CHROMATOGRAPHIC SEPARATION AND

DETERMINATION OF NOBLE METALS IN

MATTE-LEACH RESIDUES

C. POHLANDT and T. W. STEELE

Analytical Division. National Institute for Metallurgy. Johannesburg. South Africa

(Rewired I2 Noncrnher 1973. Accepred IO Decernher 1973)

Summary-The practical application of various chromatographic methods to the analysis of resi-

dues obtained from the leaching of copper-nickel mattes is described. The procedure involves the
separation of gold on a TBP-treated Porasil column. the separation of base metals by cation-
exchange. the separation of tellurium from platinum-group metals, and the separation of the non-
volatile platinum-group metals on one cellulose column.

Most metallurgical processes for the recovery of the noble metals involve their con-
centration by a smelting procedure to produce a matte, which consists essentially of cop-
per. nickel. iron and sulphur. and which has a noble-metal content of between 1000 and
3000 ppm. Further concentration of the matte by various leaching processes results in a
matte-leach residue having a noble-metal content of > l”/o. Because of the economic value
of these concentrates, the accurate determination of their noble-metal content is impor-
tant.
Relatively fast methods for the analysis of matte-leach residues have been developed at
the National Institute for Metallurgy, South Africa, and are used on a routine basis. These
methods involve the dissolution of a sample in acid under pressure or by fusion with
sodium peroxide, and atomic-absorption spectrophotometry (AAS).
However, it was felt that an alternative method independent of AAS would be useful
as an umpire method and also when. because of the complexity of a sample, direct AAS
procedures might give doubtful results. In view of the findings of a recent investigation’
it was decided to include the chromatographic separation of gold, rhodium and iridium
so that all the noble metals could be present in a sufficiently pure state to warrant their
gravimetric determination.
It was felt that this approach would result not only in a method independent of AAS
but also in an assessment of the accuracy and precision of gravimetric methods, which are
still favoured by some refineries. after separations considerably more involved than those
proposed in this paper, in the belief that they are much more accurate than direct AAS
measurement.

EXPERIMENTAL

Glass columns with sititered-glass discs or perforated porcelain discs at the bottom were used for the chroma-
tographic separations. The cation-exchange resin Bio Rad AC-50W-X8 was obtained from Bio Rad Laboratories.
Richmond. California. and the support material. Porasil C. from Waters Associates. Inc., Framingham. Mass.,
U.S.A. Whntmnn‘s fibrous cellulose CF I I aas used in the preparation of the columns. Platinum. palladium.
919
 920 C. POHLASDTand T. W. STEELE

rhodium. iridium and gold as metals were supplied by Engelhard Ind.. U.S.A. The preparation of standard solu-
tions of gold, platinum and palladium has been described elsewhere.’ Rhodium and iridium solutions were pre-
pared by dissolution of the metal in a sealed tube by chlorination.”

The chemistry involved in the separation of the non-volatile platinum-group metals on a cellulose column,
as well as column parameters and elution characteristics, have been discussed previously.’ In the following sec-
tions an account is given of the various stages of the proposed procedure for application to the analysis of matte-
leach residues. The method* is summarized in Scheme 1.

0.5 - 1.0 g of sample fused with No2 02 in on alumina crucible

Melt leached with 10% HCl

SiOz removed by dehydration and filtration

Gold separated on TBP - treated - Au eluted with HNOs

Porasil C column (0.IM HCl as sluent 1 and determined gravimetricolly
with hydrazine hydrote
I

Base metals separated on Eio Rad AG-SOW-X8 (O*lM HCL as eluent)

Tellurium separated on TBP- treated Porasil C column (10M HCL QS aluent)

OS and Ru
Solutions evaporated and organic matter destroyed - volatilized
I

Separation of platinum-group met& on cellulose column

t t t
t Pd Ir Rh
determined determined determined determined
grovimetricolly gravimetricolly grovimetricolly gravimetrically
with with with with
hydrozine dimethyl - hydrated sodium
hydrate glyoxime dioxide borohydride

Scheme I. Separation and gravimetric determination of the noble metals.

