You are on page 1of 72

2012 Wiley-VCH Verlag GmbH & Co.

KGaA, Weinheim
Article No : a21_075
Platinum Group Metals and Compounds
HERMANN RENNER, Degussa AG, (retired), Hanau, Federal Republic of Germany
G uNTHER SCHLAMP, Demetron GmbH, (retired), Hanau, Federal Republic of Germany
INGO KLEINW

ACHTER, dmc2 Degussa Metals Catalysts Cerdec AG, Hanau, Federal


Republic of Germany
ERNST DROST, dmc2 Degussa Metals Catalysts Cerdec AG, Hanau, Federal Republic of
Germany
HANS MARTIN L uSCHOW, Degussa-Huls AG, (retired), Hanau, Federal Republic of
Germany
PETER TEWS, Allgem. Gold und Silberscheideanstalt (AGOSI), Pforzheim, Federal
Republic of Germany
PETER PANSTER, dmc2 Degussa Metals Catalysts Cerdec AG, Hanau, Federal Republic
of Germany
MANFRED DIEHL, dmc2 Degussa Metals Catalysts Cerdec AG, Hanau, Federal Republic
of Germany
JUTTA LANG, dmc2 Degussa Metals Catalysts Cerdec AG, Hanau, Federal Republic of
Germany
THOMAS KREUZER, dmc2 Degussa Metals Catalysts Cerdec AG, Hanau, Federal
Republic of Germany
ALFONS KNoDLER, Forschungsinstitut fur Edelmetalle und Metallchemie, (retired),
Schwabisch Gmund, Federal Republic of Germany
KARL ANTON STARZ, dmc2 Degussa Metals Catalysts Cerdec AG, Hanau, Federal
Republic of Germany
KLAUS DERMANN, Ducera Dental GmbH und Co. KG, Hanau, Federal Republic of
Germany
JOSEF ROTHAUT, Ducera Dental GmbH und Co. KG, Hanau, Federal Republic of
Germany
RALF DRIESELMANN, dmc2 Degussa Metals Catalysts Cerdec AG, Frankfurt/M., Federal
Republic of Germany
CATRIN PETER, Klinikum der Friedrich Schiller Universitat, Jena, Federal Republic of
Germany
RAINER SCHIELE, Klinikumder Friedrich Schiller Universitat, Jena, Federal Republic of
Germany
1. History . . . . . . . . . . . . . . . . . . . . . . . . . 318
2. Properties . . . . . . . . . . . . . . . . . . . . . . . 321
3. Occurrence . . . . . . . . . . . . . . . . . . . . . . 323
3.1. Abundance . . . . . . . . . . . . . . . . . . . . . . 323
3.2. Ores and Their Origin . . . . . . . . . . . . . 325
3.3. Primary Deposits . . . . . . . . . . . . . . . . . 326
3.4. Secondary Deposits . . . . . . . . . . . . . . . . 328
3.5. Recovery of Secondary Platinum Group
Metals . . . . . . . . . . . . . . . . . . . . . . . . . . 328
3.6. Reserves and Resources . . . . . . . . . . . . . 330
4. Mineral Dressing and Beneciation . . . . 331
4.1. Treatment of Alluvial Platinum Deposits 331
4.2. Treatment of Primary Deposits . . . . . . 331
4.3. Treatment of Nickel Ores . . . . . . . . . . . 332
4.4. Treatment of Metal Scrap . . . . . . . . . . 333
4.5. Treatment of Dross . . . . . . . . . . . . . . . . 333
4.6. Treatment of Supported Catalysts . . . . 334
4.7. Treatment of Solutions . . . . . . . . . . . . . 334
DOI: 10.1002/14356007.a21_075
5. Dissolution Methods . . . . . . . . . . . . . . . 335
5.1. Dissolution in Aqua Regia . . . . . . . . . . . 335
5.2. Dissolution in Hydrochloric Acid
Chlorine. . . . . . . . . . . . . . . . . . . . . . . . . 335
5.3. Dissolution in Hydrochloric Acid
Bromine. . . . . . . . . . . . . . . . . . . . . . . . . 336
5.4. Other Dissolution Processes. . . . . . . . . . 336
5.5. Dissolution by Salt Fusion . . . . . . . . . . 336
6. Separation of Platinum Group Metals . 337
6.1. Chemistry of Platinum Group Metal
Separation . . . . . . . . . . . . . . . . . . . . . . 337
6.2. Older Separation Processes . . . . . . . . . 340
6.3. Current Separation Processes . . . . . . . . 341
6.4. Processes Used in Coarse Separation . . 343
6.5. Purication . . . . . . . . . . . . . . . . . . . . . . 346
6.6. Conversion of Salts into Metals . . . . . . 348
6.7. Partial Purication . . . . . . . . . . . . . . . . 350
6.8. Treatment of Internally Recycled Material 350
6.9. Construction Materials . . . . . . . . . . . . . 350
7. Platinum Group Metal Compounds . . . 351
7.1. Inorganic Compounds . . . . . . . . . . . . . . 351
7.1.1. Platinum Compounds. . . . . . . . . . . . . . . . 351
7.1.2. Palladium Compounds . . . . . . . . . . . . . . 352
7.1.3. Rhodium Compounds . . . . . . . . . . . . . . . 353
7.1.4. Iridium Compounds . . . . . . . . . . . . . . . . . 353
7.1.5. Ruthenium Compounds . . . . . . . . . . . . . . 354
7.1.6. Osmium Compounds . . . . . . . . . . . . . . . . 354
7.2. Organic Compounds . . . . . . . . . . . . . . . 354
8. Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . 355
8.1. Alloy Systems. . . . . . . . . . . . . . . . . . . . . 355
8.2. Special Alloys. . . . . . . . . . . . . . . . . . . . . 356
8.3. Methods of Treatment . . . . . . . . . . . . . 361
9. Quality Specications and Analysis . . . 361
9.1. Quality Specications . . . . . . . . . . . . . . 361
9.2. Qualitative Analysis. . . . . . . . . . . . . . . . 362
9.3. Quantitative Analysis . . . . . . . . . . . . . . 362
9.4. Purity Analysis . . . . . . . . . . . . . . . . . . . 363
9.5. Trace Analysis . . . . . . . . . . . . . . . . . . . . 364
10. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
10.1. Jewelry, Coinage, Investment . . . . . . . . 364
10.2. Apparatus . . . . . . . . . . . . . . . . . . . . . . . 364
10.3. Heterogeneous Catalysts . . . . . . . . . . . . 365
10.4. Fuel Cells. . . . . . . . . . . . . . . . . . . . . . . . 368
10.5. Homogeneous Catalysts . . . . . . . . . . . . 368
10.6. Automotive Emission Control Catalysts 369
10.7. Sensors . . . . . . . . . . . . . . . . . . . . . . . . . 369
10.8. Electrical Technology . . . . . . . . . . . . . . 371
10.9. Electronics . . . . . . . . . . . . . . . . . . . . . . . 372
10.10. Coatings . . . . . . . . . . . . . . . . . . . . . . . . 374
10.10.1. Coatings Produced by Electrolysis . . . . . . 375
10.10.2. Coatings Produced by Chemical Reaction 376
10.10.3. Coatings Produced by Physical Methods . 376
10.11. Dental Materials . . . . . . . . . . . . . . . . . . 376
11. Economic Aspects . . . . . . . . . . . . . . . . . 377
11.1. Supply . . . . . . . . . . . . . . . . . . . . . . . . . . 377
11.2. Demand . . . . . . . . . . . . . . . . . . . . . . . . . 378
11.3. Prices . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
11.4. Commercial Aspects . . . . . . . . . . . . . . . 378
12. Toxicology . . . . . . . . . . . . . . . . . . . . . . . 379
References . . . . . . . . . . . . . . . . . . . . . . . 380
1. History [110], [166], [167]
Figure 1 gives an historical survey of important
platinum group metal discoveries and platinum
group metal technology.
Early Times. The earliest evidence of plat-
inum is provided by a gold etui covered with
hieroglyphic inscriptions, dating from the 7th
century B.C. Around 1900, BERTHELOT (1827
1907) investigated the etui, which was kept in the
Louvre, and found that some of the inlays hith-
erto thought to be silver were in fact platinum.
In ca. 1900, jewelry made of native platinum
was discovered in Ecuador, which was part of the
Inca empire in pre-Columbian times. This prob-
ably dates from the rst ve centuries A.D.
In ancient times, the technique of washing
river sands and fusing together the grains of
platinum was undoubtedly known, as was the
making of alloys by heating alluvial platinumand
gold with a blowpipe, these methods being simi-
lar to those used in gold extraction and working.
Pre-Columbian Indians were familiar with a
powder metallurgy technique.
16th18th Century [11], [12]. In their
search for gold in the New World, particularly
in the area of present-day Colombia, the Spanish
often found alluvial (placer) platinum. The
earliest written report of the metal was made in
1557 by J. C. SCALIGER (1484 1558). Howev-
er, platinum was worked to produce jewelry and
utensils only after man had learned that the metal,
initially believed to be infusible, could be melted
and cast by rst adding other metals to lower its
melting point. Platinum was essentially regarded
as a troublesome material, accompanying gold
and silver, which lowered their workability. The
Spanish named the metal platina, the diminutive
form of plata (silver), as a derogatory term
because it was found only in small quantities or
318 Platinum Group Metals and Compounds Vol. 28
Figure 1. Historical survey of important platinum group metal discoveries and platinum group metal technology
Vol. 28 Platinum Group Metals and Compounds 319
as small granules. The terms white gold and
heavy silver were also sometimes used. When
the metal became well known in Europe in 1748,
thanks to the Spanish mathematician A. DE
ULLOA (1716 1795), the demand for platinum
increased. Its high density enabled it to be used to
adulterate gold, and its introduction into Europe
was therefore prohibited. Until 1908, the price of
platinum was lower than that of gold. Around
1750, the scientic investigation of platinum
began, initiated largely by C. WOOD (1702
1774), who learned of the metal in Jamaica in
1741. He can be regarded as the true discoverer of
platinum, having presented a paper in 1750 to the
Royal Society entitled The New Semi-Metal
Called Platina. In this initial period, fundamen-
tal investigations into the chemistry of platinum
(solubility in aqua regia, precipitation by addi-
tion of ammoniumchloride, fusion by addition of
arsenic, lead cupellation, etc.) were carried out
by W. WATSON (1715 1787), W. LEWIS
(1708 1781), and others. These workers, in-
cluding WOOD, often collaborated. Research at
this time had as its primary aim, distinguishing
and separating platinum and gold, although plat-
inum was at rst widely believed to consist of
gold contaminated with other elements.
An important development in platinum tech-
nology was the technique of converting the allu-
vial (placer) deposits into platinum sponge,
which could be satisfactorily formed by heat into
compact platinum or platinum artifacts. F. C.
ACHARD (1753 1821) discovered the method
of oxidizing an easily fusible platinum arsenic
alloy to remove arsenic. As early as 1784, he
produced the rst platinum crucible from plati-
num sponge made in this way.
19th Century. Around 1800, the accompa-
nying metals in native platinum, which generally
contains up to 80 % Pt, were discovered. W. H.
WOLLASTON (1766 1828) discovered palladium
(initially also known as new silver) and rho-
dium; S. TENNANT (1761 1815) discovered
iridium and osmium. At the same time, the
existence of platinum as a true element was
established. C. CLAUS (1796 1864) discovered
ruthenium in 1844.
In 1823, J. W. DOEBREREINER (1780 1849)
rst used the catalytic action of platinum in the
gas lighter named after him. In about 1810, the
process invented by W. H. WOLLASTON became
established: dissolving the raw material in aqua
regia, purifying it by precipitation of ammonium
hexachloroplatinate, (NH
4
)
2
[PtCl
6
], and heating
this strongly to form platinum sponge. In 1817,
this led to the formation of Johnson, Matthey &
Co., London [13], which laid the foundation of
modern platinum technology.
Until the beginning of the 19th century, al-
most all platinum was obtained from the area
now known as Colombia, which from 1739 to
1819 belonged to the Spanish Crown Dependen-
cy of New Granada. At this time, ca. 1 t/a
of platinum was extracted. ALEXANDER VON
HUMBOLDT was the most accomplished prospec-
tor and developer of noble-metal deposits in
NewGranada (1819) and of the newly discovered
platinum deposit in the Urals. In 1819, platinum
was extracted from alluvial gold, but soon after
this, the main production was switched to plati-
num placers with low gold content. In 1825,
Russia became the primary producer of platinum.
The minting of platinum coins in Russia in
1828 1845 necessitated an increase in produc-
tion, which reached 3.5 t in 1843 [1416].
Almost all Russian platinum ore was used for
coinage (15 t total). Technology for the extrac-
tion and treatment of placer deposits had reached
a high standard by this time.
After the closing of the renery in St. Peters-
burg, which was associated with the local mint
and produced a metal of ca. 97 %platinum, 1.2 %
iridium, 0.5 % ruthenium, 0.25 % palladium,
1.5 % iron, and 0.4 % copper, the rening and
working of Russian platinumore were carried out
almost exclusively in Western Europe. New
companies for the rening and working of plati-
num were founded, including Desmoutis, Paris
(1822); Baker & Co., New York (from 1904:
Engelhard, Newark, New Jersey); Heraeus,
Hanau (1851); Siebert, Hanau (1881; from
1930 part of Degussa, Frankfurt); J. Bishop &
Co., Malverne, Pennsylvania and others.
20th Century [1720]. The platinum indus-
try grew vigorously after 1880 due to increasing
demands of the electrical industry, dentistry, and
chemical technology. The primary consumer was
the United States. In 1913, annual production of
crude platinum reached 7 t. At this time, Russia
began to make itself less dependent on other
countries by constructing a modern platinum
renery and smelting point at Ekaterinburg (now
320 Platinum Group Metals and Compounds Vol. 28
Sverdlovsk). However, at the result of an ideo-
logically negative attitude toward noble metals
and a false estimate of their economic impor-
tance, platinum production was abandoned after
the Russian Revolution.
The result was that, after World War I, Co-
lombia once again became the largest platinum
producer. The raw materials were exclusively
alluvial deposits, which were extracted by pan-
ning, as they are even today. Almost all of the
Colombian crude platinum was rened in the
United States.
In 1925, production in the Urals was restarted.
New alluvial deposits were discovered in Siber-
ia. Also, mining of primary platinum became
important. Today, a large proportion of the plati-
num group metals supplied by the CIS comes
from suldic nickel deposits. For some decades,
the Soviet Union has been one of the largest
producers of platinum and especially palladium.
Production gures are not available thus far.
Estimates are approximate and are based on
export gures.
During World War I, the demand for nickel
increased, and Canada became an important
producer of palladium and platinum, because
nickel ores also contained platinum group me-
tals. Since 1890, these ores have been extracted
by the Mond Nickel Co. (since 1961, INCO,
London), later allied with the International Nick-
el Co. of Canada. From 1925, platinum metals
were produced in their own renery in Acton in
London. Another important producer of platinum
is Falconbridge Nickel Mines in Toronto.
After World War I, worldwide demand could
no longer be satised by Russia and other pro-
ducers, and new sources were developed. In
South Africa, the search was particularly well
rewarded. Platinum and osmiridium were dis-
covered at Black Reef (1888), Witwatersrand
(1892), Great Dyk (Rhodesia, 1918), and later
at Waterberg. The award of prospecting rights to
private persons led to prospecting on a wide
scale. A systematic geological survey of the
Bushveld by J. MERENSKY was highly successful,
leading to the discovery of platinumin the dunite
pipes (1924) and subsequently in the stratiform
platinum deposits known as the Merensky Reef
(1925), the largest platinum deposit in the world.
This discovery brought about the greatest
upheaval yet seen in the platinum market. It
occurred during a period of both high demand
(mainly for catalysts for ammonia oxidation) and
high prices, the result being the foundation of
about 50 producing companies. The primary
platinum-bearing rock typical of South African
deposits presented the ore treatment and smelting
technologies with completely new problems.
Technical difculties combined with a fall in the
price of platinum led to a slump. The largest of
the surviving companies formed Rustenburg
Platinum Mines Ltd. in 1931, whose output
reached 3 t/a during World War II.
After World War II, the Union of South Africa
(Republic of South Africa) became the main
producer of platinum. From1969, all of the crude
platinum produced by South Africa was rened
by Johnson Matthey in England, although
Matthey Rustenburg Reners now renes con-
siderable quantities of material produced in
Rustenburg. Recently, some new producers have
appeared in South Africa [e.g., Impala Platinum,
Western Platinum (a subsidiary of Lonrho and
Falconbridge), and Anglo-Transvaal Consolidat-
ed Investment (Anglovaal) and its subsidiary
Atok Platinum Mines].
Figure 2 shows the history of world platinum
output, and Table 1 lists the development of PGM
production according to region.
2. Properties [166], [167]
Atomic Properties [21], [22]. The electron-
ic structures of platinum group metals start from
the inert gas structures of krypton and xenon:
Figure 2. History of world platinum output (including GUS
sales to Western World)
Vol. 28 Platinum Group Metals and Compounds 321
Ru [Kr] 4 d
7
5 s
1
Os [Xe] 4 f
14
5 d
6
6 s
2
Rh [Kr] 4 d
8
5 s
1
Ir [Xe] 4 f
14
5 d
7
6 s
2
Pd [Kr] 4 d
10
Pt [Xe] 4 f
14
5 d
9
6 s
1
Two valence orbitals exist: an s shell and an
inner d shell. The small energy difference be-
tween them means that the electron shells are
lled in inconsistently, so that with some ele-
ments, one or both electrons fromthe outer 5 s or
6 s shells are taken up by the 4 d or 5 d shells.
The Platinum Group Metals show close simi-
larities in general physical and chemical proper-
ties. The very small differences in the atomic
sizes of the elements of the second and the third
row of the periodic system are explained by the
full occupation of the 4 f
14
electron orbitals of the
heavy elements Os, Ir, Pt (see Lanthanide
contraction). Due to the electronic structure of
these elements, which is also determined by
relativistic phenomena, causing splitting of p-
and d-orbitals to altered energy levels, they show,
compared to the light platinum group ele-
ments (Ru, Rh, Pd), marked differences in their
catalytic activities both in homogeneous and
heterogeneous catalysis [23] (see also Sec-
tions 10.3 and 10.5).
Because of the small energy differences be-
tween the valence shells, a number of oxidation
states occur. The following oxidation states are
known in the compounds of platinum group
metals (principal oxidation states in bold print):
Ru: 2, 0, 2, 3, 4, 5, 6, 7, 8
Rh: 1, 0, 1, 2, 3, 4, 5, 6
Pd: 0, 2, 3, 4
Os: 2, 0, 1, 2, 3, 4, 5, 6, 8
Ir: 1, 0, 1, 2, 3, 4, 5, 6
Pt: 0, 2, 4, 5
The other properties typical of transitionmetals are
very marked; for example, catalytic activity due to
their readiness to change valence, formation of
intermediate compounds with different reagents,
color, paramagnetism due to unpaired electrons,
and strong tendency to form complexes.
Comparisons within the group of platinum
metals, also including neighboring elements,
often give an insight into the relationship be-
tween electronic conguration and chemical
properties.
Many properties show marked similarities
along the two horizontal rows:
Also, the tendency toward complex formation
and higher oxidation states is more marked in the
row of heavy elements than in the row of light
elements.
Vertical similarities between the elements
also occur (e.g., in their behavior toward acids;
(see Table 3):
Similarities also exist in the following diago-
nal sequence, sometimes with ruthenium and
iridium changing places:
The chemical properties of the platinumgroup
metals and the chemistry of their com-pounds t
Table 1. Historical development of the production of platinum group metals according to region
*
(in t/a)
1800 1850 1900 1910 1920 1930 1940 1950 1960 1970 1975 1980 1985 1990 1995 1997
Colombia 1 < 1 < 1 < 1 2 2 2 1 1 < 1 < 1 < 1 < 1 < 1 < 1 < 1
Russia
**
1 2 12 11 1 3 10 6 12 30 70 70 70 70 191
Canada 1 1 1 2 6 7 12 12 12 12 12 12
South Africa 2 2 4 20 50 90 120 120 130 189
United States 1 1 1 < 1 2 2 1 1 1 1 1 10 33
World 1 2 12 12 4 10 22 20 45 93 173 203 203 222 378 413
*
Other countries account for only 1 2 % of world production.
**
Estimated.
322 Platinum Group Metals and Compounds Vol. 28
less well into such a scheme than their physical
properties.
All platinum group metals have several natu-
rally occurring stable isotopes, with the excep-
tion of rhodium, which has only one.
Physical Properties [22, 2428], [167].
The outstanding physical properties of the plati-
num group metals are of great importance for
their industrial use. These include high melting
point, low vapor pressure, high temperature co-
efcient of electrical resistivity, and low coef-
cient of thermal expansion. Table 2 lists atomic
and crystal data and physical properties of the
platinum group metals.
Osmium is the densest metal known. The
density has been recalculated on the basis of
experimental data and the atomic weight of
190.23 / 0.03 to be 22.587 / 0.009 g/
cm
3
, while for iridium the corresponding values
are 192.217 / 0.003 for the atomic weight
and a density of 22.562 / 0.009 g/cm.
Chemical Properties [2934]. Table 3
shows the chemical behavior of platinum group
metals toward various reagents. Resemblances
are most clear within the two groups of elements.
The aim is to quantify the reactions, so as to
provide useful information when choosing con-
struction materials or dissolving platinum group
metals. Some combinations of reagents that can
be used to dissolve these metals are also detailed
in Chapter 5.
3. Occurrence
3.1. Abundance [10], [31], [3639],
[166], [167]
The abundance of platinumgroup metals (PGMs),
which occupy an intermediate position based on
their atomic number and atomic weight, would be
expected to be 10
4
ppm, based on the mode of
formation of atomic nuclei [40]. They are concen-
trated in planetary regions, reaching ca. 30 ppmin
Table 2. Atomic and physical properties of the platinum group metals [35, p. 267]
Ru Rh Pd Os Ir Pt
Atomic properties
Atomic number 44 45 46 76 77 78
Atomic weight 101.07 102.905 106.42 190.2 192.22 195.08
Crystal structure hcp fcc fcc hcp fcc fcc
Lattice constant, A

