SEPARATIONS O F T H E PLATINUM METALS BY I O N EXCHANGE'

S. S. BERMANAND \;IT.
A. E . MCBRYDE

ABSTRACT
Distribution coefficients for the chlorides of ruthenium, rhodium, palladium, iridi~un(II1
and IV), and platinu~nhave been deternli~ledbetween the anion exchanger Amberlite IRA-400
and hydrochloric acid solutions of various molarities. Separations of various combinations'of
rhodium, iridium, palladiu~ll,and platinum in amounts of 0.5 mg. or less are described.
When, in the course of these separations, the four metals are present together, special pro-
cedures are required t o ensure conlplete recovery of p l a t i n u ~ l ~ .
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There have been several attempts to employ ion exchange in the separation of the
platinum metals, but only a limited degree of success has been achieved. MacNevin and
Cruinmett (1) suggested t h a t a separation of rhodium, iridium, palladium, and platiilum
might be possible owing to the graded stabilities of the chloride and ammine complexes
of these metals, but presented no experimental data. Another report by the same authors
(2) elaborated on a separation of iridium from palladium achieved by converting the
palladium to a cationic diammine, leaving the iridium as an anion, and separating the
two on this basis. Stevenson et al. (3) submitted a note on the separation of the four
metals on the cation exchanger Dowex-50, based on the formation of perchlorates of
these metals by fuming their solutioils with perchloric acid. No d a t a were given, but
For personal use only.

this separation is of questionable value because of the inability to keep even milligram
quantities of platinum and iridium from precipitating in this medium. Blasius and
Wachtel (4) achieved separations of from the other three metals by adsorbing
the platinum complex on the anion exchanger Permutit-ES in the hydroxide form. T h e
other three metals were eluted by a solution of sodium hydroxide, and the platinum
recovered by elution with nitric acid. WIacNevin and McI<ay ( 5 ) have prepared spectro-
graphically pure rhodium through the formation of a cationic rhodium species, the
other metals being left as anions. This separation is not quantitative. T h e separations
of rhodium and iridium have been discussed in a previous paper (G).
The only equilibrium data recorded c o ~ l c e r ~ l i ~
the
l g behavior of platinum metal com-
plexes toward ion exchangers are those of Kraus et al. (7). These worlters measured the
distribution coefficients of chloroplatinate (IV) and chloropalladate (11) relative to the
anion exchanger Dowex-1 in hydrochloric acid solutions.
In the followi~lgreport the measurement of the distribution coefficients of ruthenium,
rhodium, iridium, palladium, and platinum in hydrochloric acid solutions relative t o
the anion exchanger Amberlite IRA-400 is described, as well as a series of separations
of these metals.
EXPERIMENTAL
Standard Solutions
Pal1adiunz.-A stock solution was prepared by dissolving pure palladium sponge in
aqua regia, evaporating several times to dryness with hydrochloric acid, and then
dissolving the residue and diluting with 0.1 M hydrochloric acid. This solution was
standardized gravimetrically by precipitation with salicylaldoxime (8). Analyses for
palladium were generally made colorimetrically by the potassium iodide method (9),
'Manz~scriptreceioed Decevzber 3, 1957.
Contribz~tionfrom the Department of Chenzistry, Unioersity of Toronto, Toronto 5, Ontario, Canada.

Can. J. Chem. Vol. 36 (1958)

 83 6 CASADIAX JOURNAL 01: CI-IEMISTRY. VOL. 3G. 1958

but very small amounts (less than 10 pg.) were determined by the 9-nitrosodimethylalli-
line procedure (10).
P1atinz~m.-The stocl; solution was prepared by the dissolutioll of pure platinum
spoilge in aqua regia and treatment similar t o that described for palladium. The solution
was staildardized by precipitation with 4-phenylthiosemicarbazide (11). Colorimetric
analyses were made by the tin(I1) chloride method (12).
Ruthenium.-A stock solution was prepared in 0.5 M hydrochloric acid from ammonium
chlororuthenate crystallized from a solution of sodium chlororuthenate in hydrochloric
acid. The solutio~lwas standardized by the evaporation of a measured quantity, followed
by reduction of the salt to inetallic ruthenium with hydrogen. Analyses were made
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colorimetrically by the thiourea procedure (13).

