Simultaneous Spectrophotometric Determination of Palladium and Platinum… 141

Simultaneous Spectrophotometric Determination of Pd

and Pt in Mixed Solutions
M.V. Rane, V. Venugopal*, S.K. Tangri, A.K. Suri
Hydrometallurgy Section, Hall 6, B.A.R.C., Mumbai
*Radiochemistry & Isotope Group, RLG Laboratories, B.A.R.C., Mumbai

ABSTRACT: In India Platinum Group Metals (PGM) are obtained from secondary sources like spent catalyst
and scrap generated during the manufacturing processes. The recovery of palladium and platinum from spent
catalyst was attempted by solvent extraction using Alamine 336 as a solvent. This involved the analysis of
palladium and platinum in the different process streams like feed, strip, raffinate, etc. on a continuous basis. A
novel method was developed with the aim to quickly analyze large number of samples containing both, palladium
and platinum. It is based on the measurement of absorbance of the samples at two suitable wavelengths and
calculating the concentrations by solving the simultaneous equations so obtained. It is a simple, fast and accurate
method for determining these metals at microgram levels. The method has a working concentration range of 50 to
500 µg/ml of the metal ion/ions.

1. INTRODUCTION Balcerzak et al. 2001). This paper deals with a

Platinum Group Metals (PGM) have great
economical value in industry due to their
application in large number of fields. They are
used as catalyst in petroleum cracking industry
and automobiles for pollution control. Besides
these, due to their inert property they are used as
corrosion resistant materials for various appli-
cations. They are also used for making jewellery
and electrodes in the electrical as well as bio-
medical field. Substantial quantities of PGM are
formed during the fission of plutonium. Methods
are being developed for the recovery of these
metals from high level wastes in nuclear industry.
As a result, the accurate estimation of these
elements is necessary.
A large number of methods for the
determination of PGM have been developed
since the initial use of fire assay that dictated the
analytical separation of PGM for about hundred
years. A number of review articles summarizing
the merits and demerits of these methods have
been published (Beamish & McBryde 1953,
1958). With the advent of electronics, different
sophisticated instruments have been developed
resulting in more advanced techniques of
analysis. Simultaneous spectophotometric deter-
mination techniques using first, second or higher
order derivative spectra have also been tried out
(Kus & Marczenko 1987, Toral et al. 2000,
simple, and accurate two-wavelength spectro-
photometric method for the simultaneous
determination of palladium and platinum without
using derivative spectra.
The separation of palladium and platinum
was attempted by solvent extraction using
Alamine 336 in a mixer-settler setup. Samples
had to be analyzed at short intervals to monitor
the attainment of equilibrium in each stage. This
method was developed with the aim to quickly
analyze large number of samples for palladium
and platinum in the concentration range of 50 to
500 µg/ml. The advantage of this method over
the conventional methods for palladium and
platinum is that both palladium and platinum can
be determined without prior separation. How-
ever, this is not the case with the most widely
applied tin(II) chloride method (Ayres & Meyer
1951) for platinum where palladium interferes
strongly as both form coloured complexes with
tin(II) chloride. Therefore, separation of these
metal ions is necessary, if they are to be analyzed
by the tin(II) chloride method. Other methods
like phenylthiosemicarbazide, p-nitrosodimethy-
laniline (Kirkland & Yoe 1954), etc. for platinum
and EDTA (MacNevin & Kriege 1954), 2-
nitroso-1-naphthol (Cheng 1954), thiourea
(Nielsch 1954), etc. for palladium require very
specific reagents and these too are not free from
interference. Morever, these methods can be used
142  Mineral Processing Technology (MPT 2007)
to determine only one metal ion either platinum
or palladium. The two-wavelength method
avoids use of excess reagents due to which the
samples can be mixed back into the process
streams after analysis. This reduces the loss of
such valuable material during analysis and gives
good material balance for the mixer settler data.
It does not require sophisticated spectrophoto-
meter as in the case of simultaneous deter-
mination by derivative spectroscopy. However,
as the method has a limiting concentration range
of 50 to 500 µg/ml, it cannot be a substitute for
the tin(II) chloride or other methods, which are
applied for very low levels of around 1 to 5 µ
g/ml, unless the samples are pre-concentrated.
2. EXPERIMENTAL
2.1 Materials & Equipments
UV Visible Spectrophotometer CINTRA-40
(GBC, Australia), Atomic Absorption
Spectrophotometer AVANTA PM (GBC,
Australia) were used for the analysis of
palladium and platinum. All reagents were of
analytical grade.
2.1.1 Procedure
Standard solutions of palladium and platinum
were prepared by dissolving 99.95% pure metals
in aquaregia, evaporating to dryness and diluting
to the desired volume using demineralized water.
The required acidity was maintained using HCl.
Standard solutions of 500 µg/ml platinum
concentration were prepared at varying HCl
concentration i.e. 1M to 5M. Similar solutions
were prepared for palladium.
The absorption spectra of these solutions
were studied in the wavelength region of 350-700
nm at a scanning speed of 500 nm/min and
slitwidth of 2 nm. The concentration of HCl was
optimized and the two wavelengths were chosen
in a way as to obtain maximum sensitivity and
minimum interference to each other. The
absorbance values for various concentrations of
palladium and platinum were taken separately at
the two wavelengths to confirm whether it
follows The Beer’s Law. The molar extinction
coefficients were obtained from the above plots.
A computer program was developed in Excel to
calculate the unknown concentration of palla-
dium and platinum using the molar extinction
coefficients and the absorbance values of the
sample solutions at the selected wavelengths. The
reliability of the method was tested on a series of
synthetic solutions of these metals and the actual
process samples generated in the mixer settler
setup. The aqueous phase was analyzed as such
after maintaining the required acidity. The
organic phase was stripped with 5M HCl and
analyzed.
3. RESULTS & DISCUSSION
The overall shape of the absorption spectra
remained unaltered at various HCl concentrations
for both palladium and platinum.
Fig. 1: Effect of HCl concentration on the
absorption spectrum of Pd (0.5 g/l)
From the study, it was observed that in the
case of palladium there was a bathochromic shift
from 445 nm to 460nm at the maxima. In
addition to this, there was a 5% increase in
absorbance values on varying the HCl concen-
tration from 1M to 5M. The minima showed no
shift but the absorbance decreased from 0.3 to
0.25 (Fig. 1). As for platinum, the minima as well
as the maxima at higher wavelengths showed no
difference. The maxima at the lower wavelength
showed a 7% increase in absorbance for the
specified increase in acidity. No shift was
observed in this case. (Fig. 2)
Simultaneous Spectrophotometric Determination of Palladium and Platinum… 143
Metal ion Molar Extinction Co-efficient, φ (104 L
mol-1 cm-1)