a = 2.701 3.803 3.887 a = 2.735 3.839 3.924


c = 4.275 c = 4.319
c/a = 1.583 c/a = 1.579
Atomic radius, A

1.325 1.345 1.376 1.377 1.357 1.377


Mechanical properties
Density (20

C), g/cm
3
12.45 12.41 12.02 22.59 22.56 21.45
Density liquid at melting point, g/cm
3
10.90 10.70 10.49 20.1 19.39 18.91
Hardness (HV), Kg/mm
2
250 500
a
130 50 300 680
a
200 48
Youngs modulus, GPa 485 386 124 570 538 173
Modulus of rigidity, MPa 172 153 51 220 214 67
Poissons ratio 0.29 0.26 0.39 0.25 0.26 0.39
Coefcient of compressibility 0.31 0.36 0.52 0.28 0.28 0.36
Thermal properties
Melting point,

C 2310 1966 1554 3045 2410 1772
Vapor pressure at mp, mbar 5.5 3.5 20 20 4 0.1
Boiling point,

C 3900 3700 2970 5000 4130 3827
Thermal conductivity (20

C), W m
1
K
1
117 150 75 87 147 73
Coeff. of linear expansion (0 100

C), 10
6
K 9.5 8.5 11.1 6.5 6.8 9.0
Electrical properties
Specic electrical resistance (0

C), mWcm 6.7 4.34 9.725 8.2 4.7 9.825
Temperature coefcient of electrical
resistance (0 100

C), 10
3
K
4.0 4.6 3.8 4.2 4.3 3.92
Transition temperature of superconductivity 0.47 0.9 0.71 0.11
Thermoelectric voltage against Pt (0 100

C), mV 0.684 0.70 0.570 0.660 0
Work function 4.52 4.8 4.97 4.55 5.40 5.27
a
Depending on crystal orientation
Vol. 28 Platinum Group Metals and Compounds 323
Table 3. Chemical resistance of the platinum group metals
Reagent Conditions Temperature,

C Pd Pt Rh Ir Ru Os
Hydrochloric acid 36 % 20
Hydrochloric acid 36 % 100
.

.
Nitric acid 65 % 20
.
Nitric acid 65 % 100
Sulfuric acid 96 % 20
Sulfuric acid 96 % 100
.

.

Sulfuric acid 96 % 300
.
.
Hydrobromic acid 60 % 20
. .

Hydrobromic acid 60 % 100
.

.
Hydroiodic acid 57 % 20
.
Hydroiodic acid 57 % 100
.
Hydrouoric acid 40 % 20
Phosphoric acid 100
. .

Acetic acid 99 % 100
Hydrochloric acid/chlorine 20 %/saturated 20
.
.
Hydrochloric acid/chlorine 20 %/saturated 80
Hydrochloric acid/chlorine 20 %/saturated 100
. .
. .
Hydrochloric acid/bromine 20
. .
Hydrochloric acid/bromine 100
.
Aqua regia 20
Aqua regia 100
Aqua regia 150
.
Hydrochloric acid/H
2
O
2
20
Hydrochloric acid/H
2
O
2
100
Hydrobromic acid/bromine 60 % 100
Water/bromine 20
.

Ethanol/iodine 20
.

.

Sodium hypochlorite solution 20
.

.
Sodium hypochlorite solution 100
. .
Sodium cyanide solution 20
.

Sodium cyanide solution 100
.
Copper(II) chloride solution 100
.

324 Platinum Group Metals and Compounds Vol. 28


the earth. Considerable fractionation has taken
place in the earths interior, due mainly to the
siderophilic chemical character of PGMs, so that
virtually the entire mass of PGMs is in the earths
metallic core. The siliceous lithosphere is estimat-
ed to contain 0.05 0.5 ppm.
On theoretical grounds, the PGMs in the earth
are assumed to contain ca. 20 %each of plat inum,
palladium, ruthenium, and osmium, and ca. 6 %
each of rhodium, and iridium. In the case of
ruthenium and especially osmium, these values
are not reected in the deposits mined to date.
3.2. Ores and Their Origin [10], [31],
[32], [36], [4148], [166], [167]
The PGMs in the lithosphere have been trans-
ferred from the earths interior. Tectonic move-
ments of the earths crust, followed by the erup-
tion of magma, have led to their presence in
regions close to the surface. Solidication pro-
cesses, differences in melting point and density,
gas emissions, convection due to heat, and the
ow and eruption of magma, have all produced
concentration and separation effects, mainly in
marginal zones. Chemical interaction with high-
temperature silicate layers, especially their sul-
de, arsenide, antimonide, selenide, and telluride
components, has also played a major role. Al-
most invariably, the platinum group elements
have separated from ultrabasic magmas. Norite
(Mg Fe Ca Al silicate) contains mainly
suldic intrusions, whereas those in dunite (Mg
Fe silicate) are mainly sulde free. Platinum and
palladium (often with nickel, copper, chromium,
etc.) sometimes undergo hydrothermal reactions
with chlorides in the earths interior. All of these
Table 3 (Continued)
Reagent Conditions Temperature,

C Pd Pt Rh Ir Ru Os
NaOH melt air 500
. . .
KOH melt air 500
.
.
.
NaOH melt air 800
.
.

KOH melt air 800


.
.
KHSO
4
melt air 440
.

.

NaCN melt air 700
. . . .
KCN melt air 700
. . .
NaCN/KCN melt (2 : 1) air 550
. . . .
Chlorine, gaseous dry 20
.
.

Chlorine, gaseous moist 20
.

.
Bromine liquid dry 20
.

Bromine liquid moist 20
.

.
Iodine, solid dry 20
.
Iodine, solid moist 20
.

.

Fluorine, gaseous 20
.
Hydrogen sulde, gaseous moist 20
Mass loss <0.01 mg cm
2
h
1
; ideal as construction material
.
Mass loss ca. 0.1 mg cm
2
h
1
; limited use as construction material
.
Mass loss ca. 1 mg cm
2
h
1
; limited use for dissolution processes
Mass loss 10 mg cm
2
h
1
; suitable for dissolution processes.
Vol. 28 Platinum Group Metals and Compounds 325
processes have led to the formation of the prima-
ry deposits of platinum-bearing rock. Workabil-
ity depends on many factorsconcentration of
platinum metals, accessibility, size of deposit,
value and potential uses of accompanying mate-
rialsand is economical in only a few cases.
When primary deposits are altered and trans-
ported by the natural action of the hydrosphere
and atmosphere, secondary deposits, also known
as placers or alluvial deposits, are formed. Me-
chanical concentration of the heavy constituents
by owing water takes place, together with
chemical dissolution and reprecipitation of the
platinum metals. Recently, hydrothermal pro-
cesses have been shown to be considerably more
important than was at rst thought. Alluvial
deposits usually originate from dunite.
The platinum metals occur in a large number
of minerals. Workable ore deposits contain main-
ly sperrylite (PtAs
2
), cooperite (PtS), stibiopal-
ladinite (Pd
3
Sb), laurite (RuS
2
), ferroplatinum
(Fe Pt), polyxene (Fe Pt other platinum
metals), osmiridium (Os Ir), and iridium plati-
num(Ir Pt). These minerals are associated with
particular carrier materials, which are often valu-
able themselves (e.g., iron pyrites, nickel iron
pyrites, or chrome iron ore).
The minerals are seldom present in an exact
stoichiometric ratio. This is true of the platinum
group metals themselves,which are nearly always
present in varying ratios, and of the accompa-
nying elements with which they formcompounds
or alloys. Isomorphismopens up the possibility of
further variations. Isomorphic intercalations
make up a larger part of the economically work-
able reserves. Electron probe microanalysis
(EPM) has enabled a large number of denite
compounds and intermetallic phases to be identi-
ed where mixtures or homogeneous solid solu-
tions had formerly been assumed to be present.
Outside of true deposits, platinum group me-
tals are widely distributed in very high dilution as
isomorphous combinations with various metals
such as nickel, cobalt, and copper, mainly in their
suldes.
3.3. Primary Deposits [4965], [166],
[167]
The dunite bodies in the Urals are the most
important of the old Russian platinum deposits,
either as primary deposits or as material for the
formation of secondary deposits. The only im-
portant primary deposit is at Nishnij-Tagil,
which is mined in many locations. It is a projec-
tile-like intrusion of dunite through the earths
crust, which appears to reach a depth of more
than 100 km and has an area on the earths
surface of 25 km
2
. Platinum metals are concen-
trated in dunite in the formof striae, lenses, nests,
and pillars. They are present mainly as polyxene
(Fe Pt), iridium-rich platinum, and osmiri-
dium, and are often associated with serpentine
or chromite. Most of the platinum has been
obtained fromores with a platinummetal content
of 10 20 ppm. However, ores containing
400 ppm are found in some places. In the total
dunite body, the average platinum content is ca.
0.1 ppm. Other dunite bodies in this region are
not economically important either for their metal
content or for the extent of the deposit.
The dunite pipes at the eastern border of the
South African Bushveld have a similar origin to
the Russian dunite bodies and are of the same
base material. The platinum-bearing core of this
narrow intrusion often has a diameter of 20 m or
less. Veins are rarely present. The excavations at
Driekop and Onverwacht are the most well
known. Mining is difcult. Since the exploitation
of the Merensky Reef, they can be mined eco-
nomically only in certain cases. Platinum group
metals are sometimes present in the metallic state
and sometimes as sperrylite in association with
chromite. Platinum concentrations are 1
200 ppm, and locally higher.
The richest and scientically most interesting
deposits, although small in extent, are the quartz
lodes of Rietfontein on the Waterberg in the
Western Cape Province. Owing to their hydro-
thermal origin, the platinummetals are present in
native form, accompanied by hematite. The PGM
content of the ore often reaches almost
5000 ppm. Deposits of similar structure have not
been found elsewhere.
The largest known primary deposit of PGMs
is the South African Bushveld Complex, with a
total extent of ca. 250 kmfromnorth to south and
480 kmfromeast to west. This oval-shaped zone
was apparently produced by an outow of PGM-
bearing norite magma into a at basin. At the
bottom of this, the minerals sperrylite (PtAs
2
)
and cooperite (PtS) have separated along with
iron pyrites, nickel pyrites, copper pyrites, and
326 Platinum Group Metals and Compounds Vol. 28
chromite. The relatively thin PGM-bearing
layers at the edges of the outow near the earths
surface are mined. These are in both the oxidation
and the suldic zones, and begin at a depth of
< 100 m. The working depth extends to almost
1000 m. The platinumcontent of the mined ore is
3 20 ppm. Palladium is less important than
platinum; all the platinum group metals are pres-
ent. The deposit has great economic importance
owing to its consistent quality, ease of extraction,
and large extent. The Bushveld is mined at the
western and southwestern edges (Rustenburg
region) and the eastern and northeastern edges
(Lydenburg region) (Fig. 3) in two wide areas.
The Bushveld is also the worlds largest chromi-
um and vanadiumdeposit, and has large deposits
of nickel, cobalt, copper, iron, tin, uorspar, and
alusite, magnesite, and asbestos.
These deposits were discovered in 1925 by the
geologist HANS MERENSKY (1871 1952) [17].
He laid the foundations for the most important
phase in the development of platinum extraction
by his wide-ranging prospecting work and fun-
damental observations on the geology of the
Bushveld. The most important areas of PGM
deposits in the western and eastern part of the
Bushveld are known as the Merensky Reef. Not
far from these deposits lie the less important
Platreef and the UG 2 Reef (Upper Group Reef),
which has recently increased in importance due
to its very high rhodium content in many places.
This metal is in great demand and therefore very
expensive.
The UG 2 reef is a chromite layer running
parallel to the Merensky Reef, but somewhat
deeper [66], [67].
Some examples of small deposits include the
Black Reef in the Bushveld and, a few hundred
kilometers north, the Great Dyk Mine in
Zimbabwe.
The Stillwater deposit in Montana, United
States is similar in origin and structure to the
Bushveld deposit. However, PGM separation
occurred at the boundary zone of a subterranean
magma intrusion resembling a sloping lens. This
deposit extends for a length of ca. 80 km. The
Figure 3. Geology and platinum mines of the Bushveld Complex
Vol. 28 Platinum Group Metals and Compounds 327
total PGM content, with high levels of palladium
and rhodium, is higher than that of the Merensky
Reef deposit.
The nickel sulde deposits of the Sudbury,
Ontario district of Canada, yielding iron pyrites
(FeS), pentlandite (F NiS), and copper pyrites
(CuFeS
2
), are today important sources of plati-
num, and more especially of palladium. These
deposits are associated with noritic magma. The
average platinum metal content of the untreated
ore is only ca. 0.3 ppm, with a nickel content of
ca. 2 %. However, the treatment process for the
nickel ore concentrates the platinum metals to
> 50 ppm without extra cost.
Palladium-containing sperrylite (Pt PdAs
2
)
and stibiopalladinite (Pd
3
Sb) are present in the
ores, and the platinum group metals also form
isomorphic mixtures with the heavy-metal sul-
des. During formation of these deposits, the
suldes of nickel and copper acted as collectors.
The large reserves in Norilsk in Central Siberia,
which have a high palladium content, are similar
to the Canadian deposits with regard to compo-
sition and ore treatment methods. Some lead
zinc ores [e.g., in the Rammelsberg (Harz) moun-
tains], contain small amounts of platinum and
palladium.
Comparisons with other metals indicate that
PGM reserves may exist in the Antarctic [68].
The magma ow in the South African Bushveld
occurred in an early geological epoch (Cambri-
an more than 210
9
years ago), when the Afri-
can and Antarctic continents were still part of
Gondwanaland.
3.4. Secondary Deposits [166], [167]
Alluvial deposits are typical reserves of this type.
They were produced in recent geological epochs
(Quaternary Holocene) by weathering and
washing of primary deposits, mainly dunitic,
which resulted in concentration of the more
resistant and heavier components (i.e., the me-
tallic and arsenidic platinum minerals, gold,
magnetite, chromite, cassiterite, zircon, and
granite) in clay and sand. These oxidation zones
are often located above the primary deposits.
River placers are formed from the alluvial de-
posits by the erosive action of water, to yield so-
called black sands. However, typical nuggets
(mainly small granules but also sizable metallic
lumps weighing up to several kilograms) seemto
have been formed mainlyby mechanical agglom-
eration, usually involving chloridic dissolution
and reprecipitation. Very old deposits that
formed conglomerates by adhesive action are
termed fossil placers. The platinummetal content
of secondary deposits varies over a wide range.
Deep alluvium and river headwater placers are
the most productive.
For easily washable sand, a PGM content of
0.05 ppm is economic. Before World War I, the
PGM content of economic deposits was ca.
2 ppm, but today it is much lower. More platinum
metals are recovered fromriver placers than from
alluvial deposits.
Secondary deposits occur mainly in the Urals,
Siberia, Colombia, and Ethiopia. Often, the re-
covery of gold and platinum metals from such
deposits is so interdependent that sometimes one
metal, and sometimes the other, is the main
product. Osmiridium is obtained mainly in Alas-
ka and in the Witwatersrand of South Africa,
along with secondary deposits of gold.
3.5. Recovery of Secondary Platinum
Group Metals [6972]
Platinum metals not only are extracted from ore
but,due to their high value, are also recovered
from a wide range of industrial residues. These
residues are of variable composition and quality,
and recovery plants must be very exible.
Often, the recovery operation is included in
the sales contract for seminished and nished
goods, so materials are sent directly for recovery
and do not appear on the raw materials market.
For regular customers, accounts are kept of the
weights of noble metals involved. The supply of
material is facilitated, and risks due to price
variation are minimized.
Metallic Materials. Large quantities of me-
tallic materials in the form of used platinum
rhodiumgauze catalysts result fromthe oxidation
of ammonia ( Nitric Acid, Nitrous Acid, and
Nitrogen Oxides). These catalysts must be re-
processed chemically after 3 18 months of use.
At present, ca. 50 t of Pt Rh is bound up in these
gauzes. The Pd Au gauzes used to recover
Pt Rh vaporized in ammonia oxidation plants
are also recycled.
328 Platinum Group Metals and Compounds Vol. 28
The glass industry generates large quantities
of defective components for chemical recovery
(e.g., frommelting vessels and other equipment).
Spinnerets from textile ber manufacture
must normally be replaced after about one year
of operation owing to erosion of the holes.
Defective laboratory equipment, mainly cru-
cibles and dishes, makes a considerable contri-
bution, but chemical apparatus components are
of little signicance.
Considerable quantities of platinum rhodi-
um scrap are provided by the electrical measure-
ment industry, mainly in thermocouple compo-
nents. Other residues from the electrical and
electronic sectors include electrical contacts,
heater elements, and electronic components.
Manufacture of fountain pen nibs yields re-
sidues in the form of small spheres or dust that
can contain ruthenium, osmium, iridium, rheni-
um, tungsten, molybdenum, tantalum, nickel,
and cobalt as alloy components. Treatment of
these materials is among the most difcult of all
separation techniques.
Dross. Waste materials include slag, ash,
furnace residue, corrosion residue from equip-
ment, and precipitation residue. Catalyst residues
of poorly dened composition are also included.
The PGM content of these materials is usually
low; they are extremely variable and usually
nonmetallic.
Supported Catalysts [70]. Large quantities
of platinumgroup metals must be recovered from
spent catalysts. The most important of these, both
in quantity and in value, are the heterogeneous
catalysts used in the petroleum industry, espe-
cially in reforming processes, where >50 t of
platinum is bound up worldwide. The lifetime of
these catalysts is 4 8 years. Residues usually
contain 0.3 0.7 % platinum on g-Al
2
O
3
, and
usually also include palladium, rhodium, iridi-
um, and rhenium, which must also be recovered.
The other large-scale processes in the petroleum
industryhydroning and hydrocrackingyield
palladium and platinum catalysts on aluminum
silicate carriers.
Another source of material for recovery of
platinum metals is spent automobile catalytic
converters [6971]. However, the PGM content
is low(2 g per unit), and the units are enclosed in
steel sheet and widely scattered. Collection and
treatment are therefore difcult. A satisfactory
and economical solution to this problem has yet
to be found. In Germany, collection logistics are
coupled to the recycling of automobiles.
The chemical industry produces considerable
amounts of palladium catalysts on carbon car-
riers, often in a moist state that presents sampling
problems. Similar residues come from plati-
num carbon, rhodium carbon, and PtO
2
cat-
alysts, although these are sometimes unsupport-
ed. Platinum asbestos, which was formerly used
widely in sulfuric acid production, is nowof very
little importance.
Solutions [69]. Amounts of liquid residues
from homogeneous catalysts used in the oxo
process (hydroformylation) have increased rela-
tively rapidly. The rhodiumcontent of the organ-
ic solvents or oily process residues is between 50
and 1000 ppm. Sometimes, these organic solu-
tions contain iridium, ruthenium, or p alladium.
Aqueous residues, especially homogeneous cat-
alysts containing rhodium, are currently being
produced in increasing quantities.
The electroplating industry yields exhausted
electrolytes that cannot be regenerated. The most
important of these contain tetranitroplatinate(II),
rhodium(III) sulfate, and rhodium(III) phosphate.
Finally, the processes used for separating the
platinum group metals also produce waste solu-
tions that must be reclaimed (e.g., mother liquor
from crystallization). These operations form part
of the separation process.
Radioactive Residues. An as-yet unsolved
problem is the treatment of radioactively con-
taminated platinum equipment from chemical
laboratories and processes.
Fission of
235
U in nuclear power stations
produces considerable amounts of platinum
group metals; one tonne of spent reactor fuel
contains 1.2 kg of palladium, 0.5 kg of rhodium,
and 2.3 kg of ruthenium [72].
However, the radioactivity of the material has
not permitted the commercial use of this PGM
source until now [73]. The most important PGM
isotopes in spent reactor fuel are:
107
Pd (t
1/2
7 10
6
a),
102
Rh (t
1/2
3 a), and
106
Ru (t
1/2
1 a).
107
Pd is a very low-energy b-emitter,
which would not exclude its use in many major
applications; alternatively, it may be removed
by isotope separation. The active isotopes of
Vol. 28 Platinum Group Metals and Compounds 329
rhodium and ruthenium will have decayed to
background levels after intermediate storage of
ca. 30 years.
3.6. Reserves and Resources
Natural Reserves. Data concerning re-
serves (discovered by prospecting and having
assessable economic value) and resources
(which include additional supposed deposits
and those with no current economic value) are
very dependent on the time prospecting was
carried out, and also on technical and economic
parameters.
For platinum group metals, the current esti-
mate of workable deposits is 70 000 t [46], [75],
[76], 20 years ago, a gure of about one-third of
this was assumed [77].
World reserves of the individual metals can
best be estimated from the observed composi-
tions of the deposits (Table 4) and the total
amounts of PGMs that they contain (Fig. 4). This
does not include osmiridium, which usually oc-
curs with gold.
Industrial Residues. Industrial residues
have considerable potential for the supply of
platinum group metals, in addition to their ex-
traction from ore. In most sectors, the possibili-
ties are nowfully exploited. In others, recovery is
difcult because of the low PGM contents of the
waste materials (e.g., certain catalysts). Econom-
ic recovery is also difcult when small PGM-
containing components are widely distributed
(e.g., in electronics).
In particular, no satisfactory solution has
been found to the problem of collecting used
Table 4. Relative proportions of platinum group metals in selected deposits, and their grades
Bushveld complex
Merensky UG 2 South Africa, Sudbury, Norilsk, Stillwater,
Reef Reef Plat Reef Canada CIS Colombia United States Average
Platinum, % 59 42 42 38 25 93 19 45
Palladium, % 25 35 46 40 71 1 66.5 30
Ruthenium, % 8 12 4 2.9 1 4.0 5
Rhodium, % 3 8 3 3.3 3 2 7.6 4
Iridium, % 1 2.3 0.8 1.2 3 2.4 1
Osmium, % 0.8 0.6 1.2 1 <1
Gold, % 3.2 0.7 3.4 13.5 0.5
Grade, g/t 8.1 8.71 7 27 0.9 3.8 22.3
Figure 4. World platinum group metal reserves (total 70 000 t)
330 Platinum Group Metals and Compounds Vol. 28
automobile exhaust catalysts. In 1991, more
than 7 t of platinum was recovered from this
source in the United States and Europe and about
0.5 t of rhodium in the United States [248].
A total of ca. 1 t/a of rhodium is currently
produced worldwide in nuclear power stations.
Some of this is placed in intermediate storage,
and some in nal repositories.
4. Mineral Dressing and Beneciation
4.1. Treatment of Alluvial Platinum
Deposits [5], [10], [19], [3032], [36],
[41], [4348], [7886], [166], [167]
Gangue materials must normally be removed
fromthe platinum-bearing placer deposits. Some
deposits are extracted by subsurface mining.
Hydraulic classication can be carried out by
hand washing with simple equipment, such as
shovels, sieves, and troughs. This was the most
common method of treating the Colombian de-
posits and is still used today. More modern
methods involve rotary sieves, troughs, and per-
forated boxes with running water or water jets.
The most economical process is dredging
river placers. This is a simple earth-moving
technique linked with a natural inexhaustible
water supply. Large installations have capacities
of several thousand tonnes of sedimentary mate-
rial per day, with a water consumption of ca. 10
times this gure. Aboard the dredger, deposits are
treated mainly by gravity concentration with
sieves and sedimentation equipment, using stir-
rers, thickeners, washing boxes, etc.
The last stage of concentration is often magnet-
ic separation, with various eld strengths used to
separate magnetite, ferroplatinum-containing
minerals such as chromite, and nonmagnetic com-
ponents into fractions. Often, a nal hand washing
is carried out. In some types of deposit, gold
particles or gold-containing platinumparticles can
be separated as amalgam from the platinum con-
centrate. Another process involves concentrating
the platinum metals chemically by dissolving the
other components in nitric acid. The concentrates
soproducedcancontainupto90 %platinumgroup
metals. These can be used directly by reneries.
A problem may occur with high losses of
platinum carried out as very ne metal from the
gravity separation process, often exceeding the
amount of the product itself. Losses can be
reduced to some extent by recycling the lighter
fraction during hydraulic classication of the
platinum deposits.
4.2. Treatment of Primary Deposits
[46], [56], [66], [67], [86], [87], [166],
[167]
The treatment of platinum-bearing rock, which is
always supplied in lump form from primary
deposits, consists of an initial size reduction by
crushing and grinding, usually wet grinding.
After discovery of the South African primary
deposits in the Merensky Reef, attempts were
initially made to treat this platinum-bearing rock
by the methods used for alluvial deposits. Many
processes were investigated including gravity
concentration, otation, and metallurgical and
chemical processes, such as chloride formation
by calcining the powdered ore at 500 600