Rhodium and Iridium.-The preparation of standard solutions of these metals is
described in a previous paper (6).
The Resin and Columns
The resin used in this research was Amberlite IRA-400 in an ailalytical grade. The
dried resin was ground t o yield fractions of various degrees of fineness. The portion of
mesh size 70 t o 100 was used for the measurement of distributioil coefficients. I t was
found to be hygroscopic, and was dried a t 100' C. prior t o weighing, and was stored over
anhydrous magnesium perchlorate. The exchange capacity was found to be 3.78 meq.
per gram of dry resin. This was determined for 5.00-g. samples by the procedure of
For personal use only.

Fisher and I<unin (14).

For column work the resin of < 100 mesh was used. The manner of preparing the
resin to rid it of fine particles has been described in a previous paper (6). The columns
were of conventional design in two sizes, having internal diameters of 10 mm. and 5 mm.
respectively. The depth of resin in the bed varied among the different experiments, and
is stated in the descriptioil of each. The flow of liquid through the beds was maintained
a t about 50 ml. per hour.
Afeasurement of Distribution Co&cients
The distributioil coefficients of chloropalladate(1I), chloroplatinate(1V), chloroiridate
(IV), chloroiridate(III), chlororhodate, and cl~lororuthenatewere measured in hydro-
chloric acid solutions. This was done by shaking a weighed amount, approximately 0.3 g.,
of resin with measured quantities of platinum metal solutions in 25.0 ml. of hydrochloric
acid of various molarities for 40 hours. The mixtures were filtered, and 20.0-ml. aliquots
of the filtrates analyzed. The amounts of metal adsorbed on the exchanger were thus
found, and the distribution coefficients (amount of metal per kilogram of resin/an~ount
per liter of solution) were calculated. In regions of very high adsorption 300 ml.rof acid
solution was used, and 250-ml. aliquots taken for analysis.

TABLE I
DISTRIBUTIOS
COBPPIC~ENTS

D
HCI, ill Rh Ru Ir(II1) Ir(1V) Pd(I1) Pt(IV)
 BERMAN AND McBRYDE: PL.4TINGM METALS 837

The amounts of resin and solution were selected to limit loading of the resin to no
more than 2% of capacity.
The results are summarized in Table I and in Fig. 1.
A comparison of these values with those obtained by Icraus et al. (7) for Pd(I1) and
Pt(1V) shows good agreement in the low-adsorption range where these worlcers had low
degrees of loading. In the high-adsorption range where these worlcers allo\vecl the loading
t o become large there is a marked divergence, their distribution coefficieilts being much
lower than those given here.
I t is readily seen that Pt(1V) and Ir(IV) are very strollgly adsorbed throughout the
whole hydrochloric acid range, and Pd(I1) a t low hydrochloric acid concentrations.
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According to Walton (15) practically all ion-exchange distribution data can be ex-
pressed by the Rothmund-Kornfeld equation

where iWz and M, are the moles of s and y per gram of exchanger and ( x ) and (31)
are their molar concentrations in solution; K and p are constants. Theii by plotting
log(A/l,/fif,) against log((s)/(y)) one shoulcl obtain a straight line.
For personal use only.

FIG. 1. The distribution coefficiellts of rhodium, iridiiuun, platinum, palladium, and ruthenium in
hydrochloric acid solutions. A : chloroiridate(lV), B : cl~ioroplatinate(IV),C: chloropalladatc(ll), D:
chlororuthenate(lII), E: chloroiridate(I1 I), F : chlororhodate.
FIG. 2. 'I'he clistribution data plotted according to the liothmund-ICornfeId equation. A : chloroiridate
(IV), B : chloroplatinate(IV), C : chloropalladate(1 I).