463 nm 370 nm
Palladium 0.01681 0.00604
Platinum 0.00517 0.04662

The concentrations of palladium and platinum in

various mixed synthetic samples as determined
by the two-wavelength computer program are
tabulated in Table 2. Along with it are given the
values confirmed by Atomic Absorption Spectro-
scopy for palladium and tin(II) chloride method
Fig. 2: Effect of HCl concentration on the for platinum. The values obtained from the
absorption spectrum of Pt (0.5 g/l) different techniques tally well within limits of
experimental errors.
An increase in the absorbance at the maxima
would result in higher sensitivity and a decrease Table 2: Analysis data of synthetic and process
at the minima would minimize the interference samples
due to that element. As a result, the HCl concen- Conc. from two Pd by Pt by
tration was optimized to 5 M and the two Sample wavelength AAS SnCl2
wavelengths chosen were 370nm and 463nm to method (g/l) (g/l) method
(g/l)
obtain best results. It was found that both Pd Pt
palladium and platinum absorbance values at the *
SS-1 0.098 0.041 0.100 0.040
selected wavelengths are in good agreement with SS-2 0.202 0.040 0.200 0.040
Beer’s Law up to a concentration of 500ug/ml SS-3 0.146 0.078 0.150 0.080
(Fig. 3). The molar extinction coefficients are SS-4 0.195 0.077 0.200 0.080
given in Table 1. SS-5 0.101 0.115 0.100 0.120
1.2 SS-6 0.302 0.153 0.300 0.160
Pt(370nm) #
PS-1 0.055 0.060 0.058 0.057
1.0 PS-2 0.344 0.141 0.336 0.144
PS-3 0.407 0.065 0.400 0.061
0.8
PS-4 0.127 0.213 0.121 0.219
0.6 Pd(463nm) ‘*’ SS = synthetic sample ‘#’ PS = process sample.
Abs