Cin
the presence of sodiumchloride. The results were
unsatisfactory.
The modern process for the winning of PGMs
from sulde ores is shown in Figure 5. Ground
ores from the workable oxidation zone, which
contain the platinum metals in native form, are
rst subjected to gravity concentration on cor-
dyroy and James tables or by hydrocyclones, to
separate the metallic particles fromthe platinum-
bearing minerals and give a concentrate with a
high PGM content that can be processed quickly
with low losses.
Flotation is then carried out to remove the
gangue fromthe suldic minerals, which are also
associated with arsenidic and suldic platinum
metal compounds and very nely divided ele-
mental platinum metals. This concentrates the
platinum group elements by a factor of 10 50.
After ltration with a rotary lter, the platinum
metals in the otation concentrate are present at a
total concentration of several hundred parts per
million, along with a small percentage of sulfur,
copper, nickel, and iron.
This sequence of process steps is not suitable
for all types of deposits and production equip-
ment. Magnetic or electrostatic separation can
sometimes be carried out before the smelting
operations.
The pelletized material is smelted in a shaft
furnace to forma copper nickel matte. Oxygen
Vol. 28 Platinum Group Metals and Compounds 331
is then blown into the converter to oxidize the
iron sulde selectively to iron oxide, which forms
a slag. These two processes concentrate the
platinum metals in the copper nickel matte to
> 0.1 %. The blowing operation is controlled so
as to give the correct sulfur content for the next
concentration stage. In this recently developed,
slow-cooling matte separation process, a nely
crystalline, homogeneously distributed Ni
Cu Fe phase, in which the PGMs are concen-
trated in high yield, is formed in the almost iron-
free copper sulde matte phase (see Nickel,
Section 4.4.1.). The product is ground, and the
PGM-containing magnetic Ni Cu Fe phase
is recovered from the PGM-free matte by mag-
netic separation. Base metals are then removed
by treatment with sulfuric acid and oxygen. The
concentrate obtained contains 50 90 % PGMs.
The next stage is to separate the platinum group
metals from one another.
The older pyrometallurgical process is time
consuming and does not give such good separa-
tion. After air blowing the iron, the converter
matte produced is smelted with sodium sulde
and separated into copper-containing and nickel-
containing layers (tops and bottoms process).
The nickel-containing material is roasted and
then reduced in a reverberatory furnace to give
PGM-containing impure nickel. The platinum
group metals are recovered from the anode slime
produced during electrorening. A method of
this kind is apparently still used to treat suldic
PGM deposits in the Urals.
Problems arise during treatment of the high-
chromite ores of the UG 2 reef by the suldic
route; these are therefore often mixed with ore
fromthe Merensky deposit. Aprocess that shows
great economic promise for the future is to smelt
a metallic concentrate directly from the ore in a
plasma furnace [66]. Both types of ore are suit-
able, although the chromite-containing ore is
better.
4.3. Treatment of Nickel Ores [63], [64]
In the processing of sulde nickel ores, which
always contain copper, the platinum group me-
tals follow the nickel in the smelting process.
When the crude copper is electrorened, the
amount of PGMs obtained in the anode slime is
very small.
When nickel is electrorened, the platinum
group metals remain behind in the slime formed
at the nickel anode. The base metals and the silver
are dissolved by acid treatment, giving a concen-
trate that contains ca. 70 % platinum group me-
tals and differs from the nickel anode slime
obtained from platinum ores of the Merensky
Figure 5. Winning of platinum group metals from sulde
ores
332 Platinum Group Metals and Compounds Vol. 28
reef in having an appreciably higher palladium
content. Also, the concentration of platinum
group elements in the unrened nickel is about
100 times lower than that in the nickel obtained
from platinum ore from the Merensky or UG 2
reef (see Section 4.2).
When crude nickel is rened by the carbonyl
process (see Nickel, Section 6.3.), residues
with a lower PGM content are obtained. These
are suitable for concentration by smelting under
reducing conditions with lead(II) oxide and so-
dium carbonate. The lead is driven off, and the
silver is dissolved and removed. These concen-
trates are of high enough quality for separation
into individual metals.
The treatment of PGM-containing copper an-
ode slime obtained from nickeliferous pyrrhotite
( Silver, Silver Compounds, and Silver Al-
loys) is a long and costly process. The metals
copper, selenium, tellurium, arsenic and antimo-
ny must rst be removed (e.g., by forming their
sulfates in a high-temperature process), followed
by dissolution or by producing slags via smelting
in the presence of potassium nitrate with an air
blast. This yields so-called Dore metal. The
platinum group metals are then concentrated in
the anode slime produced in the subsequent silver
electrorening process ( Silver, Silver Com-
pounds, and Silver Alloys).
Copper ores can also contain very small
amounts of platinum group metals. These appear
in the copper anode slime during copper
electrorening.
4.4. Treatment of Metal Scrap [166],
[167]
Ahigh proportion of the metallic waste fromused
equipment and from seminished products can
simply by dissolved without any prior treatment
(see Chap. 5). These types of material in-clude
crucibles, dishes, thermocouple elements, gauze
catalysts, and ber spinneret nozzles.
Massive materials such as heavy-gauge sheets
or bars should be size reduced by crushing or
machining to produce swarf. For the highly
refractory metals of the platinum group (Rh, Ir,
Ru, and Os) and their alloys, mechanical methods
are usually not sufcient to produce a surface
susceptible to dissolution. This is also true of
platinum alloys with > 30 % rhodium or 20 %
iridium. In these cases, alloys of platinum or
palladium, which can be dissolved more easily,
are preferable.
Very highly dispersed noble-metal black,
which is often more soluble, is obtained by
alloying the highly refractory platinum metals
with base metals and then dissolving the latter
out. The noble-metal black must not be heated, or
the optimum surface properties for the solution
process would be adversely affected. Suitable
alloying elements include copper, lead, nickel,
zinc, aluminum, bismuth, and silver.
Commercial powdered rhodium and iridium
also cannot be dissolved by direct chemical
means, but they can be treated with chlorine at
ca. 500 600

C to form chlorides (also insolu-
ble), and these can be reduced at lowtemperature
(e.g., by hydrogen or by hydrazine in aqueous
suspension) to produce nely divided blacks that
can be dissolved in hydrochloric acid chlorine.
Concentrates of platinummetals often contain
oxides that are less soluble in oxidizing acid
mixtures than the metals. In these cases, the
material must rst be reduced by heating in a
hydrogen atmosphere or by treating with aqueous
hydrazine hydrate at ca. 80

C. For rhodium
oxides, solutions must be highly alkaline and at
their boiling point.
4.5. Treatment of Dross [88, 9396]
If platinum metals cannot be separated by chem-
ical or mechanical methods from accompanying
nonmetallic materials, as is usually the case with
low-grade waste, pyrometallurgical processes
must be used (as in ore treatment).
The most convenient and long-established
pyrometallurgical process for low-grade waste
is smelting with lead in a shaft furnace to produce
slag. Materials containing silver and gold (
Silver, Silver Compounds, and Silver Alloys;
Gold, Gold Alloys, and Gold Compounds, Sec-
tion 6.2.) are treated in this way. The lead acts as a
collector for the platinum group metals. The
presence of gold and silver also considerably
affects the distribution equilibrium of the plati-
num group metals in the melt. In the lead shaft
furnace, some of the high-melting noble metals
rhodium, iridium, and ruthenium separate as so-
called furnace shows. When the lead is oxidized
and removed as litharge, most of the Rh, Ir, and
Vol. 28 Platinum Group Metals and Compounds 333
Ru (so-called bottom metals) precipitates from
the increasingly silver-rich alloys. Considerable
amounts of rhodium and iridium pass into the
shaft furnace slag and are lost. Ruthenium and
particularly osmium are lost in large amounts in
ue dust and waste gases.
When the gold silver alloy from the above
process is electrorened to obtain silver, gold and
the platinum group metals remain in the anode
slime. If this consists mainly of gold, it is con-
verted to pure gold by Wohlwill electrolysis
( Gold, Gold Alloys, and Gold Compounds,
Section 5.3.), in which platinum and palladium
are concentrated in the electrolyte, and silver
chloride and the remaining platinum group me-
tals in the anode slime. Alternatively, the silver
can be dissolved from the gold silver alloy by
nitric acid to formsilver nitrate, which is puried
by thermal decomposition of the accompanying
nitrates; the platinum group metals remain in the
water-insoluble oxide residue.
All the concentrates mentioned above can be
dissolved, and the individual platinum group
metals obtained from these solutions.
4.6. Treatment of Supported Catalysts
[70], [71], [97100]
Spent, inactive catalysts consisting of platinum
metals supported on active carbon, or carrier-free
noble-metal catalysts that have become coated
with organic residues, are concentrated by com-
bustion. These materials are sometimes sponta-
neously ammable. When they are being burned,
strong air currents are suppressed to prevent dust
losses. If the resulting ash contains platinum
metal oxides, these are reduced to the metal.
Catalysts with incombustible carriers insolu-
ble in acid and alkali (e.g., g-Al
2
O
3
, silica gel,
asbestos, and zeolites) can often be treated with
oxidizing acid, but the noble metals dissolve
completely only in the absence of organic resi-
dues (especially tarry matter) and if the carriers
are very porous. Otherwise, the platinum metals
must be concentrated by the lead shaft furnace
process (see Section 4.5).
Reforming catalysts consist of g-Al
2
O
3
impreg-
nated with platinum, platinum rhodium, plati-
num iridium, or platinum rhenium. This carri-
er material is soluble in acid and alkali, and is
dissolved (e.g., in hot sulfuric acid or hot caustic
soda solution) leaving the noble metal as an insol-
uble residue. However, small, but not negligible,
amounts of noble metal also go into solution.
Moreover, suldic impurities in the catalyst can
lead to the release of toxic hydrogen sulde. Other
practical processes are dissolving the catalyst in
sodium carbonate solution (usually at 220

C in a
pressurized reactor), or sintering with sodium hy-
droxide or sodium carbonate. Carbon and other
products of the breakdown of mineral oil in the
spent catalyst must be burned off before treatment
withacidor alkali, because these materials interfere
withthe ltering of the platinummetal concentrate.
Spent automobile exhaust catalysts can be
processed at high temperature in a plasma or a
submerged arc furnace. In the former, a plasma is
produced between an electrode and the molten
feed material. The energy of recombination of the
plasma is released into the melt. In the resistance
furnace, slag serves as the electrical resistance in
which heat is produced. In both processes, the
oxide carrier is melted with or without addition of
a ux of lower the melting point. Iron or copper is
added as a collector, forming a metallic melt that
takes up the platinum group metals. The concen-
tration of PGMs can reach 20 %.
4.7. Treatment of Solutions [69], [101],
[102]
In homogeneous catalysis, high-boiling distilla-
tion residues are usually produced that contain no
valuable materials apart fromrhodiumand some-
times ruthenium. These residues can be carefully
burned, and the ash treated by wet chemical
processes. Other techniques for recovering rho-
dium have been suggested (i.e., liquid liquid
extraction, reductive precipitation of the metal,
and pyrolytic hydrogenation). A process used in
industry, especially for the treatment of rhodium-
containing oily residues from oxo synthesis, is
precipitation of acid-soluble rhodium telluride
by reacting the organically bound rhodium with
tellurium. This process is notable for the high
efciency of rhodium recovery.
The methods used to produce concentrates
from a variety of aqueous wastes are to a large
extent the same as those used for the internal
recycling of platinum metals in the solutions
produced in metal winning processes (see Sec-
tion 6.8).
334 Platinum Group Metals and Compounds Vol. 28
5. Dissolution Methods [36], [48],
[166], [167]
Whether separating platinum group metals or
producing compounds and catalysts, the usual
starting point is an aqueous solution.
Most raw materials can be dissolved in oxi-
dizing acids. Dissolution can be carried out at
atmospheric pressure, or at elevated pressure to
obtain higher temperature. Convective or micro-
wave heating can be used.
Highly refractory raw materials, such as rho-
diumand iridiumpowder, can be convertedintoa
highly dispersed form, by chlorination at ca.
500