This is, more or less, what happened when the data for Rh, Ru, and Ir(II1) were
plotted. However, the three other complexes produced iilteresting curves (Fig. 2). In
regions of very high adsorptioil MZ/iW,' (the squared term arises since these complexes
are doubly charged) is seen to be almost independeilt of the conceiltration ratio of
complex to chloride in solution; i.e., p = 0.
This might indicate that in these instances simple exchange equilibria are not taking
place and t h a t some mechailism other than ion exchange is the predominant factor.
 838 CANADIAN JOURNAL O F CIIEMISTRY. VOL. 36. 1958

An analogy may be seen here between this strong adsorption and the solubility of
quaternary amine platiilum metal chlorides. I t is well ltnown that Pt(1V) and Ir(1V)
form relatively iilsoluble salts with quaternary amines of the type (R,1N)J'tCl6. Since
the anion exchanger is in effect a polystyre~ledivinylbellzenequaternary amine, it may
be that the same forces that produce the insoluble salts contribute to the strong adsorp-
tion of these complexes on the resin. Palladium(I1) is ltnown to form a number of in-
soluble diammine dichloride complexes, the solubility of which is greater in concentrated
hydrochloric acid than in neutral solution. The behavior of palladium toward the resins
may be, in the same fashion, compared with the formation of ammine precipitates of
this sort.
T o further illustrate this analogy 5 ml. of 0.2 M tetrabutylammoilium chloride was
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added to 10 mg. of each of the six complexes in 5 ml. of 0.5 iM hydrochloric acid. Precipi-
tates formed in the tubes containing Pd(II), Pt(IV), and Ir(1V). When 1 1111. of concen-
trated hydrochloric acid was added to each of these, the palladium precipitate dissolved
instantly and the iridium precipitate partially dissolved. Further addition of hydrochloric
acid resulted in the complete dissolution of the iridium precipitate, but the platinum
precipitate could only be partially dissolved by this means.
LVhile the above experiment does not prove that stable resin-platinum metal com-
pounds are formed analogous to iilsoluble precipitates, the parallel between these obser-
vations and subsequent column experiments was strilting. For example, it was possible
to remove Pd(I1) from the resin by elution with concentrated hydrochloric acid. Pt(1V)
For personal use only.

and Ir(1V) cannot be completely recovered by this means. The iridium complex may be
removed by a hot extraction with hydrochloric acid, but even this rather violent treatment
will only partially remove the platinum complex.
The Separation of Palladiz~mand Platinum
The purpose of this research was to develop an ion-exchange procedure for this separa-
tion which could be integrated with the rhodium-iridium separation previously reported
(6). Also, the recovery of Pd(I1) and Pt(1V) from anion exchangers by a wet method has
long been a problem and an obstacle in the application of anion exchange in the separation
of platinum from base metals.
I t was confirmed that Pd(I1) and Pt(1V) can be quantitatively adsorbed from dilute
hydrochloric acid solutions on an anion exchanger, Amberlite IRA-400.
The Recovery of Palladium
Five milliliters of 1 M hydrochloric acid containing approximately 500 y of palladium
were fed onto 2.5-cm. resin beds in the larger columns which had been previously washed
with 25 ml. of the acid solution. Complete recovery of the palladium was achieved by
100 ml. of 12 iM hydrochloric acid.
Number of esperi~nents 5
Palladium taken 478 -y
Palladium recovered (range) 476-480 -y (see Fig. 3 )

I t was found that no platinum was eluted provided these beds were a t least 2.3 cm.
deep.
The work was repeated with 3-cm. beds in the smaller columns. Complete recovery
was achieved by 40 ml. of 12 A[ hydrochloric acid or by 60 ml. of 9 Macid (see Fig. 3).
The use of 6 M acid resulted in too much tailing to be of value. However, it was found
that 40 ml. of 12 M hydrochloric acid eluted much platinum, whereas 60 ml. of 9 M
acid eluted none.
 BHRlvIAN A N D McBIIYDE: PLATINUM MET.\LS

ML. ELUANT
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FIG.3. Some typical elution curves for chloropalladate(l1) and chloroplatinate(1V). A : chloropalln-
date(I1) el~rtetl\\.it11 12 11J hydrochloric acid solution (small c o l u m ~ ~B:
) , chloropalladate(I1) eluted with
!I Jf hydrochloric acid solution (small column), C : chloropalladatc(ll) eluted with 12 116 hydrochloric acid
solution (large column), D : chloroplatinate(lV) eluted with 2.4 ilf perchloric acid solution (small column),
E: chloro1~latr~iate(IV)
eluted with l 5 7 i (I\,/\.) zinc chloride in 9 Af hydrochloric acid solution a t 96' C.
(large column).

