler’s scrap, etc., may be Constant-Pair
obtained. It is the authors’ belief that this method can be Method
extended to include such metals as palladium, gold, silver,
rhodium, etc., with all the advantages mentioned above. I n t h e case of
Inasmuch as the authors’ method has been evolved from a d e n t a l a l l o y s the
study of many methods previously established, i t is desirable method of Gerlach
to give a brief account of these other methods. and Schweitzer (1)
A previous method for the spectrographic determination of cannot be used be-
platinum in silver alloys, as developed by de Laszlo (a), is cause the main con-
based on the fading out of weak lines a t certain concentrations stituents a r e n o t
of platinum. At threshold concentrations weak lines disappear -3208.8 Mo present in constant
B -3204.0 Pt
amount. The
until, as the concentration becomes smaller, only the persistent
lines or raies ultimes remain on the photographic plate. The method of Nitchie
degree of correlation existing between the number of fine lines and Standen (3) can
appearing in the spectrum and the concentration of platinum be employed where
is one of the main factors governing the accuracy of this a microphotometer
method. Undue stress, however, is not placed on the re- is available.
producibility of arc conditions, in going from one spectrum Obviously if an
to the next. The de Laszlo method, as used in the routine element could be
analysis of alloys containing small amounts of platinum, has f o u n d which be-
an accuracy of k 2 0 per cent of the amount present. haved like platinum
The authors have found that greater accuracy can be ob- in its arc spectrum,
tained by counting the number of lines in a given spectrum the amount of plati-
than by direct visual comparison of line intensities. This num in the sample
latter method, which enjoys widespread application, requires could be estimated
very rigorous control of arc conditions in order to reproduce from the concentra-
the background present in the standard plate. t i o n of s u c h a n
element. Some of
the lines of this ele-
Method of Constant Internal Standard m e n t would have
It remained for Gerlach and Schweitaer (1) to show “that -2893.8 Pt the same intensity
it is not practical to establish on general principles an absolute r a s s o m e of t h e
D
system of analyses which is based solely upon the measure- L -2871.5 Mo p l a t i n u m lines if
ment of the intensity of spectrum lines of the element which is b o t h were present
to be quantitatively determined.” Thus they compare in in equal a m o u n t s .
the same spectrum lines of the impurity withlines of the By noting the con-
main constituent, where the latter is assumed to be present in -2816.1 Mo
c e n t r a t i o n of the

G
constant amount or to vary only as the result of the variation a d d e d element a t
in the amount of the impurity to be determined. This ar- which equal intensi-
rangement eliminates any differences arising from changes in t i e s a r e obtained,
conditions of excitation, timing, photography, etc., since -2775.4 Mo t h e percentage of
-2771.6 Pt
these latter affect both groups of lines similarly. For alloys platinum could be