Fusion ofsample. Zirconium crucibles were previously used for fusions with sodium peroxide.’ However, since
any zircomum dissolved during fusion tends to hydrolyse at the low acid concentrations used in the proposed
procedure, particularly when left standing, it was decided to use alumina crucibles instead. The alumina crucibles
were found to be resistant to sodium peroxide attack, and complete dissolution of a sample was readily obtained.
Before leaching, the crucibles were allowed to cool to avoid breakage. Any aluminium dissolved during fusion
was conveniently removed during the separation of the base metals on the cation-exchange column.
Rrmoual of’silica. Silica, usually present in matte-leach residues in amounts up to 40x, has to be removed
at an early stage in the analysis, because it would otherwise cause difficulties in the analytical procedure. Attempts
were made to volatilize the silica by treatment of the sample with hydrofluoric acid in the alumina crucible before
fusion with sodium peroxide. However, this treatment resulted in unsatisfactory fusion, and leaching produced
an insoluble precipitate consisting mainly of aluminium and iron.
It was therefore decided to remove the silica by the conventional procedure of dehydration and filtration. It
was, however, observed that, depending on the type of sample, the silica precipitate was not always free from
noble metals and had to be treated for their recovery.
Srpuratian of’yold. Gold was initially separated by precipitation with sodium sulphitc and determined gravi-
metrically.’ but this method was considered tedious and lacking in precision. Greater advantages were expected
 Determination of noble metals 921.

if the gold could be separated chromatographicdlly from all the other metals present in a sample and then deter-
mined by a suitable method. The separation of gold on the ion-exchange resin Amberlite XAD-7 or on a TBP-
treated Porasil C column was considered.
Svpcvatiorr o/ qoltl OH SAD-7. The separation of gold from various other metals Amberlite XAD-7 has been
described bv Fritz et u/..’ who showed that gold is strongly adsorbed from I M hydrochloric acid, whereas base
metals. pIat_inum. palladium and ruthenium were not adsorbed. Gold was readily recovered by elution with a
mixture of acetone and hydrochloric acid.
We conducted further tests with respect to the behaviour of rhodium and iridium, which had not been investi-
gated by Fritz. The results of these tests (Table I) showed that complete separation of gold from base metals
and platinum-group metals was obtained and that recoveries were quantitative.
Separation qfgold 011 TBP-treated Porasil C. Various authors6-* have described the separation of microgram
amounts of gold by reversed-phase extraction chromatography with TBP as the stationary phase and a mineral
acid as the eluent. It has been shown that up to 20 mg of gold per g of TBP-treated Porasil C can be separated
from platinum-group metals and base metals when these are eluted with O.lM hydrochloric acid.* A few further
tests with mixtures of noble metals and base metals likely to be present in matte-leach residues confirmed that
complete separation is obtained on a TBP-treated Porasil C column 3 cm long (15 g) and that the recovery of
the noble metals is quantitative. as shown in Table 1. The gold can be easily eluted from the column with 14M
nitric acid.
It was thus ascertained that gold can be separated quantitatively on either XAD-7 or on TBP-treated Porasil
C. However. in the analysis ofmatte-leachresidues, it became apparent that a smaller amount of acid was needed
to wash the TBP-treated Porasil C column free from foreign metals. and that the concentration of the eluate
(0.1,~ hydrochloric acid) allowed direct transfer of the sample solution to the cation-exchange column for the
separation of base metals. whereas if the gold had been separated on XAD-7 (1M hydrochloric acid), an evapo-
ration step would have been necessary. It was therefore decided that the TBP-treated Porasil C column should
be used for the separation of gold in the analytical scheme for matte-leach residues.

Silica is removed by dehvdration and filtration. Dissolution of the residue, obtained after evaporation of the
filtrate, in 0.1M hydrochloric acid and filtration removed residual silica and probably Ag, Bi and Sb. which can
precipitate at very low- acid concentration. From published distribution coefficients’ it can be assumed that the
following species are retained on the cation-exchange column from C-1M hydrochloric acid: Al(III), Zr(IVk
Th(IV), Ba(II), Ga(I1). Fe(H). Fe(III), Ni(II), Co(H), Mg(I1). Mn(I1). Cu(II), Zn(II), Be(H), Ti(IV), Sn(IV), G&II).
Cr(II1) and large amounts of Na+ were found to be only partially retained. According to distribution coeffi-
cients published by Ishimori. ” V MO Sb. Ta. W and As, if present in 10M hydrochloric acid. would be separated
from the platinum-group metals together with Te on a TBP-treated Porasil C column. It can be further assumed
that, in addition to Ru and OS. elements such as Se and Hg would be partially or completely lost during the
evaporation steps or during wet oxidation with perchloric acid.“*”
In the analysis of matte-leach residues, only chromium was found to accompany the platinum-group metals
through the entire procedure. Since chromium is not extractable into TBP, it was retained on the cellulose
column and eluted together with rhodium. However, when rhodium was precipitated as the metal by reduction
with sodium borohydride. chromium remained in solution and did not interfere in the gravimetric determination
of rhodium.