I t was also shown that Pd(I1) could be easily recovered by elution with dilute per-
chloric acid solutions. The recoveries observed for elutioil with 40 ml. of 0.5 M perchloric
acid were as follows:
Number of experiments
Palladiu~ntaken
Palladium recovered
For personal use only.

Since perchloric acid was later shown to be a good eluant for Pt(1V) this reagent caililot
be used to separate the two metals.
Recovery of Platinum
Platinum was fed onto 2.5-cm. resin beds in the larger columns in a manner similar
to the palladium.
I t was verified that solutions of hydrochloric, nitric, or sulphuric acids, either dilute
or concentrated, elute only part of the Pt(1V). The same is true forammoniacal eluants.
Workiilg a t elevated temperatures produced only minor improvements in the recoveries.
Kraus and his co-worlters (7, 16) noted the high affinities of zinc and cadmium chloride
in hydrochloric acid solutions toward anion exchangers. Preliminary experiments with
2.5 M solutions of both these salts in 9 M hydrochloric acid showed better recoveries of
platinum than had been previously achieved. I t was found that 93% of the Pt(1V) could
be recovered by the zinc chloride solution, and that quantitative recoveries could be
achieved if the column were surrounded with a hot-water jacltet a t 96' C. The following
recoveries were made by elution with DO ml. of a 15% ((w/v) solution of zinc chloride in
9 M hydrochloric acid a t D6O C. (see also Fig. 3).
Number of experiments
P l a t i n ~ ~taken
m
Platinum recovered
Experimeilts showed that the Pt(1V) could also be quantitatively recovered by 90 ml.
of 2.4 M perchloric acid. T h e same observation was made with 3-cm. resin beds in the
smaller columns; in these cases the platinum was recovered by 60 ml. of the 2.4 M
perchloric acid (see Fig. 3).
Number of experiments 7
P l a t i n ~ ~taken
m 490 y
Platinum recovered (4 cases) 488-492 y (I)*
( 3 cases) 488-490 y (s)*
*I means larger column, s smaller.
 840 C.AXADIAN JOURN.AL O F C H E M I S T R Y . VOL. 30, 1958

Attempts to recover the Pt(1V) by a Soxhlet extractio~lwere unsuccessful. Extraction

with 6 111 hydrochloric acid produced recoveries of only about 30%. Recoveries of about
90y0 were achieved with 8 ilf nitric acid.
The recovery of platinurn by ashing the exchanger was also investigated. This methocl
had previously been reported as successful by Sussman et al. (17) but no data were given.
The resin containing the adsorbed Pt(1V) and the glass wool plug were transferred to a
small crucible and driecl under a heat lamp. The crucible was placed in a furnace a t
300" C. and the temperature raised to 900" over the course of an hour. The crucible was
removed, cooled, and set over a boiling-water bath for 1 hour after the addition of 3 or
4 ml. of aqua regia. There was no residue evident in the crucible after this treatment
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save for the bit of fused glass wool. Results of the analysis of this solution after filtration
are given below, ancl indicate that this procedure is n simple and satisfactory one for the
recovery of the metal.
Number of experi~nents
Platinum taken
Platinum recovered