C, followed by reduction with hydrogen at
100 200

C or hydrazine in aqueous suspen-
sion. Alternatively, rhodium can be oxidized to
Rh
2
O
3
and then reduced.
In some cases, melt processes at higher reac-
tion temperature must be used. A review of the
dissolution properties of platinum group metals
is given in Figure 6 and Table 3.
The cost of the dissolution step is an appreci-
able fraction of the cost of the entire process if
many small amounts must be dissolved individ-
ually for the determination of value; therefore,
the choice of method is important.
5.1. Dissolution in Aqua Regia
The following reaction takes place in aqua regia:
8 HCl2 HNO
3
PtH
2
PtCl
6
4 H
2
O2 NOCl
as does the following decomposition:
3 HClHNO
3
Cl
2
2 H
2
ONOCl
The highest rates of dissolution occur at the
boiling point of aqua regia. The rate depends only
slightly on acid concentration between 6 and
12 M, and is virtually unaffected by the presence
of dissolved platinum group metals.
The aqua regia method is preferred for
compact metallic platinum and high-platinum
alloys (sheet, wire, turnings, etc.). The reac-
tions must be carried out in a sealed apparatus
to prevent loss of material by splashing and
mist formation. Before the next stage of treat-
ment, nitric acid must usually be removed by
concentration with the addition of hydrochlo-
ric acid.
To suppress side reactions, the reactants must
not be allowed to boil too violently, although
maintaining them at the boiling point and use of
6 M acid offers the most convenient method of
sustaining consistent reaction conditions. To
avoid boiling over, especially during heating,
the initial charge of nitric acid should be added
slowly and evenly to boiling hydrochloric acid.
This method should also be used when aqua regia
is added to replace spent acid.
Finely powdered material also tends to cause
boiling over. To avoid a violent reaction when
dissolving palladium-rich alloys, dilute acids
should be used.
5.2. Dissolution in Hydrochloric
Acid Chlorine
In the reaction between platinum and a solution
of chlorine in hydrochloric acid
Pt2 HCl2 Cl
2
H
2
PtCl
6
Figure 6. Rate of dissolution of platinum and palladium in
oxidizing acids
Vol. 28 Platinum Group Metals and Compounds 335
the dissolution rates for platinum and platinum-
rich alloys have a maximum in the range 80
90

C(see Fig. 6). As the boiling point of hydro-
chloric acid (110

C) is approached, the rate of
reaction decreases rapidly, increasing again at
higher temperature. For palladium, the rate of
dissolution is considerably higher.
For these dissolution reactions, 6 8 M hy-
drochloric acid is preferred since, in this con-
centration range, both the amount of acid con-
sumed and the amount of hydrogen chloride in
the waste gas are lower than if more concentrat-
ed hydrochloric acid is used. The presence of
dissolved platinummetals does not decrease the
rate of dissolution. By careful control of addi-
tion rates, a very slight excess of chlorine can be
used, so that this method leads to lower levels of
waste gas contamination than the aqua regia
method. However, the rates of dissolution de-
crease considerably in the absence of agitation,
and the process is most suitable for easily stirred
powders, slurries, or concentrates and unsuit-
able for bulk material.
Metal dissolves more slowly in the vapor
phase or in reuxing hydrochloric acid contain-
ing dissolved chlorine (see Fig. 6).
Hydrogen peroxide can be used in place of
chlorine as oxidizing agent. Optimum concen-
trations are difcult to maintain owing to the
decomposition of hydrogen peroxide into oxygen
and water; therefore, reaction rates are very low
compared with those for HCl Cl
2
. The HCl
H
2
O
2
systemhas some limited use for palladium.
5.3. Dissolution in Hydrochloric
Acid Bromine
Palladiumdissolves more rapidlyin hydrochloric
acid bromine mixtures than in hydrochloric
acid chlorine (see Fig. 6). Bromine is more
soluble than chlorine in hydrochloric acid, en-
abling high halogen concentrations to be used. If
the temperature is kept well below the boiling
point of bromine (59

C), losses in the waste
gases become very small. Bromide formed in the
dissolution reaction can be oxidized to bromine
by chlorine in an easily controllable reaction,
recovered by distillation, and recycled. Since the
conversion of bromide to bromine
2 Br

Cl
2
Br
2
2 Cl

or
H
2
PtBr
6
3 Cl
2
H
2
PtCl
6
3 Br
2
can take place in parallel with the dissolution
process, bromine can be present in substoichio-
metric amounts.
Platinum and its alloys with rhodium or iridi-
um are more resistant to hydrochloric acid
bromine than to hydrochloric acid chlorine.
5.4. Other Dissolution Processes
Concentrated nitric acid is suitable for dissolving
palladium (see Fig. 6).
Concentrated sulfuric acid dissolves nely
divided rhodium at ca. 300

C, but strongly
heated rhodium powder is largely insoluble in
sulfuric acid.
Concentrated hydrobromic acid is the only
reagent that can directly dissolve oxides of the
platinum group metals such as PdO, PtO
2
,
Rh
2
O
3
, and IrO
2
. Platinum can be dissolved in
a mixture of hydrobromic acid and bromine
above 100

C in a pressurized reactor. Metallic
rhodium is quite soluble in concentrated hydro-
bromic acid near its boiling point.
Powdered ruthenium or osmium can be trea-
ted with an alkaline solution of potassium per-
oxodisulfate (K
2
S
2
O
8
) to formsolutions of ruthe-
nate or osmate. In acidic media, osmium is oxi-
dized by peroxodisulfate or chromic acid to form
OsO
4
.
Perchloric acid has been reported to be a
solvent for platinum and its alloys, ruthenium,
and osmium.
5.5. Dissolution by Salt Fusion [34]
Aqueous dissolution processes are not successful
for all types of concentrates and raw materials.
Often, reactions in molten salts are more effec-
tive. For many raw materials, molten salt meth-
ods are selective and therefore also suitable for
separation.
Rhodium can be converted into water-soluble
rhodium(III) sulfate at ca. 600

C by melting
with potassium or sodium hydrogensulfate,
which is converted to the pyrosulfate with loss
of water. Platinum, iridium, and ruthenium are
not attacked.
336 Platinum Group Metals and Compounds Vol. 28
Ruthenium is converted into water-soluble
K
2
[RuO
4
] when reacted with KOH KNO
3
.
Osmium reacts similarly. This reaction can be
used to treat nely divided osmiridium, especial-
ly after preliminary treatment with molten zinc,
in which the iridium remains undissolved (see
also Section 4.4). Potassium salts are more ef-
fective than sodium salts. Alkali-metal carbo-
nates can be used instead of alkali-metal
hydroxides.
Ruthenium and osmium are very readily at-
tacked by molten Na
2
O
2
. The reaction can be
prevented frombecoming too violent by addition
of NaOH or Na
2
CO
3
to reduce the melt tempera-
ture. Iridium can be oxidized to acid-soluble
iridate by fusion with Na
2
O
2
.
Iridium can also be converted to acid-soluble
iridate by treatment with fused BaO
2
or BaO
2

Ba(NO
3
)
2
. This has the advantage of enabling the
cation to subsequently be removed simply by
precipitation as BaSO
4
. The process is also used
to treat osmiridium, although osmium is con-
verted to OsO
4
and must be recovered from the
waste gas.
When mixtures of powdered platinum group
metals are heated at 700

C in a chlorine atmo-
sphere, acid-soluble chlorides of palladium and
platinum, and acid-insoluble RhCl
3
, are formed.
Chlorination of iridium and ruthenium produces
substoichiometric acid-insoluble products.
All of the platinum group metals form water-
soluble complex chlorides when treated with
sodium chloride in a chlorine atmosphere.
6. Separation of Platinum Group
Metals [31], [103], [263]
After the platinum group metals have been dis-
solved, the individual metals must be recovered.
Depending on the raw material, the solution may
contain all or some of the PGMs, together with
gold, silver, and base metals.
Over the past 200 years, numerous separation
processes have been developed and used [31],
[32], [36], [41]. Many of the individual steps are
still very important in modern processes. Others
are of historical interest, but may be used in
special cases to treat very small quantities. In
addition to the large-scale separations carried out
by mining companies and reneries a number of
small companies exist.
In general, coarse separation is followed by a
purication stage. The process used for coarse
separation is determined largely by the compo-
sition of the starting solution, and the purication
process depends on the particular PGM. The
purication stage is necessary because, with few
exceptions, an individual platinum group metal
of commercially acceptable purity cannot be
isolated from complex solutions in a single step.
In practice, the composition of the raw mate-
rial changes frequently and profoundly, especial-
ly in the recovery of secondary metal. Here, the
crude separation process must be very exible. In
separation plants that are parts of mining opera-
tions, the rawmaterial is usually fairly consistent
over a long period of time.
The most important separation processes to-
day make use of various combinations of precip-
itation, crystallization, solvent extraction, and
distillation.
To achieve the necessary performance eco-
nomically, a high selectivity, a good yield of
noble metal, and (to minimize loss of the interest-
earning potential of high-value materials) a short
treatment time are required.
6.1. Chemistry of Platinum Group
Metal Separation [104115]
Of the many known reactions in PGMchemistry,
certain ones have been developed to separate the
metals or have been shown to be especially useful
for this purpose. This is true both for crude
separation and for purication; in many cases
the same reaction is equally important in both
stages.
Dissolution Properties. Differences in re-
activity toward chemical reagents, especially
oxidizing acids and molten salts, can often be
utilized for coarse separation of platinum group
metals. Good separation is possible only if plati-
num and palladium do not form mixed crystals
with the refractory PGMs.
Solution Equilibria. In the crystallization
process (by either evaporation or precipitation),
the solubilities of chloro complexes of the plati-
num group metals are very important, as is the
possibility of altering these solubilities. The
temperature dependence of these solubilities is
Vol. 28 Platinum Group Metals and Compounds 337
generally quite large and can be utilized or must
be considered, in many stages of the process. In
the range between roomtemperature and 100

C,
solubilities differ by about a factor of 10 (Fig. 7).
An even more useful phenomenon in separation
technology is the effect on solubility of the
addition of a common ion, which is utilized in
precipitation crystallization (Sections 6.3 and
6.4). Solubility can usually be varied over two
orders of magnitude (Fig. 8). The solubility of
AgCl is affected not only by the concentration of
the acid, but also by that of H
2
PtCl
6
.
Redox Reactions and Stability of Com-
plexes [88], [116]. Many separations are made
possible by valence changes in redox systems.
This applies mainly to precipitation crystalliza-
tion, but also to solvent extraction and distilla-
tion. In practice, the kinetic and thermal stabili-
ties of the valences in complexes are important,
as is the redox stability (Table 5).
Hydrolysis [96], [104], [117]. Hydrolytic
effects can frequently reduce the completeness
of a desired reaction, thereby adversely affecting
separation. Most chloro complexes of PGMs are
susceptible to hydrolysis at high temperature,
thereby reducing their redox stability. The pos-
sible stepwise hydrolytic conversion of
[RhCl
6
]
3
to [Rh(H
2
O)
6
]
3
, and of [PtCl
6
]
2
to
[Pt(OH)
6
]
2
, must be taken into account. Similar
hydrolytic effects are also common with ruthe-
nium and iridium. The reactions outlined here
generally take place with widely varying rates.
This is true for reaction in both directions (e.g.,
for hydrolysis and for the reverse reaction in the
presence of acid). For example, when a suspen-
sion of (NH
4
)
2
[PtCl
6
] is heated, the concentra-
tion of dissolved platinum (after being cooled to
20

C) increases in 24 h from 2.2 g/L to twice
Figure 7. Solubility of platinum group metal chloro com-
plexes in water as a function of temperature
. . . . unstable solution equilibrium; stable solution
equilibrium
Figure 8. Dependence of the solubility of platinum group
metal chloro complexes on the concentration of NH
4
Cl and
HCl at 20

C
. . . . unstable solution equilibrium; stable solution
equilibrium
338 Platinum Group Metals and Compounds Vol. 28
this amount, and after 96 h it increases fourfold.
This is due to partial hydrolysis to give soluble
compounds. The reverse reaction, brought about
by heating with hydrochloric acid at its azeotro-
pic concentration, occurs at similar rates.
Ion Exchange Chromatography. The use
of ion exchange is limited mainly to the separa-
tion of PGMs from base metals [118]. For exam-
ple, selective adsorption of [PtCl
6
]
2
on strongly
basic anion-exchange resins is possible, followed
by elution with sodiumhydroxide solution, yield-
ing [Pt(OH)
6
]
2
. The separation of a PGM mix-
ture into individual PGMs by chromatography is
described in [119], [120].
Organic Precipitation Agents [121], [122].
Palladium can be selectively precipitated by di-
methylglyoxime, but the precipitate is difcult to
lter. Separation systems have also been reported
that depend on the formation of complexes of the
PGMwith substituted formazanes and substituted
benzoylthiourea. Precipitable organometallic
compounds can often be recovered by solvent
extraction instead of precipitation.
Distillation and Sublimation. The only in-
dustrial use of distillation or sublimation at pres-
ent is the separation of RuO
4
and OsO
4
, usually
by steamdistillation. These substances have high
vapor pressures even at room temperature, so a
noncondensable carrier gas cannot be used be-
cause of the high carryover of material. A possi-
ble future process is the separation of PGM by
using sublimation of PGM uorides [123].
Reduction to Metal. Since the PGMs are all
electrochemically noble metals, selective reduc-
tion and cementation by base metals are not
possible. In the past, collective cementation from
aqueous solution by zinc was often an important
step, both for separation and for the recovery of
PGMs fromrecycled solutions. However, the use
of zinc as a cementation agent is nowruled out for
environmental reasons. Where cementation can-
not be avoided, iron, aluminum, or Fe Al alloys
can be used instead. In aqueous media, hydra-
zine, formate, or boranate can be used to reduc-
tively precipitate elemental PGMs.
Solvent Extraction [124133]. Many liq-
uid liquid extraction systems have been de-
scribed that can be used for solvent extraction
of metals. Much research into the platinumgroup
metals has been carried out, mainly aimed at their
separation. The extraction processes do not usu-
ally involve a true Nernst distribution of the
extractable compounds between the organic and
the aqueous phases. More often, the extractable
compounds (generally organometallic) are
formed in the extraction system itself. The re-
actants are dissolved in an inert organic phase or,
if they are themselves liquids, can be used as
such. The system is generally diluted with an
inert solvent to lower the viscosity.
The extractants and extraction mechanisms
are classied in the following groups:
1. Compound formation
2. Anion exchange
3. Cation exchange
4. Solvation
5. Solvent extraction without reaction
Of the many systems investigated, very few
are of practical use.
The organic phase often increases signicant-
ly in viscosity as metal content increases and is
usually diluted by a hydrocarbon mixture in the
150 200

C bp range.
Table 5. Stability of platinum group metal chloro complexes
Metal Oxidation state Complex Redox stability Kinetic stability Thermal stability
Pt IV [PtCl
6
]
2
stable very stable very stable
Pt II [PtCl
4
]
2
unstable unstable
Pd IV [PdCl
6
]
2
unstable stable unstable
Pd II [PdCl
4
]
2
stable very stable
Ir IV [IrCl
6
]
2
stable stable
Ir III [IrCl
6
]
3
stable stable
Rh III [RhCl
6
]
3
stable stable unstable
Ru IV [RuCl
6
]
2
unstable unstable
Vol. 28 Platinum Group Metals and Compounds 339
The extracted metal is stripped from the or-
ganic phase by an aqueous phase.
6.2. Older Separation Processes [31]
Some separation methods, shown in Figures 9,
10, 11, were commonly used for separating
PGMs in earlier times. Modications of these
may still be used today or included with more
modern individual stages in an integrated pro-
cess. In special cases, they can contribute to the
solution of separation problems.
Separation Process A (Fig. 9) [36], [43].
The process used by INCO in the Acton renery
in England has been known for a long time. It is
especially suitable for treatment of the anode
slime from the electrolysis of nickel. Here, se-
lective dissolution of Pt Pd can be achieved Figure 9. Older separation process A
Figure 10. Older separation process B (Siebert)
340 Platinum Group Metals and Compounds Vol. 28
since the refractory PGMs are concentrated in
separate particles. Some special process steps are
used, including alloying with lead, and selective
dissolution of rhodium, rutheniumand iridiumby
salt fusion.
Separation Process B (Fig. 10). A process
formerly used by the platinumsmelting company
Siebert/Degussa is characterized by the recycling
of unacceptably large amounts of platinumdue to
the relatively high solubility of sodium chloro-
platinate. Recovery of the rarer platinum group
metals by cementation led to serious pollution of
the wastewater. The cemented metals were usu-
ally dissolved with NaCl Cl
2
. An advantage of
the process was the efcient separation of
iridium.
Separation Process C (Fig. 11) [36], [134],
[135] is suitable only for raw materials with low
palladium, rhodium, and iridium content, be-
cause of the difculty of handling their hydrox-
ide precipitates, which have adsorptive proper-
ties. It has been used only in small separation
plants for secondary metal and yields very pure
platinum.
6.3. Current Separation Processes
Modern separation processes (see Figs. 12, 13,
14) are designed for high separation efciency,
minimum recycle, reduced holdup times of ex-
pensive PGMs, and minimization of losses of
noble metals. Ecological considerations are often
crucial, even when costs must be kept low. Thus,
cementation on zinc, an extremely expensive
process even if the cost of necessary wastewater
treatment is excluded, has to a very large extent
been eliminated from PGM separation processes
for environmental reasons.
Separation Process D (Fig. 12) [31], [88].
All process steps can be carried out on the same
solution by using simple, similar process opera-
tions, which is economically benecial. The
process is very exible, which is an advantage,
particularly for the recovery of secondary metal
when the ratio of PGMs changes continuously. If
the ruthenium content is high, RuO
4
should be
removed by distillation as the rst step of the
separation process.
Separation Process E (Fig. 13). Solvent
extraction with dialkyl sulde is used. Unlike
process D, this provides a practically quantitative
and sharp separation of palladium, which yields
favorable conditions for the purication of pal-
ladium and platinum. Solvent extraction of iridi-
umcan be carried out almost quantitatively and is
very useful when iridium content is low. Under
these conditions, use of precipitation crystalliza-
tion would result in excessive amounts of iridium
Figure 11. Older separation process C (Gilchrist)
Vol. 28 Platinum Group Metals and Compounds 341
remaining as soluble (NH
4
)
2
[IrCl
6
] in the mother
liquor.
Separation Process F (Fig. 14) [136]. A
process used mainly in mining operations (i.e.,
with primary raw materials) has, as its most
notable feature, solvent extraction of platinum,
which is the metal present in highest concentra-
tion. Oximes are better than thioethers for solvent
extraction; the higher rate of complex formation
enables column technology to be used. Also, the
separation process can be set up as an integrated
unit. Ion exchange, which is also carried out on
columns, results only in separation of base
metals.
Similar separation processes based on solvent
extraction are in industrial use or development
[129133], [137143].
Figure 12. Modern separation process D
Figure 13. Modern separation process E
342 Platinum Group Metals and Compounds Vol. 28
6.4. Processes Used in Coarse
Separation [31]
Separation of Silver. Insoluble silver chlo-
ride is formed in the dissolution process and is
removed by careful ltration from the starting
solution in concentrated hydrochloric acid. How-
ever, this acid at its usual concentration leads to
unacceptably high levels of silver remaining in
solution due to H[AgCl
2
] formation. Lowering
the free hydrochloric acid concentration, prefer-
ably by evaporation and dilution, considerably
reduces the solubility of silver chloride. The
settling rate and ease of ltration are improved
by occulating agents.
Traces of silver (usually together with Cu and
Pd) can be extracted from chloride solutions of
platinum group metals at pH 5.5 by dithizone in
chloroform.
Separation of Gold. The usual process for
gold separation involves reducing Au (III) to
elemental gold in acid solution. Reducing agents
that can be used include iron(II) salts, oxalic acid,
sulfur dioxide, and ascorbic acid. Sodiumnitrite,
hydrogen peroxide, sodium formate, and ethyl
alcohol are also used [133]. The separation pro-
cess is improved if reducing agents and reaction
conditions are chosen such that Pt (IV) is not
reduced to Pt (II). Otherwise, Pt (II) must be
reoxidized to Pt (IV). The separation of gold
from PGMs is becoming increasingly important
[143].
Selective Dissolution Reactions and Melt
Reactions. Dissolution processes usually do
not give very sharp separation of platinum group
metals.
Problems with salt fusion lead to poor diffu-
sion conditions. In dry chlorination of platinum
group metals, the chlorides are thermodynami-
cally stable over only a small range. Also, in
reaction of the metals with sodium chloride and
chlorine, temperatures must be chosen such that
unreacted metal particles are not blocked by
molten salt. In practice, achieving complete re-
action in a single stage is usually impossible.
Separation of Platinum, Iridium, and Pal-
ladium by Precipitation Crystallization
[144146]. The same basic process has been used
for the separation of the largest quantities of plati-
numgroupmetals since the beginningof separation
technologyprecipitation crystallization of ammo-
nium hexachloro complexes (NH
4
)
2
[MCl
6
]. This
process can be optimized in many ways by inu-
encing solubilities (e.g., by valence changes, addi-
tion of a common ion, or changing the temperature
and rate of precipitation).
The rst step in separation is usually to pre-
cipitate platinum as (NH
4
)
2
[PtCl
6
]. If the
Figure 14. Modern separation process F (Matthey Rusten-
burg reners)
Vol. 28 Platinum Group Metals and Compounds 343
dissolved platinum is present as Pt
II
, it must rst
be oxidized to Pt
IV
(e.g., by chlorine). Excess
dissolved chlorine is driven off by boiling,
which also causes the palladium that had been
oxidized to palladium(IV) to be reduced to
palladium(II). Any iridium(IV) present must be
selectively reduced to iridium(III), for example,
with iron(II) salts or ascorbic acid. The ammo-
nium hexachloroplatinate(IV) is precipitated
preferably by slow addition of concentrated
ammonium chloride solution at room tempera-
ture with stirring. The hydrochloric acid con-
centration should be 1 M, and the platinum
content should be 50 200 g/L. After precipi-
tation, the excess of NH
4
Cl in the solution
should be at least 0.5 mol/L. The mother liquor
is removed from the salt by washing with semi-
saturated cold ammonium chloride solution.
The deep-yellow ammonium hexachloroplati-
nate(IV) is recovered with a purity of 99.0
99.5 % in > 99 % yield.
Attempts have been made to precipitate the
(NH
4
)
2
[PtCl
6
] slowly by gradual formation of
NH