Table I. Separation of gold from platinum-group metals on XAD-7 or TBP-treated Porasil C

Au Pt Pd Rh Ir
Added. Found. Added Found, Added, Found. Added, Found. Added, Found,
Method rng rng “%7 mg mg mg nig mg 1~ mg
XAD-7 Base metals 9.7 969 53.6 53.4 25.2 25.4 9.92 9.92 2.52 2.52
absent
Base metals 10.0 IO.2 50.3 ‘- 30.3 - 10.0 - 2.5 -
present
TBP-Porasil Base metals 10.0 10.0 536 53.6 25.2 26.2 9.92 9.92 2.52 2.80
absent
Base metals IO.0 I@2 50.3 - 30.3 - 10.0 - 2.5 -
present

Not determinrd.
922 C. POHLAXDT and T. W. STEELE

Separation oftellurium
Sii tellurium, usually present in a matte-leach residue, is not retained on the cation-exchange column under
the experimental conditions described, it was considered a possible interference in the gravimetric determination
of rhodium and iridium. Moreover, it had been observed previously I3 that tellurium can seriously interfere in
the determination of platinum if the ratio of tellurium to platinum exceeds I : 45.
It was therefore decided to investigate the separation of tellurium from platinum-group metals by reversed-
phase extraction chromatography with tri-n-butyl. phosphate (TBP) as the stationary phase and hydrochloric
acid as the eluent. The system TBP-HCl has been widely investigated with respect to the behaviour of the noble
metals, and of tellurium and selenium. W” Although the separation of tellurium and platinum-group metals
had not been attempted, it appeared from published distribution coe@icients*.‘O that it would be possible to
separate them at hydrochloric acid concentrations of more than IOM. To confirm this prediction, the behaviour
of tellurium and the platinum-group metals on a TBP-treated Porasil C column with IOM hydrochloric acid
as the eluent was it$vesti@ted.
Sodium chlorate was a&&d to the sample solutions in a few experiments to show whether the presence of
an oxidizing agent would affect the separation. On columns 5 cm long and I.2 cm wide (approximately 3 g of
TBP-treated PorasilX tellurium was found to be retained as a narrow yellow band, while the platinum-group
metals were eluted with approximately 50 ml of IOM hydrochloric acid. The results in Table 2 show that. within
the limits of experimental error for the methods of’determination, complete separation was obtained. The plati-
num-group metals were determined by AAS, and tellurium, after elution with hydrochloric acid of concentration
less than 2M. was determined gravimetrically by prbcipitation with hydrazine hydrate.
It can also be seen in Table 2 that the presence of sodium chlorate did not affect the separation and that rhe
recoveries were quantitative.

Sepuratiori c$plutirium. pulludium. iridium trud rhodium ou ow columrf

It has been shown previously’ that rhodium and iridium are not separated on a cellulose column when eluted
with TBP. In the present investigation, the separation scheme was extended to include the separation of the two
metals to facilitate their respective gravimetric determination (see Scheme 2).
Payne’* has described a semi-chromatographic separation of iridium from rhodium by first extracting the iri-
dium with an oxidizing solution (a mixture of methyl isobutylketone. hydrochloric acid and sodium chlorate)
and then passing the organic extracts containing the iridium through a cellulose column. An attempt was made
to modify Payne’s method by oxidizing the iridium directly on the column to its mobile quadrivalent state and
to elute it with TBP-toluene mixture (rather than with methyl isobutylketone as in Payne’s method) from the
rhodium. After. elution of the platinum and palladium, 1CLI5 ml of an oxidizing solution consisting of chlorine
dissolved in TBP and toluene was allowed to penetrate the column bed. After 5 min, elution was continued with
the TBP-toluene without the oxidant. Under these conditions the brown. oxidized iridium band moved slightly
ahead ofa very broad yellow chlorine band while rhodium remained unaffected in the upper part of the column.
Rhodium was next eluted with water. and the iridium was stripped from the organic eluate with water. That
the proposed procedure is quantitative can be seen from the mean amounts recovered when twelve synthetically
prepared sample solutions containing gold, platinum, palladium. rhodium and iridium were analyscd (Table 5).
Determination of the noble metals
The precipitation of platinum and palladium with hydrazine hydrate and dimethylglyoxime respectively has
been described previously.‘3 The separation of rhodium from small amounts of iridium by the selective reduction
of the former with sodium borohydride has been reported by McKay. I9 Since, however, the subsequent precipi-
tation of iridium proved to be difficult, the two metals were first separated chromatographically as described
earlier. Rhodium was then precipitated with sodium borohydride according to McKay’s method, and iridium
was precipitated as the hydrated dioxide as described by Beamish. Lo An indication of the accuracy obtainable
for comparatively small amounts of rhodium and iridium is given in Table 3.