Separation of Palladiz~mand Platinum

Separations were carried out in both large and small colurnns. Mixtures of the metals
containing G mg. of sodium chloride (to prevent baking of the metal on the bottom of the
beaker) were evaporated to dryness and the resiclue dissolved in one or two milliliters of
water. This solution was fed onto the resin becl with a dropper. The larger beds n7ere
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2.5 cm. deep and were eluted with 100 ml. of 12 ill hydrochloric acid followecl by 90 ml.
of 2.4 d l perchloric acid. The smaller columils c o ~ ~ t a i n eresin
d beds 3 cm. deep, and were
eluted with 60 ml. of 9 M hydrochloric acid follolved by 75 ml. of 2.4 ill perchloric acid.
The results are su~nmarizedbelow:
Nurnber of experiments
Platinum taken
Platinum recovered ( 4 cases) 487-496 (1)
(3 cases) 490-491 -i (s) 97-102 7
Palladiu~ntaken 478 y 96 y
Palladium recovered ( 4 cases) 468-480 y (I)
( 3 cases) 476-47s -y ( s ) 95-96 7

Separations of T~ariozisMixtures of Plakinzim iMetals ,in Solzition

From the satisfactory results obtained in the rhoclium-iridium ancl palladium-platinum
separations it was felt that separations of all combinations of the four metals could be
achieved, although separations of mixtures containi~lgboth rhodium and iridium would
obviousl~ihave to be carried out in two stages. This turned out to be an overly optimistic
assumption when iriclium, palladium, and p l a t i n ~ ~are
m all present, but, generally, some
very satisfactory separations were made.
Rhodium altd Palladium
This separation was first done on 2.3-cm. beds in the larger columns. The beds were
washed prior to use with 10 ml. of 2 M hydrochloric acid. A solution containing the two
metals in 5 ml. of 2 M hydrochloric acid was fed onto the bed, and the latter eluted with
90 ml. of the acid solution t o remove the rhodium. Elution was continued with 100 ml.
of 12 M hydrochloric acid to recover the palladium. A previous experiment showed that
no palladium was eluted by 90 ml. of the 2 M hydrochloric acid. The results of this
separation are tabulated below.
Further separations were carried out in the smaller columns with 3-cm. resin beds which
were previously washed with 10 ml. of 2 M hydrochloric acid. In this case the solutio~ls
 BERMAN A N D McBRYDE: PL:\TINUM METALS 841

were evaporated to dryiless with G mg. of sodium chloride, redissolved in one or two
milliliters of water, and fed onto the bed with a dropper. Elutions were made with 50 ml.
of "M hydrochloric acid followed by 50 ml. of 9 M hydrochloric acid. The results are
included in the following table.
Number of experiments 6
Rhodiurn taken 409 -j
Rhodium recovered ( 3 cases) 499-500 1 (1 )
(3 cases) 500-501 y (s)
Palladium taken 478 -1
P a l l a d i ~ ~recoverecl
m (3: cases) 478-479 y (I)
(3 cases) 476-478 y (s)
I t was noticed in this separation that as the rhodium was being eluted with the 2 M
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hydrochloric acid the palladium band slowly moved and diffused part way down the
bed. This is the only instance in this work where a platiil~immetal band was seen to move.
Owing to this partial nligratioll it was possible to recover the palladium with 40 ml. of
0 M hydrochloric acid (Fig. 4) in contrast to the 60 ml. needed in the palladium-platinum
separation.
For personal use only.

ML, ELUANT
FIG.4. Elution curves for the separation of rhodium, palladium, and platinum (small colurnn). R h :
eluted with 50 ml. 2 111 hydrochloric acid solution, Pd: eluted with 50 ml. 9 1
11hydrochloric acid solution,
Pi:-eluted with 75 rnl. of 2.4 il/l perchloric acid solution.