4
ions in the reaction medium (e.g., by
hydrolysis of urea or hexamethylenetetramine).
In this way, an almost ideally homogeneous
precipitation medium is produced. However,
the purities and yields achieved do not justify
the cost.
To precipitate iridium as (NH
4
)
2
[IrCl
6
], iridi-
um(III) is converted to iridium(IV) by treatment
with an oxidizing agent at ca. 100

C, while
palladium remains in the divalent state at this
temperature. Black (NH
4
)
2
[IrCl
6
] is ltered
off from the cold solution. It is more readily
soluble than the corresponding platinumsalt, and
therefore sufcient excess of NH
4
Cl (0.5
1.0 mol/L) and good cooling (20

C) must be
used, and the minimum amount of concentrated
NH
4
Cl solution must be used for washing.
Chlorine is then passed into the solution at room
temperature, the excess NH
4
Cl in solution being
> 1 mol/L, and palladium is precipitated in the
pure state in the form of the sparingly soluble,
brick-red ammonium hexachloropalladate(IV),
(NH
4
)
2
[PdCl
6
]. The separation from rhodium
(III) is, however, not sharp.
The main problem encountered in this precip-
itation is the difculty of producing sufciently
large crystals for ltration, which can be favored
by adding the palladium solution to the NH
4
Cl
solution. High temperature favors crystal growth
but must be avoided to prevent the following
reaction from occurring:
Avirtually quantitative yield is obtained if the
crystals are isolated quickly and washed with a
cold concentration NH
4
Cl solution saturated
with Cl
2
.
The same basic separation process can be
carried out by using potassium chloride instead
of ammonium chloride. Using potassium chlo-
ride has advantages and disadvantages:
.
As the solubilities of potassium hexa chloro
salts are lower than those of corresponding
ammonium salts, separation yields are better
.
Precipitation of (NH
4
)
2
[PdCl
6
] by passing
chlorine through an NH

4
-containing solution
is dangerous, because explosive nitrogen
trichloride is formed. This can be oxided by
using potassium chloride [147]
.
Potassium ions are introduced into the puri-
cation processes (see below) and are more
difcult to remove than immonium ions
Separation of Rhodium. Ammonium hex-
achlororhodate, (NH
4
)
3
[RhCl
6
], can be isolated
fromrhodiumsolutions in hydrochloric acid such
as those obtained after removal of the other
platinum group metals. Ammonium chloride is
added, followed by concentration and crystalli-
zation. Much of the remaining (NH
4
)
2
[PtCl
6
] and
(NH
4
)
2
[IrCl
6
] is precipitated at the same time.
Chlorides of the base metals mostly remain in
solution. The (NH
4
)
3
[RhCl
6
] can be selectively
redissolved in water at roomtemperature to form
an almost saturated solution. This gives a puried
solution of rhodium. Both (NH
4
)
2
[PtCl
6
] and
(NH
4
)
2
[IrCl
6
] are recovered by ltration.
The rhodium can also be isolated as chloro-
pentamminerhodium(III) chloride, [RhCl
(NH
3
)
5
]Cl
2
, or potassium hexanitrorhodate(III),
K
3
[Rh(NO
2
)
6
], but the precipitations must be
carried out in weakly alkaline solution. These
methods are unsuitable for solutions that contain
large quantities of base metals because, under
reaction conditions, these form insoluble hydro-
xides that are difcult to lter.
Cementation of rhodium by other metals (see
Section 6.3) can also be carried out. However, all
of the noble metals and the copper remain with
344 Platinum Group Metals and Compounds Vol. 28
the rhodium. An advantage is that precipitation of
rhodium is complete in this process.
Distillation of Ruthenium(VIII) Oxide.
The most important industrial process for the
isolation of ruthenium is distillation of the very
volatile ruthenium(VIII) oxide, RuO
4
, from
aqueous solution. This compound is formed in
solutions of potassium ruthenate(VI), K
2
[RuO
4
],
and hexachlororuthenate(III), K
3
[RuCl
6
], by
oxidation with chlorine at around neutral pH or
with sodium chlorate at pH 0 3. Oxidation can
also be carried out in dilute sulfuric acid solution
with potassiumpermanganate, or with potassium
chlorate in sulfuric acid solution, but these meth-
ods are less satisfactory for safety reasons. The
volatile RuO
4
is absorbed by dilute hydrochloric
acid, and is converted into water-soluble chlor-
oruthenate complexes.
Even in the absence of potassium permanga-
nate, chlorate, or their reaction products, the
distillation of RuO
4
is hazardous. The presence
of NH

4
salts can lead to the formation of
explosive chlorides of nitrogen. Therefore, re-
moving ruthenium at the start of a separation
process is often preferable. The formation of
chlorine dioxide, chlorate, and perchlorate is
also possible. Moreover, RuO
4
can explode by
spontaneous decomposition, especially at
> 100

C and on contact with organic sub-
stances. To improve safety, work should be
carried out under an inert gas and by avoiding
the presence of large quantities (e.g., using a
continuous process).
Distillation of Osmium(VIII) Oxide. As a
rule, osmiumis present in only a fewprimary and
secondary raw materials. Osmium should, if
possible, be isolated as the rst step of a separa-
tion process, so that later operations will not lead
to loss of volatile OsO
4
.
Solutions obtained from digestion of ores
normally contain osmates. Treatment of solu-
tions in dilute sulfuric acid with oxidizing agents
such as CrO
3
, K
2
S
2
O
8
, or HNO
3
causes osmium
(VIII) oxide to be formed and to distill off. From
this distillate, OsO
4
can be isolated directly as a
water-insoluble oil (mp 40

C). Alternatively, it
can be absorbed in potassiumhydroxide solution,
forming K
2
OsO
4
, or can be converted to metallic
osmiumby reaction with formaldehyde solution.
Owing to the toxicity of OsO
4
, its escape into the
atmosphere must be prevented by use of the best
possible absorption equipment. No danger of
explosion exists.
Also, OsO
4
can be formed and distilled off by
heating ne osmium powder in a stream of
oxygen.
Solvent Extraction. Liquid liquid extrac-
tion is often characterized by distribution coef-
cients that vary greatly from element to element.
These can usually be modied by chemical meth-
ods to give conditions favorable for the separation
of PGMs. However, the separation factors result-
ing from the ratios of the distribution coefcients
rarely enable a single separation stage to provide
purities that fulll modern requirements for metal
quality. Although separations are generally better
than those effected by precipitation crystalliza-
tion, coarse separation by solvent extraction must
be followed by purication.
In practical industrial separation processes,
mainly four extractants are used [109],
[130133], [143146]. The most long-standing
process is the separation of Pt (IV) and
Ir (IV) from Rh (III) with tributyl phosphate
(TBP) [148], [149]. The extraction of H
2
[PtCl
6
]
and H
2
[IrCl
6
] must be carried out in 4 6 MHCl
(Fig. 15). If the usual mixture of 1 part TBP with
Figure 15. Extraction of platinum group metal chloro com-
plexes by tributyl phosphate
Vol. 28 Platinum Group Metals and Compounds 345
3 parts hydrocarbon solvent is used, the capacity
of the organic phase is limited in practice to ca.
10 g of Pt Ir and it is therefore less suitable for
extraction treatment of solutions whose main
constituent is platinum (e.g., normal renery
feed solutions).
Trioctylamine is used widely for the sol-
vent extraction of large amounts of platinum
from renery solutions [150152]. It is also
used for the solvent extraction of Ir (IV)
(Fig. 16). Stripping can be facilitated by
changing the stripping solution or the valence
of the metal. Diluent solvents are also em-
ployed when carrying out solvent extraction
with amines.
For the solvent extraction of palladium, thioe-
sters are currently used (e.g., di-n-hexyl sulde or
di-n-octyl sulde) [110], [151155]. They pro-
duce good separation from other PGMs and have
a high capacity for the metal. A disadvantage is
the poor kinetics of complex formation, the
reaction times required being 30 mins or more.
Hence, mixer settler equipment must be used
rather than column equipment. Stripping with
aqueous ammonia produces [Pd(NH
3
)
4
]Cl
2
; this
can be converted easily to [Pd(NH
3
)
2
Cl
2
], which
is then puried.
The method used for high-tonnage production
of copper by solvent extraction with oximes is
also successfully used for palladium (Fig. 17).
However, high concentrations of palladium in
the organic phase cannot be achieved.
Numerous other solvent extraction systems
have been investigated, some of which are un-
dergoing industrial development [114], [115],
[149], [156159].
6.5. Purication
Methods used for purication of the products
from the separation process employ the same
principles (i.e., valence change, temperature
change, addition of common ions, and modica-
tion of complexes by chemical reaction).
Purication of Platinum. Recrystalliza-
tion of sodium hexachloroplatinate(IV),
Na
2
[PtCl
6
], from hot water is effective, but large
amounts of platinum must be recycled.
Very effective purication is achieved by the
oxidative hydrolysis of the metallic impurities
palladium, rhodium, iridium, ruthenium, and
base heavy metals, which are removed as insol-
uble hydroxides (see Fig. 11). Precipitation from
hot aqueous solution is carried out by addition of
sodium bromate at pH 6.5 or by passing through
chlorine at slightly alkaline pH. The oxide hy-
drates adsorb considerable amounts of platinum.
The yield of platinum therefore depends on the
purity of the feed material.
Figure 16. Extraction of platinum group metal and gold
chloro complexes by trioctylamine
Figure 17. Extraction of palladium(II) and platinum(IV)
chloro complexes by an aldoxime (LIX TN 1911) a) Plati-
num(IV); b) Palladium(II)
346 Platinum Group Metals and Compounds Vol. 28
The classical method of purication is by
repeated precipitation of (NH
4
)
2
[PtCl
6
] or
K
2
[PtCl
6
]. The crude salt is converted into me-
tallic platinum, dissolved to form H
2
[PtCl
6
] (see
Chap. 5), and reprecipitated. By repeating this
many times, very high purities are obtained,
although the cost is also high. Also,
(NH
4
)
2
[PtCl
6
] can be converted directly to
H
2
PtCl
6
by oxidation of the NH

4
or by cation
exchange. In the oxidative decomposition of
NH

4
(e.g., by heating the aqueous solution with
addition of Cl
2
or HNO
3
), care must be taken to
use a carrier gas or distillative conditions to
prevent accumulation of explosive nitrogen
halogen compounds.
Conventional crystallizations from water are
possible, but the solubility of (NH
4
)
2
[PtCl
6
] is
relatively low, so that despite favorable temper-
ature coefcients (see Fig. 7), large volumes
must be used. Modied crystallization methods
are more economic (e.g., utilization of the con-
siderably higher solubilities in water above
100

C at higher pressure). The purication ef-
fected by crystallization is enhanced by hydro-
lysis. In neutral or very slightly acidic media
above 90

C, the conversion of the chloro com-
plexes of the platinum group metals (especially
metals other than platinum) into hydroxo com-
plexes and oxide hydrates begins. These cannot
form mixed crystals with (NH
4
)
2
[PtCl
6
]. The
extent of hydrolysis of hexachloroplatinate(IV)
increases with increasing temperature and reac-
tion time. Therefore, high temperature and long
reaction time lead to a lower yield of crystalline
product. The reaction is reversible in the presence
of hydrochloric acid.
When the products of solvent extraction by
substituted amines are stripped, solutions of plat-
inum compounds in hydrochloric acid are ob-
tained. From these, pure (NH
4
)
2
[PtCl
6
] is pre-
cipitated by addition of NH
4
Cl.
Puricationof Palladium [160]. Impure am-
monium hexachloropalladate(IV), (NH
4
)
2
[PdCl
6
],
can be dissolved directly for purication. This is
achieved by the following reaction:
3 (NH
4
)
2
[PdCl
6
[20 NH
3
3[Pd(NH
3
)
4
[Cl
2
12 NH
4
ClN
2
Acidication of a solution of [Pd(NH
3
)
4
]Cl
2
precipitates the sparingly soluble, pale yellow
trans-diamminedichloropalladium(II):
[Pd(NH
3
)
4
[Cl
2
2 HCl[PdCl
2
(NH
3
)
2
[2 NH
4
Cl
The impure salt should be dissolved quickly at
room temperature with agitation to prevent ap-
preciable quantities of the (NH
4
)
2
[PtCl
6
] present
as an impurity from dissolving. Undissolved ma-
terial, mainly hydroxides and (NH
4
)
2
[PdCl
6
], is
ltered off. Hydrochloric acid is added to the
solution until a pH of 1 is reached, causing
[PdCl
2
(NH
3
)
2
] to precipitate as easily lterable
crystals. Possible causes of poor purication are
too high a concentration of (NH
4
)
2
[PdCl
6
] in the
impure material, too prolonged a reaction with
ammonia, too high a concentration of ammonia,
or problems with ltration of the hydroxidic
precipitate before precipitating [PdCl
2
(NH
3
)
2
].
High temperature is also detrimental. If the acid
concentration is too high, the yield is reduced due
to further reaction to formsoluble (NH
4
)
2
[PdCl
4
].
Other possible methods for dissolving
(NH
4
)
2
[PdCl
6
] are
2 (NH
4
)
2
[PdCl
6
[N
2
H
4
2 (NH
4
)
2
[PdCl
4
[4 HClN
2
or
(NH
4
)
2
[PdCl
6
[(NH
4
)
2
[PdCl
4
[Cl
2
Pure (NH
4
)
2
[PdCl
6
] can be obtained in almost
quantitative yield by passing chlorine through the
solution and adding NH
4
Cl.
The purication of (NH
4
)
2
[PdCl
6
] by repre-
cipitation is useful in the presence of silver and
most base metals. In the presence of rhodium,
platinum, iridium, and copper, however, better
purication is achieved by precipitating
[PdCl
2
(NH
3
)
2
], although higher losses of palla-
dium to the mother liquor must be tolerated.
Dichlorodiamminepalladium(II),
[PdCl
2
(NH
3
)
2
], can be produced by direct
precipitation from an impure solution of palladi-
umresulting fromcrude separation or inadequate
purication. It is dissolved in aqueous ammonia
solution to form [Pd(NH
3
)
4
]Cl
2
and reprecipi-
tated by hydrochloric acid.
An ammoniacal stripping solution is used
after solvent extraction of palladium by dialkyl
sulde. Palladium can be precipitated from this
by acidifying to pH 1, thus producing [Pd
(NH
3
)
2
Cl
2
] directly in a highly pure form.
Purication of Iridium. The purication
of crude ammonium hexachloroiridate(IV),
(NH
4
)
2
[IrCl
6
], is carried out by precipitation of
Vol. 28 Platinum Group Metals and Compounds 347
the unwanted elements as suldes; these consist
mainly of other platinum group metals and heavy
base metals. This converts hexachloroiridate(IV)
to hexachloroiridate(III), which must be reoxi-
dized to precipitate (NH
4
)
2
[IrCl
6
]. The suldes
are precipitated from slightly acidic solution by
hydrogensulde. Toensure optimumprecipitation
conditions for all elements present, the sulde
precipitation must usually be carried out repeated-
ly. Iridium can be puried by liquid liquid ex-
traction [161]. It is extracted relatively easily in the
tetravalent state, but not in the trivalent state (cf.
Fig. 15). Reduction by Fe
2
, As
3
, or ascorbic
acid at room temperature causes selective reduc-
tion of Ir (IV) or Ir (III); Pt (IV) is unaffected.
Purication of Rhodium [162]. Ammoni-
um hexachlororhodate(III), (NH
4
)
3
[RhCl
6
], can
be crystallized from water or hydrochloric
acid. However, the yields are poor, as is the
degree of separation fromplatinumand iridium.
Precipitation of [Rh(NH
3
)
5
Cl]Cl
2
or (NH
4
)
3
[Rh
(NO
2
)
6
] is more effective, although yields are
not good, and treatment of the mother liquor is
problematic.
Good results are obtained when H
2
[PtCl
6
] and
H
2
[IrCl
6
] are removed by liquid liquid extrac-
tion, and base metal cations by strongly acidic
ion-exchange resins. At one time, treatment of
crude rhodium with chlorine at 700

C was an
important process. The reaction product con-
sisted mainly of insoluble RhCl
3
from which the
chlorides of platinum, palladium, and base me-
tals were dissolved by treatment with hydrochlo-
ric acid. Satisfactory purication could usually
be obtained only by repeating the process.
Crude potassium hexanitritorhodate(III),
K
3
[Rh(NO
2
)
6
], can be converted to hexachlor-
orhodate(III) by heating with hydrochloric acid.
This can be followed by reprecipitating K
3
[Rh
(NO
2
)
6
] or precipitating [RhCl(NH
3
)
5
]Cl
2
.
6.6. Conversion of Salts into Metals
[31], [36], [41], [108], [118]
The end products of PGM separation are metal
compounds, but all platinum group metals are
marketed almost exclusively in the form of me-
tallic sponge or powder.
Conversion to the metals is carried out mainly
by thermal decomposition of the ammonium
chloro complexes (calcination). These com-
pounds have decomposition temperatures
(Fig. 18), of 200 500

C. The size and geom-
etry of the charge affect the reaction course. The
low thermal conductivity of the charge means
that the reaction proceeds slowly, but smooth
production of the desired decomposition pro-
ducts is ensured. Also, the negative heat of
reaction of the decomposition tends to slowdown
the process. In practice, favorable conditions are
achieved by external heating at 900 1000

C.
In earlier days, the thermal decomposition of
PGM compounds was carried out in gas-heated
mufe furnaces that were not very leaktight. The
best of these were provided with a collection
chamber for NH
4
Cl (sublimation temperature
340

C) and included a waste gas system [43].
Today, tubular fused silica reactors, enclosed in
an electrically heated furnace, are used. Astream
of inert gas can be passed through at a controlled
rate, and absorption equipment is present for
NH
4
C and HCl. Automated plants are in opera-
tion [163], [164].
Thermal treatment of PGMcompounds canalso
be carried out in the presence of hydrogen. For
Figure 18. Thermal decomposition of platinum group metal
complexes
348 Platinum Group Metals and Compounds Vol. 28
safety reasons, a mixture of hydrogen and nitrogen
below the ignition temperature is preferable.
Another possibilitytoconvert PGMcompounds
into metals is chemical reduction with, e.g., hydra-
zine inaqueous media. This process must be usedif
the nal products of purication are salts other than
the ammonium salts (e.g., K
2
[PtCl
6
]).
Platinum. The compound (NH
4
)
2
PtCl
6
can
be converted to platinum sponge by thermal
decomposition at 800