Table 2. Separation of tellurium from platinum group metals

NaCIO, Te Pt Pd Rh Ir
added, Added, Found, Added, Found, Added, Found, Added, Found, Added, Found,
mg mg my W my mg nty mg W 111g mg

50 1.0 1.2 9.95 IO.02 - - - - - -

50 5.0 4.8 9.95 9.92 5.0 5.08 3.60 3.55 I.0 1.1
50 5.0 4.9 9.95 10.02 5.0 5.12 - -
Nil 5.0 5.1 9.95 990 5.0 5.05 - - - -

-Not determined.
 Determination of noble metals 923

Pt. Pd, Rh, Ir in 5 M hydrochloric acid

Solution transferred to column

t
Elution with TBP - tdluene (1:l)

t
Discarded 1 ~a. 50 ml

1
Pi - 30-60 ml

i
Pd 4 75-125 ml

1
Addition of approx. 15 ml of oxidizing solution (chlorine in TBP - toluene 1
t
Elution with TBP - toluene (1:l)

1
lr * co. 50 ml

+
Elution with water

t
Rh - co. 50 ml

Scheme 2. Separation of platinum-group metals on cellulose.

Gold in the presence of a small amount of nitric acid was successfully precipitated with hydrazine hydrate,
and some of the results are shown in Table 4.
Provided that in the determination of rhodium. iridium and gold, use is made of small porcelain crucibles
having porous bottoms and a constant weight under the experimental conditions, relatively accurate results can
be obtained for amounts of metal larger than 2 mg.

RESULTS
The precision obtainable with the proposed analytical procedure was tested by the
analysis of twelve synthetically prepared samples containing platinum, palladium, rho-
dium, iridium, and gold in the amounts shown in Table 5. The results obtained for rho-
dium, iridium and gold show that the difference between the mean amounts recovered and
the amounts added is well within the expected precision of the analytical procedure. Plati-
num and palladium were not determined in this analysis.

Table 3. Accuracy obtainable with mg amounts of Rh and Ir

Rhodium Iridium
Added. Found. Difference, Added, Found, Difference,
my my nrg mg W mg

I.0 1.25 + 0.25 1.0 1.24 +024

I .o I .24 + 0.24 1.0 1.32 + 0.32
2.0 2.10 f0.10 2.0 2.08 + 008
2.0 2.14 +0.14 2.0 1.99 -0.01
2.0 2.10 +0.10 2.0 2.04 + 0.04
3.0 3.08 + 0.08 3.0 3.11 +0.11
3.0 2.96 - 0.04 3.0 3.05 + 0.05
924 C.POHLASDT and T.W. STEELE

Table 4. Gravimetric determination of gold with hydrazine hydrate

Au added. Au found Difference.

mg ‘rig in9

6.06 6.08 + DO2

7.07 7.14 + 0*07
8.08 8.13 + 0.05
IO.10 1009 -0.01

Table 5. Analysis of synthetic samples

Mean amount
Amount added, recovered, Difference. Coeff. of variation,
Element 0,
me mg mg ,‘O

Gold 10.10 LO.09 -@Ol I.2 (1.01

Platinum 49.55 49.20 -0.35 1.3
Palladium 54.56 54.21 -035 0.5
Rhodium 40 4.04 + 0.04 I .47 (0.91
Iridium 2.0 2.05 + 0.05 2.49 12.81

Table 6. The determination of noble metals in matte-leach residues

1
i
Sample Au. Pt. ’ Pd, Rh, Ir,
No. “,’ IIi I>, 0i
% /O i0 ‘0 /O
Proposedprocedure 1.47 18.4, 7.84 0.86 0.29
1 AAS 1.35 18.1, 8.06 0.81 0.19
Proposed procedure I.52 18.1, 7.67 0+3.S 0.27
2 AAS 1.28 18.2, 7.82 @82 0.19
Independent lab. 1.51 18.6, 7.91 0.87 0.23
Proposed procedure I.10 14.06 5.73 0.61 0.21
3 AAS 1.16 14.2, 5.97 0.61 0.18
Independent lab. I.15 14.5, 589 0.62 0.20

The coefficients of variation given in brackets in Table 5 were obtained previously8 by

the proposed procedure, but with an atomic-absorption finish, instead of gravimetry.
The difference in the coefficients of variation for rhodium is probably due to AAS
analysis being applied to a rhodium level of 10 mg, instead of 4 mg.
The proposed procedure was also applied to the analysis of samples of matte-leach resi-
dues. The results obtained are shown in Table 6 and can be compared with those obtained
when the noble metals were determined in the presence of one another by AAS, and with
results obtained by an independent laboratory.