Rhodizon and Platinum

This separation was not attempted, but since the separation of rhodium, palladium,
and platinum is feasible (see below) there is no reason why it should not be easily accom-
plished.
Iridium and Palladium
in a rnalliler similar to the separation
This separation was done i l l the larger colui~~ils
of rhodium and palladium. T h e iridiunl was reduced to the tervalent state by hydroxyl-
arnine prior to feeding onto the column. T h e bed was eluted with 00 ml. of 2 M hydro-
chloric acid to recover the iridium, and then 100 ml. of 12 114 hydrochloric acid for the
palladium. The results are suinmarized as follows:
Number of experiments 3
Iriclium taken 454 -/
Iridii~rnrecovered 452-454 -/
Pall,ldii~rntaken -178 y
I'alladium recovered 474-478 7
Iridium and Plat inzlm
This separation was not triecl, but experiments described below indicate that it is
quite feasible.
 842 CANADIAN JOURNAL OF CHEMISTRX'. VOL. 36, 1958

Rhodium, Palladium, and Platinum

One separation of these three metals was made to gather data for Fig. 4. This is the
only three-metal separation that can be made with only one column. A solutioll corltainiilg
the three metals was evaporated to dryness with ti mg. of sodium chloride. The residue
nras redissolved in 2 ml. of 2 116 hydrochloric acid solution and fed with a dropper onto
a small 3-cm. resin bed which had been previously washed with 10 ml. of the acid solution.
The bed was eluted with 50 ml. of 2 144 hydrochloric acid, followed by 50 ml. of 9 dl
l~ydrochloricacid, and then 70 rnl. of 2.4 i
W perchloric acid.
12hodium, Iridiz~m,and Palladium
Solutions of these three metals were evaporated to dryness with G mg. of sodium
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chloride and the residues redissolvecl in 1 ml. of water. The iridium was recluced with a
few drops of 1% hydroxylammoniu~nchloride solution, and the solutions fecl onto 3-cm.
beds in small columns. These beds hacl been previously washed with 10 ml. of 2 M h~.clro-
chloric acid. The be+ were eluted with 80 ml. of the acid solution to recover the rhodiu~ll
and iridium, followed by 50 ml. of 9 M hydrochloric acid for the palladium. The first
effluents were evaporated to clr>.ness and the residues redissolved in 2 ml. of 0.8 111'
hydrochloric acid (also containing cerium(1V) sulphate a t a concentration of 0.001 M).
These solutio~lswere fed with a dropper onto small colum~lscontaining 3-cm. beds of
resin which had been prepared with quadrivalent cerium, and the rhodium-iridium
separation was carried out as described in the previous communication (ti).
The procedure was repeated but the palladium was eluted with 50 ml. of 0.5 ill per-
For personal use only.

chloric acid. The rhodium and iridium were not determined in these experiments. 'The
various results are summarized below.
N ~ ~ m b of
e r experiments
Iridi~imtalcen
Iridium recovered
Rhodi~nntalren
IZhodium recovered
Palladium talien
Palladium recovered 476-479 y (elut& with HC1)
476-479 7 (3 eluted with I-IC104)

Rhodium, Iridium, and Platinum

The procedure was exactly as described above except that the beds were eluted with
80 ml. of 2 &I hydrochloric acid followed by 75 ml. of 2.4 M perchloric acid for the
platinum.
Nurnber of experiments
Iridium talcerr
I r i d i ~ ~ nrecovered
r
Rhodium talcen
Rhodium recovered
I'lxtinum taken
P l a t i n ~ ~recovered
m

Rhodium, Iridium, Palladium, and Platinum

Solutions containing these four metals were evaporated to dryness with ti mg. of sodium
chloride, and the residues redissolved in 1 ml. of ivater. A few drops of hydroxylamine
solution were added to reduce the iridium, and the solutions were then fed onto 3-cm.
beds in small columns. The beds were eluted with 80 ml. of 2 M hydrochloric acid followed
by 50 ml. of 9 Ad hydrochloric acicl, and then with 75 ml. of 2.4 A6 perchloric acid. T h e
first effluents were treated for a separation of rhodium and iridium as described above.
Good results were obtained for the recovery of rhodium, iridium, and palladium, but
the platinum recoveries were all low by about 25%.
 B E R M A S A N D McBRYDE: PLATINUM METALS 843