C, according to
3 (NH
4
)
2
[PtCl
6
[3 Pt2 NH
4
Cl16 HCl2 N
2
Excessive carryover of platinum can be
avoided by introducing ammonium hexachloro-
platinate(IV) into the reaction zone at ca. 300

C
and heating it rapidly. Waste gas is washed with
water to extract ammonium chloride, both for
environmental reasons and to prevent the loss of
traces of platinum.
If the reaction is carried out in a hydrogen
atmosphere, elemental platinumis formed below
the sublimation temperature of NH
4
Cl (ca.
350

C). Platinum carryover is then appreciably
less, and more ammonium chloride is formed:
(NH
4
)
2
[PtCl
6
[2 H
2
Pt2 NH
4
Cl4 HCl
If NH
4
Cl is not sublimed but is removed by
dissolving in water, nely divided platinumpow-
der can be produced by this process. Calcination
of the hexachloroplatinate(IV) of an alkali metal
is not recommended, because the alkali metal
chloride produced is difcult to remove by aque-
ous dissolution from the platinum sponge.
Hexachloroplatinates can usually be reduced
in aqueous solution or suspension according to
(NH
4
)
2
[PtCl
6
[N
2
H
4
6 NaOHPt6 NaCl2 NH
3
N
2
6 H
2
O
The reaction proceeds best above 80

C, with
excess NaOHmaintained at 2 Mand the reaction
controlled by adjusting the rate of addition of
N
2
H
4
. The reaction must be ushed with nitro-
gen, because hydrogen can be formed in a side
reaction. The platinumblack formed is washed to
remove salts, and either dried to produce powder
or heated strongly to produce sponge. Overall,
wet chemical reduction is more expensive than
calcination but should be used if alkali metal
hexachlorometallates are present, because their
decomposition products cannot be sublimed.
Palladium. The thermal decomposition of
dichlorodiaminepalladium(II), [Pd(NH
3
)
2
Cl
2
],
begins at ca. 290

C in an inert atmosphere.
Process conditions are the same as for
(NH
4
)
2
[PtCl
6
]. The reaction is
3[Pd(NH
3
)
2
Cl
2
[3 Pd4 NH
4
Cl2 HClN
2
For the calcination of ammonium hexachlor-
opalladate(IV), which loses chlorine at ca.
280

C, the temperature should be increased
extremely slowly over the range 100 300

C.
If calcination is carried out in air, the palladium
sponge formed contains large amounts of PdO,
which must be reduced by strong heating in a
hydrogen atmosphere.
The wet chemical reduction
2[Pd(NH
3
)
2
Cl
2
[N
2
H
4
2 Pd4 NH
4
ClN
2
and the reduction of (NH
4
)
2
[PdCl
6
] proceed
quantitatively in strongly ammoniacal solution
above 50

C. Sodium formate in alkaline solu-
tion can also be used as reducing agent. A nitro-
gen atmosphere must be used in both cases to
prevent formation of explosive gas mixtures.
Chemical reduction often produces pyrophoric
palladium black, which must be dried in an inert
gas atmosphere.
Iridium. The best method of producing irid-
ium is to reduce ammonium hexachloroiridate
(IV), (NH
4
)
2
[IrCl
6
], in a hydrogen atmosphere
ca. 800

C, yielding the metal powder. Calcina-
tion in air gives an oxide-containing material.
Wet chemical reduction with hydrazine is possi-
ble only in strongly alkaline sodium hydroxide
solution and does not always go to completion.
Rhodium. Ammonium hexachlororhodate
(III) is subjected to the same process of thermal
reduction as used for (NH
4
)
2
[IrCl
6
].
Wet chemical reduction with hydrazine ac-
cording to
4 (NH
4
)
3
RhCl
6
3 N
2
H
4
24 NaOH4 Rh3 N
2
12 NH
3
24 NaCl24 H
2
O
must be carried out with a large excess of hydra-
zine and NaOH at ca. 100

C to ensure complete
reaction.
Vol. 28 Platinum Group Metals and Compounds 349
Ruthenium. Ammonium hexachlororuthe-
nate(III IV) is reduced, preferably in a hydro-
gen atmosphere, at ca. 800

C. Aqueous solutions
of ruthenates(IV) (e.g., produced by adding RuO
4
to an alkali-metal hydroxide solution) are treated
with ethanol to precipitate hydrated RuO
2
, which
is reduced in a hydrogen atmosphere at 800

C.
Osmium. Osmium tetroxide that has been
absorbed in potassium hydroxide solution is
precipitated as potassium osmate(IV) by adding
ethanol. This is reduced by strong heating in a
hydrogen atmosphere or reacted with NaBH
4
in
aqueous solution [165]. The product must be
washed with water in both cases.
6.7. Partial Purication
Platinum Rhodium Mixtures. For in-
dustrial use, platinum and rhodium are often
alloyed together, and separating these elements
during the recovery process may be unnecessary.
The solutions obtained by dissolving metallic
platinum rhodium scrap can be used. The neu-
tral solutions are treated with a sodium-loaded
ion exchanger to replace all unwanted cations
with sodium. Sometimes, Na

is replaced by H

,
giving a solution of H
2
[PtCl
6
] and H
3
[RhCl
6
]
suitable for further treatment (e.g., reduction by
hydrazine to give Pt Rh powder).
Similar processes can be used for treating
some single metal catalysts (e.g., material from
the calcination of carbon palladium).
Surface Cleaning. Some returned metallic
materials with only surface contamination re-
quire merely surface cleaning, thereby avoiding
a wet separation process. They can be treated
with acids, such as hydrouoric acid, or with
fused salt (e.g., NaHSO
4
), although some of the
outer layer of platinum dissolves.
6.8. Treatment of Internally Recycled
Material
A buildup of base metals occurs in recycled mate-
rial such as mother liquor from precipitation and
crystallization. These base metals originate from
the raw materials and from salts formed in the
reactions, and also include small quantities of
platinumgroupmetals fromtheseparationprocess.
The quantity or recycled noble metals should
normallynot exceed1 %of the metal inthe starting
material. The extent of recycle must be limited,
because losses are relatively high when noble
metals are recovered from this type of material.
Solutions containing platinum metals with
only small amounts of other materials should be
concentrated by evaporation in the presence of
hydrochloric acid. They can be combined with
fresh raw material for separation.
If the solutions contain only ammonium chlo-
ride and platinumgroup metals, they can often be
reused directly as a precipitating agent after
concentration in acid conditions.
If the solutions contain large amounts of salts
of alkali metals, alkaline earths, or other metals
along with platinum and palladium residues, it is
advantageous to separate the ions [PtCl
6
]
2
and
[PdCl
4
]
2
from the other materials by using
strongly basic ion exchangers. Good separation
is achieved if only the two chloro complexes are
present. For rhodiumand iridiumthis condition is
often not achieved, because of hydrolysis to give
hydroxo complexes, so this method cannot be
used unless special precautions are taken.
In earlier times, noble metals were recovered
fromsuch solutions by cementation with zinc in a
hydrochloric acid solution. Aluminumis nowthe
preferred reducing agent because of the high cost
of zinc, which must be present in large excess,
and the resultant environmental problems. Noble
metals can also be recovered with sodium boro-
hydride. Alternatively, they can be reduced by
hydrazine in alkaline solution. If no precautions
are taken, hydroxides of base metals are also
precipitated, but these can easily be redissolved.
Copper is also precipitated in this reduction
process. After redissolving the metals, the latter
can be reprecipitated as copper(II) oxalate or
another copper(I) or copper(II) salt that is spar-
ingly soluble in slightly acidic solution.
All materials from which noble metals have
been recovered must be monitored carefully for
possible noble-metal content before disposal, so
that no irrevocable losses occur.
6.9. Construction Materials
Many of the operations described above pose
special problems in the choice of materials for
equipment and vessels.
350 Platinum Group Metals and Compounds Vol. 28
Plastics resistant to mineral acids can often be
used. Vessels and reactors lined with hard rubber
are resistant to acids and saturated chlorine solu-
tions at 90

C. Unsuitable metals for commonly
occurring solutions of platinum and other plati-
num group metals include stainless steel, titani-
um, zirconium, the Hastelloys, and silver,
because these materials cause cementation of
platinumgroup metals. Tantalumis an exception.
It is resistant to dissolved halogens and does not
cement platinumgroup metals fromsolution. It is
a suitable material for steam-heated heat exchan-
gers. Equipment constructed of borosilicate glass
and glass-lined steel reactors are chemically
resistant to all of these materials. For solutions
containing large amounts of ruthenium or osmi-
um, other construction materials are recom-
mended, including graphite for some items.
For treating raw materials with acidic molten
salts or salts that have a chlorinating action, and
for calcination, the use of fused silica equipment
is best. Treatment with molten oxidizing alkaline
salts is carried out in silver or nickel crucibles.
7. Platinum Group Metal
Compounds [5], [6], [30], [32], [36],
[41], [88], [105107], [166], [263270]
Because of the many possible oxidation states of
platinumgroup metals and their tendency to form
complexes, the range of compounds is extremely
wide.
7.1. Inorganic Compounds
7.1.1. Platinum Compounds
Hexachloroplatinic(IV) acid, H
2
[PtCl
6
]
6 H
2
O, M
r
517.92, theoretical platinumcontent
37.68 %, platinum content of commercial prod-
uct ca. 40 % [commercial names: chloroplatinic
acid, hydrogen hexachloroplatinate(IV)], forms
reddish brown crystals (mp ca. 150

C), which
deliquesce in moist air and are readily soluble in
water or alcohol. The usual commercial product
is an aqueous solution with a platinumcontent of
25 %.
Production (see Chap. 5). Platinum sponge
is treated with moderately concentrated hydro-
chloric acid saturated with chlorine in a stirred
vessel at ca. 80

C. The solution obtained is
evaporated until it reaches 150

C. When cooled,
it changes into solid H
2
PtCl
6
4.5 H
2
O, which
contains ca. 40 % platinum, no mother liquor is
produced. If the platinum is dissolved in aqua
regia instead of hydrochloric acid chlorine, the
nitric acid and NOCl formed must be removed
completely, preferably by repeated evaporation
to a syrupy consistency and redissolution in
hydrochloric acid.
Uses. Hexachloroplatinic(IV) acid is the
most industrially important platinum compound.
It is used in the production of most other platinum
compounds and preparations. It is used primarily
to make catalysts by impregnating support ma-
terials and as a precursor hydrosilylation
catalysts.
Hexachloroplatinates(IV). Ammonium
hexachloroplatinate(IV), (NH
4
)
2
[PtCl
6
], and, to
a limited extent, the orange-red salt sodium
hexachloroplatinate(IV), Na
2
[PtCl
6
], are impor-
tant in platinum separation processes (see
Chap. 6).
Platinum Chlorides. Platinum(IV) chlo-
ride, PtCl
4
, is produced by careful dehydration
of H
2
PtCl
6
6 H
2
O at ca. 300

C in a stream of
chlorine. It is a red-brown, crystalline, hygro-
scopic powder with a relatively narrow range of
thermal stability.
Above 380

C, PtCl
4
liberates chlorine and
forms platinum(II) chloride, PtCl
2
, which is sta-
ble between 435 and 580

C. Platinum(III) chlo-
ride, PtCl
3
, is probably formed as an intermediate
in this reaction. Above 580

C, further decom-
position occurs to yield metallic platinum. Plati-
num(IV) chloride is the only chloride of platinum
that is soluble in water.
Platinum(II) chloride can also be obtained
from a solution of H
2
[PtCl
4
] by careful evap-
oration under vacuum. Chlorides of platinum
can be produced by reacting chlorine with
nely divided platinum. The chloride obtained
will be the one that is stable at the reaction
temperature.
Oxides of Platinum. The most industrially
important oxide of platinum is platinum(IV)
oxide hydrate, PtO
2
H
2
O, a hydrogenation
Vol. 28 Platinum Group Metals and Compounds 351
catalyst. To prepare this substance, a solution
of 9 parts sodium nitrate and 1 part platinum
as H
2
[PtCl
6
] is evaporated to dryness. The
product mixture is nely powdered and added
to molten NaNO
3
(10 parts) at 520

C with
agitation. The product is dissolved in water,
washed, and carefully dried to give a brown
powder, insoluble in aqua regia, with poorly
dened stoichiometry.
Platinum(II) oxide, PtO, and platinum(II) ox-
ide hydrate, PtO H
2
O, are also known, but have
little or no industrial importance.
Other Platinum Compounds. The follow-
ing compounds are used in aqueous electrochem-
istry: potassium tetranitroplatinate(II), K
2
[Pt
(NO
2
)
4
]; dinitrodiammineplatinum(II), [Pt
(NH
3
)
2
(NO
2
)
2
]; and sodium hexahydroxoplati-
nate(IV), Na
2
[Pt(OH)
6
].
Potassium tetracyanoplatinate(II),K
2
[Pt
(CN)
4
], can be used in electroplating by molten
salt electrolysis. Barium tetracyanoplatinate(II),
Ba[Pt(CN)
4
], is used in the manufacture of uo-
rescent screens. Many other cyano complexes are
known. Simple cyanides such as Pt(CN)
2
and Pd
(CN)
2
also exist.
Potassium tetrachloroplatinate(II),K
2
[PtCl
4
],
is a starting material for the synthesis of most
Pt (II) compounds. Platinum(II) acetylacetonate
is used in the pyrolytic production of platinum
surface coatings (see Section 10.10.2) and is
superior to other platinum compounds in this
application.
Dichlorodiammineplatinum(II), [PtCl
2
(NH
3
)
2
], is of historical interest and was
known in two forms: Peyrones chloride
and Reisets second chloride. In 1893,
WERNER recognized that these were cis and
trans isomers. cis-Diammine dichloroplati-
num, also known as cisplatin or cis-platinum,
is used in cancer therapy. Carboplatin (cis-
diammine-1,1-cyclobutanedicarboxylatoplati-
num), a second-generation cancer drug shows
fewer side effects than cis-Platinum. Drugs for
oral application like JM 216 are still in clinical
trials [271].
7.1.2. Palladium Compounds [168]
Tetrachloropalladic(II) acid, H
2
[PdCl
4
],
is stable only in solution. Commercial solutions
in hydrochloric acid contain 20 % palladium and
are dark brown.
Production. The method of producing
H
2
[PdCl
4
] solution is similar to that for H
2
[PtCl
4
]
solution. The metal is dissolved in HCl Cl
2
or
HCl HNO
3
, the rate of dissolution being higher
than with platinum (see Fig. 6). If dissolution
occurs below ca. 50

C, hexachloropalladic(IV)
acid is formed rst.
Uses. The solution of tetrachloropalladic(II)
acid is the most industrially important palladium
preparation. It is the starting material for almost
all other palladium compounds, particularly
catalysts.
Palladium(II) Chloride, PdCl
2
, M
r
177.31,
theoretical palladium content 60.0 %, palladium
content of commercial product 59.9 %, is a
brown to brownish violet powder, insoluble in
water, but readily soluble in hydrochloric acid
and solutions of alkali-metal chlorides. It sub-
limes at 590

C. Decomposition begins at
600

C and is complete at 740

C.
Production. The best method of production
of PdCl
2
is careful evaporation of a solution of
H
2
[PdCl
4
] in hydrochloric acid, preferably in a
rotary evaporator.
Uses. Anhydrous PdCl
2
is the starting mate-
rial for a number of palladium compounds.
Palladium Oxides. Poorly dened oxide
hydrates are obtained by adding alkali to aqueous
solutions of Pd (II) compounds. The Pd (IV)
oxide hydrates obtained from Pd (IV) solutions
release oxygen. A catalytically active palladium
preparation analogous to PtO
2
x H
2
O can be
obtained by evaporating a solution of H
2
[PdCl
4
]
and NaNO
3
, and fusing the product.
Stoichiometric palladium(II) oxide, PdO,
which is crystallographically well dened, is
obtained by reaction of palladium black with
oxygen or air at 750

C. Decomposition occurs
at 850

C.
Ammine Complexes of Palladium. The
addition of ammonia to solutions of palladium
chloride rst causes the formation of a pink
precipitate of the binuclear complex
352 Platinum Group Metals and Compounds Vol. 28
[Pd(NH
3
)
4
PdCl
4
], known as Vauquelins salt,
which is converted to soluble tetramminepalla-
dium(II) chloride, [Pd(NH
3
)
4
]Cl
2
, by further ad-
dition of NH
3
. Acidication of this solution
yields the sparingly soluble light-yellow trans-
diamminedichloropalladium(II), [PdCl
2
(NH
3
)
2
].
These compounds and reactions are important in
the industrial separation of palladium (see
Chap. 6) and in electroplating processes.
Other Palladium Compounds. Ammoni-
um hexachloropalladate(IV), (NH
4
)
2
[PdCl
6
], is
important in separation technology. It is an oxi-
dation product of tetrachloropalladate(II) (see
Chap. 6). Palladium(II) sulfate, palladium(II)
nitrate, and palladium(II) acetate are of some
importance in preparative chemistry. The ready
formation of palladium hydride is exploited in-
dustrially for example for the purication of
hydrogen.
7.1.3. Rhodium Compounds [169]
Hexachlororhodic(III) Acid, H
3
RhCl
6
.
Wet separation processes and molten salt disso-
lution usually produce (NH
4
)
3
[RhCl
6
] or
Na
3
[RhCl
6
] 12 H
2
O in crystalline form. Both
compounds form deep-red crystals, which are
very soluble in water. Free hexachlororhodic
(III) acid, H
3
[RhCl
6
], can be obtained by cation
exchange, by oxidative decomposition of the
cation in the case of the NH

4
salt (see Section
6.2) or by dissolution of nely divided rhodium
powder in hydrochlorine acid and chlorine gas.
The composition of the chloro complexes of
rhodium depends strongly on the concentration
of hydrochloric acid, the temperature, the dura-
tion of reaction, and the previous treatment
of the solution. By starting with a strongly
acidic medium, the following transformations
are possible:
[RhCl
6
[
3
[RhCl
5
(H
2
O)
2

[RhCl
4
(H
2
O)
2
[

[RhCl
3
(H
2
O)
3

[RhCl
2
(H
2
O
4
)[

[RhCl(H
2
O)
5
[
2

[Rh(H
2
O)
6
[
3
The color varies from raspberry red to brown.
Rhodium Chlorides. Anhydrous, brownish
red rhodium(III) chloride, RhCl
3
, which is insol-
uble in water and mineral acids, is obtained by
heating rhodium powder to 700

C in a chlorine
atmosphere.
So-called soluble rhodium chloride, with the
approximate composition RhCl
3
2.5 H
2
O, is
obtained by evaporating a solution of H
3
[RhCl
6
]
in hydrochloric acid, preferably in a rotary evap-
orator. This compound is the most important
commercial rhodium product, and is used as the
starting material for other rhodium compounds
and catalysts.
Rhodium Sulfate. Rhodium(III) sulfate,
Rh
2
(SO
4
)
3
, can crystallize with varying
amounts of water; it can be obtained by dissol-
ving Rh(OH)
3
x H
2
O in sulfuric acid or by the
action of hot sulfuric acid on freshly precipitat-
ed rhodium black. It is used in rhodium plating
baths.
Chlorotris(triphenylphosphine)Rhodium(I),
RhCl[P(C
6
H
5
)
3
]
3
, is formed by the reaction of
triphenylphosphine withsoluble rhodium(III) chlo-
ride in ethanol solution under reux. It separates as
deep-red crystals.
This complex, and rhodium compounds with
similar structures, are important homogeneous
catalysts (see Section 8.1).
7.1.4. Iridium Compounds
Hexachloroiridic(IV) Acid, H
2
[IrCl
6
], is
produced in aqueous solution by the methods
used to obtain H
3
[RhCl
6
] (i.e., from the ammo-
nium or sodium salts). It is by far the most
important iridiumcompound. The oxidation state
is relatively easily changed (in either direction),
the very intense dark brown [Ir
IV
Cl
6
]
2
changing
to the lighter colored [Ir
III
Cl
6
]
3
or vice versa.
The compounds are used as precursors in the
preparation of coated anodes for the production
of chlorine and sodium hydoxide. The ammoni-
um salts of both anions are important in separa-
tion technology (see Chap. 6).
Iridium(III) Chloride, IrCl
3
. A product
stoichiometrically decient in chlorine is ob-
tained by heating iridium powder in a stream
of chlorine at 650