CONCLUSION
It has been shown that the noble metals can be separated by a simple chromatographic
procedure in a sufficiently pure state to permit gravimetric determination with a relatively
high degree of accuracy and precision. However. because of the absence of any interfering
 Determination of noble metals 925

elements after the ~hromatographic separation, the same degree of accuracy and precision
can be obtained when the metals are subsequently determined by AAS. Moreover, this
work has shown that, while accurate results have been obtained with the proposed pro-
cedure, they are not outstandingly more accurate than those obtained by the much faster
method of direct AAS measurement.
The proposed procedure, nevertheless, is very useful as an umpire method when an
analysis independent of AAS is required. and also when, because of the complexity of a
sample. or because of unsuspected interferences, the more direct AAS procedure may give
doubtful results.

AcknowledHanr~llt-The authors wish to thank the Director General of the National lnstitute for Metallurgy.
Johannesburg. for permission to publish the work described in this paper.

REFERENCES
1. C. Pohlandt and T. W. Steele. J. S. ,4f;-. Chem. Inst., 1972. 25, 198.
2. R. V. D. Robert and T. W. Steele. Naf. insr. Metali. Joba~?l?eshIfrg, Rrpt. No. %I. May 1970.
3. R. C. Mallett. R. Breckenridge. 1. Palmer and K. Dixon, ihid., No. 1401, March 1972.
4. C. Pohlandt. ibid., No. 1.574.Nov. 1973.
5. J. Fritz and W. G. Millen. ~u~anrff. 1971.18, 323.
6. I. Fidelis. R. Gwozdz and S. Siekierski. ~~~~~~~Y~~u. 1963.8, 327.
7. I. Akdza. T. Kiba and T. Kiba. Bull. Chem. Sot. Japan, 1970,43,2063.
8. C. Pohlandt and 1. W. Steele. Talanra. 1972.19. 839.
9. F. W. E. Strelow. J. S. 4/i, C/WJll. IJlSr., 1961. 14; 51.
10. T. Ishimori. Japan. At. Energy Res. Insr. Rept., 1047, 1963.
11. C. E. F. Lundell and J. I. Hoffman, O~r~~nes~~~~~~0~s ~~C~ze~icul Anafysia Wiley, New York, 1938.
12. T. T. Gorsuch. A~7nl.w. 1959. 84, 135.
13. C. Pohlandt. R. V. D. Robert and A. M. Vallee, Natl. Inst. Metall., Jo~nnesburg Rept., No. l500, Jan. 1973.
14. C. T. Hu and H. C. Hsieh. Ko Hszceh Turjy Pm 1963.8, 54.
15. C. T. Hu and H. C. Shi. Hucr Hsrteh Hsuelt Puo. 1964. 30, 352.
16. C. T. Hu and C. L. Liu. k’o H.%Jdi Tuug Pao. 1964, 12, 1103.
17. L. N. Moskvin, Radjo~~j~~l~~u.1964, 6, 110.
18. S. T. Payne. halyst. 1960.85, 698.
19. E. S. McKay and R. W. Cordell. Tala~m, 1971. 18, 841.
20. F. E. Beamish. The AiIa~~zi~a~Chernisrrg qfthe No&f@Metals. Pergamon. London, 1966.

Zusammenfassung-Die praktische Anwendung verschiedener chromatographischer Methoden

auf die Analyse von Riickstanden aus der Auslaugung von Kupfer-Nickel-Stein wird beschrieben.
Gold wird dabei an einer TBP-~handelten Porasildule abgetrennt, die unedlen Metalle durch
Kationenaustausch; Tellur wird voa den Metallen der Platingruppe und die nichtfltichtigen Metalle
der Platingruppe werden voneinander auf einer CelluIoses&ule getrennt.

R&sum&-On decrit I’application pratique de diverses methodes chromatographiques ii l’analyse

de residus obtenus A partir de Epuisement de mattes cuivre-nickel. La technique comprend Ia
separation de l’or sur une colonne de Porasil traitee au TBP, la separation des mttaux basiques
par echange de cations. la separation du tellurium des mitaux du groupe du platine, et la sepa-
ration des metaux du groupe du piatine non volatils sur une colonne de cellulose.