Further examination showed t h a t some platinum was being eluted along with t h e
palladium b u t had not been noticed since this small quantity produced a negligible
interference in the palladium determinations. I t is believed t h a t this early elution of the
platinum was due t o a partial reduction of the quadrivalent metal t o the bivalent state
by the hydroxylamine used t o reduce the iridium. T h e bivalent platinum evidently has
much the same affinity for the resin a s the bivalent palladium.
An unsuccessful search was made for a reducing agent which would reduce the quadri-
valent iridium but not a n y of the quadrivalent platinum. Best results (94% recovery
of the platinum in the "platinum fraction") were obtained by the slow reduction of
the iridium in neutral solution by sodium oxalate.
An a t t e m p t t o reoxidize the platinum on the exchanger with cerium(1V) after the
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removal of t h e tervalent iriclium was also ~~nsuccessful.

One separation of the four metals was carried out in which the "palladium fraction"
was evaporated t o a few ~nilliliters,boiled with nitric acid t o oxidize the platinum, and
evaporated twice t o dryness with hydrochloric acid. T h e residue was dissolved in a few
milliliters of 2 M hydrochloric acid, and this solution treated as described above for t h e
separation of palladium and platinum. In this way platinum was completely recovered
in two fractions.
Taken Fo~und
Rhodium 499 y 501 y
Iridium 4547 451y
Palladium 478 7 479 7
l'latinu~ll 490 y 363 plus 127 = 490 y
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Hydrolytic Sefiaration oJRhodium, Iridzum, and Palladium from P l a t i n u m on a Microgram

Scale
T h e generally accepted procedure of precipitating rhodium, iridium, and palladium
a s hydrated oxides as a method of separating these metals from platinum has never
been applied on a microgram scale. In view of the relative difficulty encountered in t h e
four-metal separation clescribed above it was decicled t o investigate the possibility of
removing t h e platinum by this method prior t o applying an ion-exchange separation for
the remaining three metals.
T h e procedure followed was generally t h a t described in :lfifilied inorganic analysis
(18), pp. 376-377, except t h a t a carrier was employed t o aid in the precipitation of the
small quantities of the metals present. Both titanium(IV) sulphate and cerium(1V)
sulphate were used for this purpose. T h e cerium salt was finally chosen because its
precipitate was easier t o handle.
A solution of platinum was evaporated t o d r j ness with 6 mg. of sodium chloride in a
30-ml. beaker. T h e residue was dissolved in 1 ml. of 2 M hyclrochloric acid and diluted
t o about 5 ml. with water. T h e solution was then heated t o boiling and about 5 mg. of
cerium(1V) sulphate was added followecl by 5 ml. of a filtered solution of sodium bromate.
A filterecl 10% solution of soclium bicarbo~latewas added slowly until the first trace of a
permanent precipitate formed. Then 5 ml. more of the sodium bromate solution was
addecl. Adclition of bicarbonate mas continuecl until no further precipitation was evident.
Another 5 ml. of bromate solution was added, and the misture was boiled for 10 minutes.
T h e mixture was allowed t o cool, the precipitate t o settle, and t h e \vllole xvas then
filtered through a porcelain filter crucible of medium porosity. T h e precipitate was
washed with 0.1 M sodium chloride solution. T h e filtrate was boiled with l~ydrochloric
acicl t o destroy the brornate, and analyzed for platinum. Complete recovery of the
platinum was obtained.
 844 CANADIAN JOURNAL O F CI-IEMISTRY. VOL. 36, 1858

Solutions of the four metals were treated as above, a n d again all t h e platinum was
found in the filtrates, indicating i t s separation from t h e other three metals.
T h e oxide precipitate from one of these experiments was dissolved in concentrated
hydrochloric acid, evaporated t o dryness, a n d the three metals separated as described
above. A quantitative separation of t h e four metals was accomplished b y this means.
Talien Found
Rhodium
Iridiuin
Palladium
Platinum

These experiments indicate t h a t the ion-exchange s e p a r a t i o ~ l smay be integrated with

a Gilchrist-Wichers t y p e of scheme (18) for the a ~ l a l y s i sof t h e platinum metals on a
Can. J. Chem. Downloaded from cdnsciencepub.com by 82.210.178.95 on 05/14/21

microgram scale.