C. The chlorination reac-
tion is assisted by the presence of carbon
monoxide.
Vol. 28 Platinum Group Metals and Compounds 353
7.1.5. Ruthenium Compounds
Ruthenium(VIII) Oxide, RuO
4
is formed
by the oxidation of aqueous solutions of ruthe-
nates. It has a melting point of 25.5

C and is
therefore a liquid at room temperature. It is both
toxic and explosive (see Section 10.1).
Soluble Ruthenium(IV) Chloride. So-
called soluble ruthenium chloride consists main-
ly of Ru(OH)Cl
3
with some RuCl
3
H
2
O, and is
prepared by reacting RuO
4
with hydrochloric
acid and evaporating the solution. The compound
(NH
4
)
2
[RuCl
6
] can be precipitated by adding
NH
4
Cl. Solutions of ruthenium chloride in hy-
drochloric acid are used in the production of
coated anodes.
Potassium Ruthenate(VI), K
2
[RuO
4
], is
formed by fusing ruthenium with KOH KNO
3
or by dissolving RuO
4
in potassium hydroxide
solution.
7.1.6. Osmium Compounds
Osmium(VIII) Oxide, OsO
4
, is the most
important osmium compound. It is formed
even at room temperature by the oxidation of
osmium powder by air. It is prepared by
strongly heating osmium in a stream of oxygen
at 500 800

C. The melting point is 40.6

C,
and the boiling point 131.2

C. Sublimation
takes place even at room temperature. OsO
4
used as an oxidation catalyst or as an aqueous
solution to stain organic tissue for microscopic
analysis.
Potassium osmate(VI), K
2
[OsO
2
(OH)
4
], is
formed by the reaction of OsO
4
with potassium
hydroxide solution and alcohol.
7.2. Organic Compounds [170], [171]
The PGMs form numerous compounds with
direct metal-carbon links both as carbonyls and
as organometallic compounds. Many of these are
of industrial importance in homogeneous cataly-
sis (see Section 10.5). Complex organic com-
pounds of ruthenium and osmium can facilitate
electron-transfer mechanisms in molecular struc-
tures and also serve as sensitizer materials for
photoinduced hydrogen production (see
Section 10.9).
Osmium bipyridyl redox polymers com-
bined with a redox enzyme can be used as
miniature in vivo sensors for implantation into
diabetes patients for continuous monitoring of
their blood glucose levels (wired enzyme bio-
sensor, [271]). The divalent and trivalent com-
plexed osmium ions can exchange electrons at
high rates. The osmium polymer connects
electrically the redox centres of the enzymes
by introducing electron relays close to the
enzyme active site. A sol gel based ampero-
metric biosensor incorporates an osmium re-
dox polymer as mediator for detection of
lactate [272].
Ruthenium phthalocyanine complex com-
pounds have proven effective as drugs for pho-
todynamic cancer therapy. It is administered
intraperitoneally, followed by laser irradiation
of the tumor tissue. The compound acts in the
presence of light as sensitizer to induce the
photochemical destruction of the unwanted
tissue [273].
Ruthenium complexes with polyaminocar-
boxylate ligands act as effective nitric oxide
scavengers. The binding property for nitric oxide
enables macrophage cells to kill tumor cells and
may also form the base for drugs against other
nitric oxide inuenced diseases including hyper-
tension, epilepsy, diabetes, arthritis, and septic
shock [274].
Giant, dendritic organic coordination com-
plexes of ruthenium and osmium (dendrimers,
[276279]) with up to 22 ruthenium atoms have
been synthesized, which may be used for the
production of thin lms.
354 Platinum Group Metals and Compounds Vol. 28
Ruthenium forms catalytic active complex
compounds with C
60
molecules [280282].
8. Alloys [28], [3032], [8891], [166],
[167], [172184]
8.1. Alloy Systems
All the platinum group metals are innitely
miscible with one another in the liquid state.
When the molten alloys solidify, or when a
mixture of the powdered metals is sintered, plat-
inum, iridium, palladium, and rhodium, which
crystallize in the face-centered cubic system,
form mixed crystals with each other. At lower
temperature, miscibility gaps are observed in
many cases.
Vol. 28 Platinum Group Metals and Compounds 355
Some phase diagrams of the binary alloys of
platinum according to Massalski [90] are shown
in Figures 1933; of industrial importance are
mainly the binary alloys Pt Rh, Pt Ir, Pt
Pd, Pt Au, but Pt alloyed with base metals (Ni,
Co, W) and a fewternary or higher alloys are also
used.
8.2. Special Alloys
Platinum and palladium are the most important
base components of industrially utilized PGM
alloys. Special properties of interest concern
corrosion resistance, mechanical strength, high
temperature resistance, electrical conductivity,
thermoelectric power, and magnetic behavior.
Platinum palladium alloys are used in
jewelry, for electrical contacts, and for equip-
ment parts for glass production and construction
elements in highly corrosive environments.
Platinum and palladium alloys with W, Re,
Ni and other metals of Groups 6 and 8 10 are
suited for use in high-temperature strain gauges
[283]. Pt alloys are used in spark plugs for
automotive engines.
Dispersion-strengthened platinum and plat-
inumalloys are produced by coprecipitation of the
metals and refractory oxides, for instance, with
ZrO
2
(zirconium oxide grain-stabilized platinum,
Figure 19. Phase diagram of binary platinum group metal
alloys: Ag Pt
Figure 20. Phase diagram of binary platinum group metal
alloys: Au Pt
Figure 21. Phase diagram of binary platinum group metal
alloys: Fe Pt
Figure 22. Phase diagram of binary platinum group metal
alloys: Co Pt
356 Platinum Group Metals and Compounds Vol. 28
Figure 23. Phase diagram of binary platinum group metal
alloys: Pt Rh
Figure 24. Phase diagram of binary platinum group metal
alloys: Ag Pd
Figure 25. Phase diagram of binary platinum group metal
alloys: Au Pd
Figure 26. Phase diagram of binary platinum group metal
alloys: Fe Pd
Figure 27. Phase diagram of binary platinum group metal
alloys: Ni Pd
Figure 28. Phase diagram of binary platinum group metal
alloys: Cu Pd
Vol. 28 Platinum Group Metals and Compounds 357
ZGS, Johnson Matthey). Dispersion-strengthened
platinum alloys with Zr and additional Y are
superior in temperature stability and have higher
recrystallization temperatures [285].
Platinum can also be effectively dispersion
hardened by incorporating very small amounts
(0.04 0.08 wt %) of refractory carbides (TiC,
ZrC). The strengthening is due to a partial de-
composition and reaction of the carbide with the
matrix. The low carbide concentration offers the
advantage that ductility, electrical conductivity,
and the recrystallization behavior are not seri-
ously impaired.
Platinum gold and platinum gold
rhodium alloys have higher strength than pure
Figure 29. Phase diagram of binary platinum group metal
alloys: Pd H
Figure 30. Phase diagram of binary platinum group metal
alloys: Ag Rh
Figure 31. Phase diagram of binary platinum group metal
alloys: Fe Rh
Figure 33. Phase diagram of binary platinum group metal
alloys: Ir Pt
Figure 32. Phase diagram of binary platinum group metal
alloys: Ir Rh
358 Platinum Group Metals and Compounds Vol. 28
platinum at 1000

C, ner grain structure, and
better resistance to wetting by molten glass.
Platinum iridium alloys nd different ap-
plications in electrochemistry, chemical technol-
ogy, medicine, and jewelry. Iridium contents (in
wt %) are for laboratory ware 0.4 0.6 %, jew-
elry 5 15 %, medical applications 10 %, elec-
trical contacts 10 25 %, electrodes 10 %, pens,
needles, springs 25 30 %. Maximum hardness
(ca. 360 HB) is reached with 30 % iridium.
W Th Al-doped platinum 26 wt %
iridium and platinum 30 wt % rhodium are
used to encapsulate plutonia fuel pellets for
spacecraft heat sources [290].
Platinum rhodium alloys with 10 % rho-
dium are used as catalyst for the oxidation of
NH
3
, as the standard element in thermocouples
(Pt Rh of different compositions or Pt), and as
heater elements in electrically heated high-tem-
perature furnace. Pt Rh alloys with additions of
Au are especially resistant to wetting by molten
glass. They are used in machine parts for the
production of high-tech glasses for computer
monitors, cathode ray tubes, television screens,
liquid crystal displays, and plasma panels; glass
bers for telecommunication; and for use in
glass-reinforced construction materials.
Platinum ruthenium alloys. Ruthenium
strengthens platinum very effectively; 10 % ru-
thenium increases the hardness to 168 HV. The
alloy PtRu5 has the same strength, hardness, and
corrosion resistance as the alloy PtIr10 (hard
platinum). Applications are jewelry items, elec-
trodes for electrochemistry, spark plug electro-
des, electrical contacts, and wear-resistant wires
in potentiometers. Higher alloy compositions up
to 14 % ruthenium and ternary types with 15 %
rhodium and 6 % ruthenium are used for electri-
cal contacts and potentiometer wires for heavy-
duty applications.
Platinum cobalt multilayers on various
substrates are used for ultrahigh-capacity hard
disks, for magneto-optical storage, and perpen-
dicular recording applications. Special proces-
sing enhances domain wall pinning effects and
leads to higher coercivity [286]. Pt Fe alloys
have maximumcoercivity at 39.5 wt %platinum
[287].
A new class of magnetic behavior, random
quantum spin chain paramagnetism, is exhibited
in one-dimensional compound Sr
3
CuPt
1x
Ir
x
O
6
prepared as solid solution of the antiferromag-
netic Sr
3
CuPtO
6
and the ferromagnetic
Sr
3
CuIrO
6
. The platinum: iridium ratio deter-
mines the magnetic behavior of the solid solution
[288]. Alloys of the type Cr
1x
Ir
x
O
2
(0 < x
< 0.3) are ferromagnetic materials with high
coercivity [289].
Platinum nickel alloys have been proven
in electrical switches and as high-strength and
highly temperature resistant construction mate-
rials in the chemical industry. Compositions
range from trace amounts up to 20 % nickel with
maximum tensile strength of about 1725 MPa
after 90 % cold reduction.
Platinum tungsten alloys, commonly used
in compositions with 5 8 wt % Co, have ex-
cellent wear resistance. They are used for poten-
tiometers, glow wires in copiers, diode switches,
heater elements and cladding on rods for fuel
elements in nuclear reactors.
Platinum electrodes are hardened with iridi-
um for use in spark plugs and as corrosion
resistant electrodes.
In equiatomic Ti Ni alloys, (known for the
shape-memory effect), substitution of nickel by
2 atom% ruthenium stabilizes the high temper-
ature B2-type phase at room temperature [292].
Partial replacement of Ni by palladium in the
equiatomic TiNi alloy improves the shape mem-
ory properties [293].
Platinum alloys are components in catheters
for pacemakers, in dental gold alloys, in marker
bands, in guidewires and in temporary and per-
manent implants.
Palladium gold alloys are the basis of pre-
cision resistance alloys. Addition of iron accent-
uates the formation of long range ordering. The
alloy Au50Pd45Mo5 has a resistivity of
100 mWcm and a temperature coefcient of re-
sistance (TCR) of 0.00012 K
1
between 0 and
100

C.
The tensile strength reaches values of about
1060 N/mm
2
.
Palladium silver alloys are used as capac-
itor electrode layers, as silver conductor paths,
and as resistor elements in thick-lm circuits.
The palladium silver alloy with 40 atom%Ag
has the highest electrical resistivity at room
temperature. It nds use for precision resistors
in electrical technology. The resistivity between
20 and 100

C is nearly constant and amounts to
42.5 mW cm; between 20

C and 800

C the
resistivity changes from 42.5 to 44 mW cm.
Vol. 28 Platinum Group Metals and Compounds 359
Ternary alloys containing silver and copper
with up to 10 to 25 % palladium are hard solders
for high-strength.
Palladium ruthenium with 4.5 wt % ru-
theniumis a standard jewelry alloy in the United
States. Alloys with ruthenium contents up to
12 % serve as material for electrical contacts
and as catalysts for the reduction of nitric oxide.
Palladium alloys with 60 80 wt % Pd for
use in dentistry contain copper and gallium as
hardening elements and tin to lower the melting
temperature. Best corrosion resistance is attained
with a single-phase structure in the composition
range of Cu 4 6 wt %, Ga 5 7 wt %, and Sn
6 wt %. Addition of 1 wt %palladiumto silver
tin copper amalgam alloys improves hetero-
geneous phase formation and the thermal stabil-
ity [294].
Palladium alloys with iron and with cobalt
show ferromagnetism.
By alloying palladium with 0.1 wt % cobalt,
the palladium atoms surrounding a cobalt atom,
are strongly magnetized to magnetic moments in
the order of 10 mB, which is about six times
larger than that of a single cobalt atom.
Palladium and certain palladium alloys are
unique in their capability to dissolve large
amounts of hydrogen up to about 2800 times
their own volume [295297]. Hydrogen enters
palladium interstitially. The hydrogen atoms are
located in the octahedral holes of the fcc lattice.
Above 295

C, palladium and hydrogen form a
continuous serious of solid solutions with fcc
structure. Below that temperature, the phase
splits into a fcc palladium-rich phase and an fcc
hydrogen-rich phase, and the result is a miscibil-
ity gap which broadens with decreasing temper-
ature. The occupation of interstitial sites by
hydrogen atoms causes expansion of the palladi-
um lattice. The lattice parameters increase with
increasing hydrogen content from 3.891 A

for
pure palladium up to 4.06 A

at 75 atom% hy-
drogen [298]. Thermal cycling of Pd H alloys
in the duplex phase region causes high mechani-
cal stresses due to changes of the lattice dimen-
sions with changing amounts of dissolved hydro-
gen. Pure palladium, when repeatedly heated and
cooled in hydrogen-containing atmosphere, be-
comes brittle and cracks.
Palladium silver alloys with 20 25 wt %
silver dissolve larger amounts of hydrogen than
pure palladium and are resistant to thermal cy-
cling [299]. Pd Ag23 exhibits extremely high
hydrogen permeability and is used for semiper-
meable membranes for the extraction and puri-
cation of hydrogen up to 99.99999 % purity.
Palladium silver permeation membranes are
provided in the form of bundled tubes with
wall thickness of ca. 75 mm, sealed at one
end. Hydrogen is pressed from outside through
the tubes, dissociating and diffusing through
the alloy to the inner side of the tubes, leaving
most impurities outside the membrane [300],
[301].
The solubilities of the hydrogen isotopes in
palladium and palladium silver alloys differ
to an appreciable degree. Diffusion membranes
of palladium or palladium silver alloys can
therefore be used for separation and concentra-
tion processes of different hydrogen isotopes
[302]. The equilibrium hydrogen/deuterium
separation factors vary from ca. 2.4 at 25

C to
3.7 at 80

C [303]. For the hydrogen/tritium
ratio, a value of 2.8 was measured at 25

C
[304].
The ternary alloy Pd Ti Al is ferromag-
netic, in contrast to the antiferromagnetic alloy
Pd Ti [25].
Pt and Pt alloys are electrocatalysts in low-
temperature fuel cells. The phosphoric acid fuel
cell (PAFC) contains a Pt Co Cr alloy on
the cathode side and straight platinum on carbon
as the anode. The higher activity of alloys
compared to pure platinum on the cathode side
is due to the fact that the non-noble metal
components are leached from the alloy crystal-
lite surfaces, leaving a highly reticulated and
active surface [306], [307]. The catalytic activi-
ty is effected by the preparation method and the
crystal structure of the three-component alloy
[308]. The proton exchange membrane fuel cell
(PEMFC) contains a platinum ruthenium-
loaded graphite anode and pure-platinum-load-
ed graphite cathode [309]. The ruthenium alloy
protects the catalyst against poisoning by the
carbon monoxide which may be present in the
hydrogen supply. Platinum ruthenium alloys
are also used as the anode catalyst in the direct
methanol fuel cell (DMFC [310]). They prevent
the formation of linearly bonded carbon mon-
oxide (PtC=O) during the electrosorption of
methanol on the platinum.
360 Platinum Group Metals and Compounds Vol. 28
Iridiumalloys are used in microelectrodes for
testing water quality by square-wave anodic
stripping voltammetry [311].
Alloying of titanium and high-strength titani-
um alloys (e.g., Ti 6Al 4V) with 0.1 % ru-
thenium effects improvements in the corrosion
resistance against hydrochloric acid solutions
and can supersede corresponding Ti-Pd alloys.
Selective dissolution generates on the surface
cathodic sites of low hydrogen overvoltage. This
accelerates hydrogen ion reduction and thus
causes a substantial shift in the corrosion poten-
tial towards higher nobity, where the protective
surface oxide lm is stable. Applications are
apparatus parts for processing corrosive chemi-
cals [291].
Platinum metals based intermetallics in al-
loyed or composite microstructures show inter-
esting properties in high temperature strength
and oxidation resistance as needed for materials
in high temperature service. Prototypes are Ir
IrN-composites with refractory metals. Pt Al
Ru-alloys, ferritic alloys with Ru, and eutectic
Ru RuAl and Ir IrAl alloys [312].
8.3. Methods of Treatment [88], [107],
[166], [167]
The starting material for the manufacture of
PGM alloys from platinum and palladium is
generally metal sponge. The remaining ele-
ments rhodium, iridium, ruthenium, and osmi-
um are supplied as powders. Platinum and pal-
ladium are also available in ingot form.
Owing to their high melting points, the plati-
numgroup metals are almost invariably melted in
an induction furnace, either under vacuum or
with argon as a protective gas. The vigorous
mixing action produced by inductive heating is
an additional advantage in producing alloys.
Crucible materials can be aluminum oxide; zir-
conium oxide; or magnesium oxide. Pure cal-
cined calcium oxide was also used in the past.
The molten metal is poured into water-cooled
copper molds. The refractory platinum group
metals, rutheniumand osmium, are seldomneed-
ed as pure, solid metals, but may be compacted by
sintering. Electric-arc melting and electron-
beam melting are sometimes used. Electron-
beampurication has recently become an impor-
tant method of treating iridium. This melting
process causes selective evaporation of trace
elements and impurities at ca. 2700