0.4
Pd(370nm) The possible interferences from various
metal ions like Ni(II), Co(II), Cu(II), Fe(II) and
0.2
Fe(III) was calculated from their absorbance
Pt(463nm)
0.0 values at 463 nm and 370 nm. The results were
0.0 0.1 0.2 0.3 0.4 0.5 tested experimentally. It was found that Ni(II)
Concentration (g/l) and Co(II) did not interfere seriously. Concen-
Fig. 3: Verification of Beer’s law for Pd and Pt in trations of Ni(II) comparable to that of platinum
5M HCl medium, at λ = 463 nm & 370 nm. can be tolerated with a nominal error of less than
2%. Similar results were obtained when Co(II)
Table 1: Molar Extinction Co-efficients for Pd and was not more than 20% of the palladium
Pt concentration. However, Cu(II), Fe(II) and Fe(III)
interfered seriously and prior removal of these
144  Mineral Processing Technology (MPT 2007)
impurities is necessary to proceed with the deter-
mination of palladium and platinum.
4. CONCLUSION
A unique two-wavelength method has been
developed for the determination of palladium and
platinum simultaneously. A major advantage of
this method compared to the other methods
commonly used is that it eliminates the need to
separate these two metals before analyzing them.
It is a very economical method as minimum
reagents are required and the samples can be
directly returned to the solvent extraction circuit.
It is a simple and fast method to analyze large
number of samples.
5. ACKNOWLEDGEMENT
The authors are thankful to Dr. S. Banerjee,
Director, Materials Group & Director, Bhabha
Atomic Research Centre for his keen interest and
guidance during the course of this work.
REFERENCES
[1] Ayres, G.H. and Meyer,A.S.,Jr.,
Spectrophotometric study of the Pt (IV)-Tin (II)
chloride system. Anal. Chem., 23, 299-304
(1951).
[2] Balcerzak, M., Bystronska, D., Swiecicka, E.,
Derivative spectrophotometric methods for the
determination of rhodium, palladium and
platinum in mixtures. Chem. Anal., 46, 547-560
(2001).
[3] Beamish, F.E. and McBryde, W.A.E., A critical
evaluation of colorimetric methods for the
determination of platinum metals. Anal. Chim.
Acta, 9, 349-367 (1953).
[4] Beamish, F.E. and McBryde, W.A.E., A critical
evaluation of colorimetric methods for the
determination of platinum metals II. Anal. Chim.
Acta, 18, 551-564 (1958).
[5] Cheng, K.L, Spectropotometric determination of
palladium with 2-nitroso-1-naphthol. Anal.
Chem., 26, 1894-1895 (1954).
[6] Kirkland, J.J. and Yoe, J.H., Spectrophotometric
study of p-nitrosodimethylaniline as sensitive
colorimetric reagent for platinum. Anal. Chem.,
26, 1340-1344 (1954).
[7] Kus, S. and Marczenko, Z., Simultaneous
determination of palladium and platinum as
dithizonates by fifth-derivative spectro-
photometry. Analyst, 112, 1503-1506 (1987).
[8] Kus, S. and Marczenko, Z., Determination of
microgram amounts of platinum as dithizonate
in the presence of palladium by second-
derivative spectrophotometry. Analyst, 114, 207-
210 (1989).
[9] MacNevin, W.M. and Kriege, O.H., Chelation of
platinum group metals. Anal. Chem., 26, 1768-
1770 (1954).
[10] Nielsch, W., Die photometrische Bestimmung
des Palladiums mit Thioharnstoff. Mikrochim.
Acta, 532-538 (1954).
[11] Toral, M. Inés, Richter, P., Lara, N., Escudero,
M. Teresa., Soto, César., Simultaneous
determination of platinum and palladium by
second derivative spectrophotometry using 3-
(2'-thiazolylazo)-2,6- diaminopyridine as
chromophore ligand. Anal. Lett., 33, 93-109
(2000).