i
having elements with many lines of decided intensity varia- found. Such a
tion this method is excellent. In cases of elements having few method would re-
lines, however, it becomes a matter of considerable difficulty quire no calibration
to find enough suitable pairs to compile a reference table of -2719.0 Pt c u r v e a n d would
any value. In precious metal alloys where gold is the main secure the full ad-
constituent (present in varying amounts), the above method v a n t a g e of the in-
cannot be used. ternal standard
Nitchie and Standen (3) modified Gerlach and Schweitaer’s O Q O O O r N l P
method. The p r e -
method by adding to the sample in solution a constant amount O O
W ~ ;N
. NU3 1b 00 000 0 0 liminary work
of an element not originally present. The added element F necessary i n t h e
furnished spectrum lines of constant intensity which served FIGURE
1 selection of a suit-
28
JANUARY 15, 1937 ANALYTICAL EDITION 29
able internal standard is somewhat long and tedious, but once o erator five to seven solutions are required in obtaining a suit-
this has been done the determinations which follow are a a&lematch.
matter of simple routine. Table I shows the quantitative results obtained by the
constant-pair method for a group of dental alloys. The
Selection of Internal Standard analyses given in the second column are taken as correct,
Confining attention to the work done in the proper selection since they represent a t least six determinations of platinum.
of an internal standard for platinum, the authors were able to These determinations were carried out by cupellation of the
note the following facts: The element chosen as the internal alloy and precipitation of the platinum from the solution as
standard must be absent from the sample or alloy which is ammonium chloroplatinate after removal of the gold.
the subject of analysis. Its spectrum must contain a sufficient
number of suitable lines not too far removed from the platinum TABLEI. QUANTITATIVE
RESULTS
WITH DENTAL
ALLOYS
lines usually employed in analysis. It must be subject to the Platinum Platinum
by by
same sampling conditions as the element being determined- Sample Cupellation, etc. Spectrograph Difference
the two elements must be soluble in the same acids or a t AC
A7
0.0250 0.0227 -0.0043
0.0300 0.0350 +0.0050
least be capable of giving a clear solution when their separate A8 0.0115 0.0130 +0.0015
solutions are mixed or diluted. A3 0.0300 0.0280 -0.0014
-0.0020
A9 0.0102 0* 0088
Among the elements examined as to their suitability to act AI 0 0400
I 0.0370 -0.0030
AP 0.0129 0.0124 -0.0005
as internal standards for platinum, aluminum, manganese,
and nickel were eliminated because of the differences in their
rates of volatilization as compared with platinum. The lack The method as carried out should give an accuracy of
of suitable lines eliminated tungsten. Tin, bismuth, and *17 per cent of the total amount of platinum present, by
antimony were rejected on account of their failure to meet the visual comparison of line intensities. It is probable that this
sampling conditions specified above. Molybdenum was found accuracy could be greatly improved by determining line
to be suitable and the final selection of this element was justi- intensities using a densitometer.
fied by the results explained below.
Summary
Selection of Constant Pair A spectrographic method has been developed in which a
rapid estimation may be made of platinum in precious metal
Solutions were made by dissolving separately in aqua regia alloys, using molybdenum as the internal standard. Condi-
2-gram samples of pure molybdenum and platinum. These tions governing the proper selection of elements used as
solutions were diluted to various concentrations and mixed internal standards are stated.
in equal volumes, so that a series of solutions containing from
0.4 to 0.03 per cent of each metal was obtained. Spectro- Acknowledgment
graphic examination of these solutions as shown in Figure 1
revealed the following pairs of lines. The authors wish to acknowledge with thanks ‘the helpful
criticism and advice of C. C. Nitchie, Bausch and Lomb
Pair A B C D Optical Co., Rochester, N. Y.
Platinum 2719.0 3204.0 2771.6 2893.8 ’
Molybdenum 2816.1 8208.8 2775.4 2871.5 Literature Cited
(1) Gerlach and Sohweitzer, “Foundations and Methods of Chemical
Of these the matched constant pair marked D was selected Analysis by the Emission Spectra,” p. 152, Leipzig, Leopold
because the lines were sufficiently sensitive to record small Voss, 1929.
changes in composition over the range studied; they were not ( 2 ) Laszlo, H. de, IND.ENO.CHEM.,19, 1366 (1927).
basic or ultimate lines subject to reversal, masking or halation (3) Nitohie and Standen, Ibid., ilnal. Ed., 4, 182 (1932).
effects were absent, and their close proximity to each other RECEIVED
November 5, 1935.
ensured uniform conditions in the emulsion.
I n addition to D, the authors have selected as matched
pairs A , B, and C, which were found to be very useful as an
aid to checking results. At the higher concentrations pair
A has the same intensity, whereas pair B has the molybdenum
line slightly more intense than the platinum line, and in pair
C the platinum line is more intense than the molybdenum
line. These pairs are therefore useful in estimating roughly
the amount of platinum present in the solution.

Apparatus and Experimental Results

The spectrum from 2480 t o 3300 A. was Ehotographed on a
25-om. (10-inch) plate using a Bausch and omb Littrow-type
quartz spectrograph of 70-mm. aperture and 183-cm. focal length.
Three-minute exposures were found to be sufficient to volatilize
all the Dlatinum and molybdenum contained in the crater of the
graphitk rod.
A 1-gram sample of the alloy dissolved in aqua regia was diluted
to 25 cc. Three solutions, each of 10 cc., were prepared by taking
equal volumes of alloy and molybdenum solutions, the latter at
high, medium, and low concentrations. Spectra were obtained
from these solutions by pipetting 0.15 cc. into each carbon crater
and arcing when dry, using a current of 11.5 amperes. These
spectra serve to indicate the approximate amount of platinum
in the solution. A final plate was then made using the molgb-
denum solutions over a narrower range of concentration until a
matched pair of lines was obtained. In the hands of an experienced