Separation of Rhodium and Ruthenium

I t has been noted t h a t this separatioil is of interest t o radiochemists since rhodium
is a daughter of ruthenium b y b e t a decay. Some qualitative experiments were made to
determine t h e feasibility of making t h e separation b y ion exchange.
Ruthenium behaves toward the exchanger much like i r i d i ~ u n .T h e quadrivalent com-
plex is strongly adsorbed b u t appears t o be partially reduced by the resin so t h a t relatively
large losses occur in t h e feed effluent. T h i s can be remedied by the addition of a n oxidant
such as cerium(1V) t o t h e feed solution. A t t e m p t s t o elute t h e quadrivalent ruthenium
with hydrochloric acid were unsuccessful, a s was a n a t t e m p t t o reduce i t on the resin
For personal use only.

with a 1% solution of hydroxylammonium chloride. T h e tervaleilt complex has a very

low affinity for the resin, ancl a separatioil of it from tervaleilt rhodium cloes not seem
t o be possible.
It is possible t h a t a procedure similar t o t h a t evolved for t h e separatioil of rhodium
a n d iridium could be developed t o separate t h e two metals in solution, b u t t h e problem
of the quantitative removal of the quadrivalent rutheilium from t h e resin requires further
study.
XCICSOWLEDGMENTS
T h i s i~lvestigatioilwas assisted by a g r a n t from t h e University of Toronto's Advisory
Committee on Scientific Research, for which grateful ack~lowledgment is made. One
author (S.S.B.) was holder in 1955-56 a n d 1956-57 of a fellowship given t o t h e uiliversity
b y Canaclian Industries Ltd., for which our thanks are here recorded.

REFERENCES
1. MACNEVIN, 117. M. and CRUMMETT, W.B. Anal. Chem. 25, 1628 (1953).
2. MACNEVIN, W. M. and CRUMMETT, W. B. Anal. Chim. Acta, 10, 323 (1954).
3. STEVENSOX, P. C., FRANK, A. A,, BORG,R., and NERVII~, W. J. Am. Chem. Soc. 75, 48761(1953).
4. BLASIUS, E. and ~VACHTEL, U. Z. anal. Chem. 154, 341 (1954).
5. MACNEVIN, W. M. and McICAY,E. S. Anal. Chern. 29, 1220 (1957).
6. BERMAN, S. S. and MCBRYDE, W. A. E. Can. J . Chem. 36, 845 (1958).
7. KRAUS, I<. rl., NELSON, F., and SMITH, G. W. J . l'hys. Chem. 58, 11 (1954).
8. HOLZER, 'I. Z. anal. Chem. 23, 299 (1951).
9. FRASER, J. G., BEXMISH, F. E., and ~/ICBRYDE,\v. A. E. AnaI. Chem. 26, 495 (1954).
10. YOE,J. I-I. and I<IRI<LAND, J. J . Anal. Chem. 26, 1335 (1954).
11. FRASBR, J. G. M.A. Thesis, University of Toronto, Toronto, Ontario. 1951.
12. AYRES,G. 1-1. and MBYER, A. S. Anal. Che~n.23, 299 (1951).
13. AYRES,G. 13. and YOUXG, F. Anal. Chem. 22, 1277 (1950).
14. FISHER, S. and I<UNIN, R. Anal. Chem. 27, 1191 (1955).
15. WALTON, 13. F. Chap. 1. In Ion exchange. Edited by F. C. Nachod, Acadenlic Press, Inc., New York.
1949.
16. KRAUS, I<. A. and WIOORE, G. E. J. Am. Chem. Soc. 75, 1460 (1953).
17. SUSSMAN, S., NACHOD, F. C., and WOOD, W. Ind. Erlg. Chem. 37, 618 (1945).
18. GILCHRIST, R. Chap. 20. 171 Applied inorganic analysis. 2nd ed. By Hillebrand, Lundell, Bright, and
Hoffman. John Wiley Sr Sons, Inc., New York. 1953.