C.
Platinum, palladium, and most of their alloys
can be mechanically shaped by forging, rolling,
drawing, and by deep drawing, etc., at room
temperature, with intermittent heating. Form-
ability decreases with increasing proportions of
the other platinum group metals in the ascending
series palladium, rhodium, iridium, ruthenium,
and osmium. Special techniques are used for
weaving and knitting Pt Rh catalyst gauzes
and for drilling extremely small holes in the
platinum alloy spinneret nozzles used in the
production of bers.
Platinum and the other metals can also be
processed by powder metallurgy. The process of
inert gas spraying is used to produce powders.
Particle sizes are around 50 mm.
Platinumand palladiumcan be fusion welded
without special precautions by TIG, plasma,
and laser welding. Platinum metal can also be
diffusion welded by hammering at red heat. A
protective gas must be used with rhodium and
iridium.
9. Quality Specications and Analysis
[5], [36], [185198]
9.1. Quality Specications [185], [200],
[201]
In industry, the purity and neness of platinum
and platinum metals are even today often de-
scribed by the classications technically pure
(99 %), chemically pure (99.9 %), physically
pure (99.99 %), and spectroscopically pure
(99.999 %). These are taken fromthe recommen-
dations of the Physikalisch-Technische Reich-
sanstalt [29].
Present practice is to use the following
qualities:
99 % (now hardly used)
99.9 %
99.95 %
99.98 %
99.99 %
99.999 %
99.9999 % (only in exceptional cases)
Vol. 28 Platinum Group Metals and Compounds 361
Other specications are used for particular
applications (e.g., physical properties if used in
sensors or microelectronics [202], [203]).
Apart from osmium ASTM standard speci-
cations are available for the chemical composi-
tion of some grades of the other rened PGMs
(Table 6).
Most commercially available platinum and
palladium have purities of 99.95 99.98 %.
Higher purities usually sell at higher prices. Plati-
num and palladium are generally supplied as
ingots or bares (stamped with the purity). Other
platinum metals are supplied mainly as powder.
Platinum and palladium ingots of 500
1000 g are preferred for investment purposes in
Japan [1].
9.2. Qualitative Analysis
The older wet chemical qualitative reactions
have not entirely lost their usefulness.
Platinumcan be identied by the precipitation
of Pt
IV
as yellow crystalline K
2
[PtCl
6
] or
(NH
4
)
2
[PtCl
6
] from dilute hydrochloric acid so-
lution by the addition of a KCl or NH
4
Cl solution.
Other quadrivalent platinumgroup ions interfere.
Analogous to Cassius gold purple, platinum
forms platinum purple in weakly acid solutions
by reduction with SnCl
2
, Zn, or Al. The detection
limit is ca. 1 mg/L, but Pd, Rh and Au can
interfere.
The chemical detection of palladium uses
precipitation of Pd
II
as the yellow, ammonia-
soluble dimethyldioxime complex. In contrast
to the corresponding Pt
II
compound, the Pd com-
plex precipitates at low temperatures.
There is no simple specic detection reac-
tion for the mainly trivalent rhodium. If other
colored ions are absent, it can be recognized
by its raspberry pink color in solutions of
rhodium(III) chloride or hexachlororhodate
(III) complexes. If KOH is added to a Rh
III
chloride solution, no precipitation occurs at
rst; the brown hydroxide precipitates only
when ethanol is added. This distinguishes
between Rh and other PGMs.
Iridium can be detected by heating a solution
in concentrated sulfuric acid to fuming and, after
cooling, adding ammonium nitrate. Renewed
warming of the solution produces an intense blue
color by formation of anionic complexes of Ir
IV
.
Chemically, even microgram quantities of ruthe-
nium can be detected in hydrochloric acid solu-
tion by the formation of a blue complex of Ru
III
with thiourea.
Osmium interferes with Ru detection with
thiourea by formation of a red complex of Os
III
,
which can be used for identication of Os. It can
be separated from Ru by distillation from nitric
acid solution. The stinging odor of (the toxic)
osmium tetroxide is also characteristic.
In the PGM industry spectrochemical meth-
ods are used almost exclusively for qualitative
analysis. The detection sensitivity for platinumin
solutions by using the 265.85 nmemission line is
only slightly higher with inductively coupled
plasma optical emission spectroscopy (ICP-
OES) than with ame atomic absorption spec-
troscopy (FAAS). X-ray uorescence (XRF) of-
fers quick detection or identication facilities for
PGMs in metallic or nonmetallic materials. The
244.8 nm, 340.46 nm, and 363.47 nm lines are
used amongst others for the spectro-analytical
detection of palladium by classical spectrogra-
phy, FAAS, or ICP-OES. The surest way of
detecting rhodiumspectroanalytically is by using
the 343.49 nm line with the above-mentioned
methods. Frequently used lines of Ir are at
212.68 nm, at 215.27 nm, and at 224.27 nm. For
Ir, the detection limit of ICP-OESis two orders of
magnitude better than with FAAS. The spectro-
analytical detection or identication of Ru by
means of FAAS or ICP-OES offers no problems,
as a series of lines, e.g., at 240.27 nm or
349.89 nm, are available. Among all PGMs, Os
has the lowest detection limit when ICP is used.
9.3. Quantitative Analysis [313]
The methods of analysis used for economic
control reasons when buying and selling crude
products, alloys, compounds, etc., must reect
the high value of PGMs.
Table 6. ASTM standard specications for platinum group metals
Metal Standard Grades
Pt B 561 - 94 99.95, 99.99
Pd B 589 - 94 99.95
Rh B 616 - 96 99.80, 99.90, 99.95
Ir B 671 - 81 (Reappr. 1993) 99.80, 99.90
Ru B 717 - 96 99.80, 99.90
362 Platinum Group Metals and Compounds Vol. 28
Chemical Assay Methods. For commonly
occurring combinations of elements, mandatory
methods of analysis and sampling have been
developed. The classical methods of separation
and gravimetrical determination outlined briey
below are today of minor importance. PGMs
present in concentrations from mg/g to a few
percent are often subjected to preliminary con-
centration by re assay with lead (see Gold,
Gold Alloys, and Gold Compounds, Section
9.3.), nickel sulde, or copper as collector prior
to the determination.
Platinum Base Metal Alloys. Platinum is
precipitated as (NH
4
)
2
[PtCl
6
] from a nitrate-free
solution of H
2
[PtCl
6
] by addition of NH
4
Cl, the
precipitate is heated strongly, which converts it to
platinum, and then weighed [314]. Another pos-
sibility to determine platinum gravimetrically is
the reduction with mercury(I) chloride [315]. For
Pt on a-Al
2
O
3
catalysts used in the petroleum
industry, the possible method of determining
platinum is by the coloration produced with tin
(II) chloride, which is determined photometrical-
ly after extraction with ethyl acetate or after
preliminary separation of platinum by reduction
with formic acid.
Platinum Rhodium Alloys. A nely divid-
ed black metal is obtained by fusion with zinc
followed by treatment with hydrochloric acid.
Platinum is dissolved in aqua regia,
(NH
4
)
2
[PtCl
4
] is precipitated and heated strongly
to yield platinum. The remaining noble metal is
reductively precipitated from the mother liquor,
combined with the residue remaining after aqua
regia treatment, and treated with chlorine at
650 700

C. The RhCl
3
obtained, which is
insoluble in aqua regia, is heated strongly in a
hydrogen atmosphere to produce the metal,
which is weighed.
Platinum Palladium Alloys. Palladium is
quantitatively precipitated with dimethylglyox-
ime from a dilute solution in aqua regia. It is
ltered off, washed thoroughly, calcined, re-
duced to the metal by hydrogen, and weighed.
The dimethylglyoxime in solution is decom-
posed by aqua regia, and platinum is converted
to (NH
4
)
2
[PtCl
6
], precipitated as sulde, isolated
as the metal by reduction with hydrogen, and
weighed.
Platinum IridiumAlloys. Platinum irid-
ium alloys are converted into a nely divided
state by fusion with zinc, and removing the zinc
with HCl, and the platinumis dissolved with aqua
regia. Iridium remains undissolved and, after
reduction with hydrogen, is weighed.
The classical dissolution for alloys like Pt Ir
and Pt Rh beginning with a fusion with zinc
can be replaced advantageously by dissolving the
alloys in a mixture of HCl and HNO
3
under
pressure in a sealed glass tube which is heated
in a drying furnace, or by dissolution in a PFA or
quartz vessel by using a microwave furnace.
The PGMcontent of commercial compounds
and preparations is usually determined gravi-
metrically by reduction in solution with hydra-
zine or by reduction of the solid sample with
hydrogen. Reductive precipitation from solu-
tion in strong hydrochloric acid by treatment
with zinc turnings is an exact method if carefully
carried out.
Physical Methods. Physical methods, espe-
cially spectroscopic ones, are increasingly being
used, because they are inexpensive and, with
improvements in the equipment, have sufcient
accuracy for economic purposes. If brought into
solution by suitable acid treatment and/or fusion,
such as Na
2
O
2
fusion, and after separation from
interfering base metals, the PGMs can be deter-
mined simultaneously by X-ray uorescence, or
ICP-OES. Application of the principle of internal
standardization ( Gold, Gold Alloys, and Gold
Compounds, Chap. 9.) is mandatory for precise
work. The measurement procedures outlined in
[316] for Pt and in [317] for Pd can be applied also
tothe ICP-OESof Rh, Ir, and Ru. The difcult and
time-consumingseparationof the PGMs fromone
another is no longer necessary. Therefore, analy-
sis of complex materials containing precious
metals, such as PGM ore concentrates containing
gold, offers no problems. XRF can also be used
for direct anlysis of metallic materials with suf-
cient accuracy for production control in the
manufacturing of dened alloys. Calibration of
this method may however be difcult.
9.4. Purity Analysis
The precious metal content of commercial grades
of PGMs can be determined more precisely by
Vol. 28 Platinum Group Metals and Compounds 363
measuring the total content of impurities by physi-
cal methods than by direct determination of the
main constituent. The most important of these
methods are emission spectroscopy, e.g., with
spark or glow discharge excitation. Recently, DC
arc spectrometry became important again, because
the application of a solid-state detector [318] en-
ables simultaneous background corrections. Spark
ablation ICP-OES offers an alternative method.
When PGMs have been brought into solution (if
necessary by dissolution in a mixture of HCl and
HNO
3
under pressure by conventional heating in a
sealedglass tube or byusinga microwave furnace),
the metallic impurities can be determined simulta-
neously with a ICP-OE spectrometer with a solid-
state detector [charge injection device (CID) or
segmented-array charge-coupled device (SCD)].
Another solution technique of interest here is ICP-
MS. Atomic absorption spectroscopy is of minor
importance. Mass spectrometry with glow dis-
charge ablation (GD-MS) is used in special cases,
e.g., for 99.995 % or purer metals.
9.5. Trace Analysis
The determination of traces of precious metals is
of great importance in mineral prospecting. Here
metal contents of only a few mg/g are of interest.
Methods such as graphite tube AAS, neutron
activation analysis, total reection X-ray uores-
cence analysis, and ICP mass spectrometry (ICP-
MS) are used after appropriate enrichment pro-
cedures (e.g., by re assay with nickel sulde as
collector).
The analysis of traces of precious metals in
waste materials from the precious metal proces-
sing industry, especially reneries, has always
been very important in monitoring the economics
of the process.
Trace analysis of platinum, palladium, and
rhodium has become important in recent years.
Whereas boththe occurrence andthe use of PGMs
have hitherto been located, automobile exhaust-
gas catalysts now constitutes a widespread use.
Although no toxic effects on the environment
have thus beenreported, methods of analysis must
be continually improved as permitted levels in the
soil and the atmosphere become increasingly
strict. The collection of the PGMs in a nickel
sulde phase by re assay followed by GFAAS or
ICP-MS is suitable for analysis in the ng/g range.
10. Uses [3], [5], [30], [31], [204], [167]
10.1. Jewelry, Coinage, Investment
[166]
In recent decades, platinum has been in such
demand for jewelry and high-quality watchmak-
ing that more than one-third of all the platinum
consumed has been used for this purpose. Of this
amount, Japan uses about 90 %, with the United
States taking the next largest share. Most of the
alloys employed contain 95 % platinum and are
stamped PLAT 950. The mechanically more
stable alloys Pt 95 Cu 5 (Pt96/Cu 4), the hard-
er alloys PtW 95/5, Pt 96 Pd 4, and Pt 90
Ir 10 are used for mounting precious stones. Pt/
Co is used for jewelry casting. A relatively new
alloy has a Pt content 99.9 %; the hardness for
jewelry is obtained with a small amount of sili-
con. Forming costs for platinumare considerably
higher than those for gold because the metal is
more difcult to work, and recycling costs are
high. These factors markedly affect total cost.
Very good resistance to corrosion and erosion
is required of alloys used for the nib tips of high-
quality fountain pens [166]. These alloys are
based on ruthenium, iridium, and osmium.
In the Russian Empire in 1828 1845, a total
of 15 t of platinumwas formed into 3-, 6-, and 12-
rouble pieces by sintering, minted, and brought
into circulation.
The neness was 99%platinumor 99.2%PGM
[15]. Between 1977 and 1980, platinumcoins were
again minted for the Moscow Olympic Games.
These were 150-rouble pieces, neness: 9999,
1
/
2
ounce, in ve designs. Since then, platinum coins
have been ofcially minted in other states (e.g., a
Platinum Noble in the UK, a Platinum Maple Leaf
in Canada, and a PlatinumKoala in Australia). The
standard issue of all these coins contained one troy
ounce (31.1035 g) of ne platinum. Small ingots,
usually containing 99.995% platinum, are also
minted, intended mainly for small investors. The
use of palladium for this purpose has recently
begun on a small scale.
10.2. Apparatus [205208]
Laboratory Technology. Platinum cruci-
bles, dishes, boats, and electrodes (for electrogra-
vimetry) have long been basic items of equipment
364 Platinum Group Metals and Compounds Vol. 28
in chemical laboratories. Inearlier times, the purity
of platinum was variable. Moreover, equipment
made of pure platinumis not dimensionally stable,
so today the more stable alloys Pt 97 Ir 3, Pt 95
Au 5, and occasionally Pt 99.7 Ir 0.3, are
mainly used [209].
Another type of dimensionally stable plati-
num is dispersion-hardened platinum, which
contains 0.1 to 0.2 wt % of high-melting oxide
(e.g., ZrO
2
, Y
2
O
3
) in nely divided form [88].
The presence of this material reduces the mobili-
ty of crystal imperfections. It is produced by
precipitation, internal oxidation, or mechanical
mixing followed by sintering of the powder. The
metal can be unalloyed platinum, or alloys of
platinum with rhodium or gold. Rhodium and
iridium crucibles can resist extremely aggressive
conditions in nonoxidizing atmospheres.
Chemical and Electrochemical Appara-
tus [210], [319]. The platinum metals and their
compounds are of limited use in chemical pro-
cess technology owing to their high cost. How-
ever, platinum components are essential in uo-
rine chemistry. Bursting disks for protection
against excessive pressure are occasionally made
of platinum or palladium. Single crystals for the
optical industry and for laser technology are
grown in crucibles of platinum, rhodium, or
(most commonly) iridium [210]. For the electro-
chemical production of peroxo compounds, such
as hydrogen peroxide and peroxosulfate, massive
platinum anodes or hollow platinum wires are
used, although such use has decreased [319].
Glass Technology [210213]. The corro-
sion and erosion resistance of platinum metals
toward molten glass is not matched by any other
material [88]. High-purity optical glass is best
melted in crucibles of unalloyed platinum. Spe-
cial iron-free glass for sodium vapor lamps, X-
ray windows, and cathode-ray tubes is melted in
Pt Rh vessels.
In the automated production of bottles by
large holding furnaces, the use of platinum com-
ponents ensures problem-free operation over
long periods. These components include com-
plete feeder systems, stirrers, plungers, skim-
mers, pouring funnels, thermocouple protection
tubes, and level-measuring devices. Nowadays
dispersion-hardened platinum in increasing
quantities is used in glassmaking technology.
In the manufacture of glass bers and glass
wool, the spinnerets are made of Pt Rh. Rock
wool and slag wool are made by a centrifugal
spinning process with platinum centrifuges.
Textile Technology. Nozzles made of plat-
inum alloys such as Au 70 Pt 30 and Pt 92
Ir 8 are used for spinning viscose bers [214].
Soldering Materials. Gold and palladium
have been used in some special solders.
10.3. Heterogeneous Catalysts [92],
[215220]
All platinum group metals have strong catalytic
activity, especially for hydrogenation reactions.
The catalytic properties of the platinum metals
group elements can be regarded in relation to
those of the elements of group 8 10 of the rst
row of the periodic system. A clear correspon-
dence to the differences in their catalytic behav-
ior has been found in their behavior in coordi-
nation formation, in complex formation, and in
chemisorption behavior. The bond dissociation
energies of the related compounds, complexes,
and adsorbed atoms or molecules are weaker for
the elements of the rst two rows than for those
of the third row. Insofar, closer relation exists
between the catalytic characteristics of the ele-
ments Fe, Co, Ni and Ru, Rh, Pd compared with
the elements of the third row. This special
energetic situation allows easier intermolecular
exchange of p- and ps electrons, which takes
place in numerous heterocyclic and homoge-
neous catalytic reaction. Examples are the reac-
tion of carbon monoxide with hydrogen, hydro-
formylation, reactions with methanol, and the
catalysis of reactions with unsaturated hydro-
carbons. The heterogeneous catalysts, including
supported catalysts, are of major importance in
chemical technology. As of 1998, 220 240 t
of platinum group metals are in use worldwide
in the form of supported catalysts. Next in order
of importance are bulk metallic catalysts in the
form of wire gauzes, highly dispersed carrier-
free metals, and oxides. Platinumand palladium
are technically much more important than rho-
dium, ruthenium, iridium, and osmium. Often,
two or more platinum group metals are com-
bined (Table 7).
Vol. 28 Platinum Group Metals and Compounds 365
Supported Catalysts. The properties of
supported catalysts are very dependent on the
interaction between noble-metal catalysts and
support material. Classical support materials
were asbestos and pumice stone. Important sup-
port materials today include aluminum oxides,
activated carbon, silicates (e.g., zeolites), and
silica, also in combinations and as washcoats.
Powdered support materials are used as suspen-
sion catalysts; porous pressed shapes, pellets, and
monolithic structures in newer applications are
used as xed-bed catalysts. Reactions catalyzed
by platinum group metals are listed in Table 8
[319].
The largest demand for platinum catalysts
comes from the petroleum industry [221],
[222]. These are used in reforming high-boil-
ing fractions from the distillation of crude oil
at atmospheric pressure. The most important
reactions are the dehydrogenation of alkylcy-
clohexanes, the isomerization and dehydroge-
nation of alkylcyclopentanes, and the dehydro-
genation and cyclization of alkanes, all of
which form aromatics, as well as hydrogena-
tive cleavage of alkanes and naphthenes, and
dealkylation of alkylaromatics. The resulting
product mixtures are gasolines with high oc-
tane numbers. The most important catalysts
are Pt g-Al
2
O
3
Pt, Re/g-Al
2
O
3
, and Pt, Sn/
g-Al
2
O
3
. Other catalysts such as Pt, Ir/
g-Al
2
O
3
, Pt, Pd/g-Al
2
O
3
or Pt, Ge/g-Al
2
O
3
may also be used.
Another use for PGM catalysts in the petro-
leum industry is in hydrotreating processes. In
addition to base-metal catalysts, platinum and
palladium catalysts supported on g-Al
2
O
3
or
aluminum silicates (zeolites) are also common.
Supported palladium catalysts are used in hydro-
gen peroxide production.
In the pharmaceutical industry, palladium/
active carbon hydrogenation catalysts are widely
used, mainly with a palladium content of 5 %.
Other catalysts used include rhodium/activated
carbon, platinum/activated carbon, palladium
platinum/activated carbon, and iridium/activated
carbon, sometimes promoted by other elements,
e.g., vanadium, iron, or bismuth. Lindlar cata-
lysts (Pd, Pd/CaCO
3
) play an important role
in pharmaceutical industry. Platinum on electri-
cally conducting carbon black is used as catalyst
in fuel cells. Furthermore precious metal formu-
lations are used for exhaust gas catalysts, e.g., to
control automotive emissions ( Automobile
Exhaust Control).
Solid Metal Catalysts [223226]. Plati-
num rhodium gauzes are used as catalysts for
the large-scale oxidation of ammonia to nitric
oxide (Ostwald and Brauer process) in the man-
ufacture of nitric acid ( Nitric Acid, Nitrous
Acid, and Nitrogen Oxides).
The oxidation reaction
takes place in reactors in which many ne-
mesh gauzes are stacked above one another.
The rate of loss of noble metal varies between
0.2 and 2.0 g per tonne of nitrogen reacted,
depending on process conditions. If a rhodi-
um platinum alloy is used, the rate of loss of
Table 7. Modication of the catalytic activity of the platinum group metals by additional metals
Base metal Additional metal Reaction Effect of additive
Pt 5 20 % Rh ammonia oxidation increased NO yield
lower Pt losses
Pt Ge, Sn, In, Ga dehydrogenation and hydrocracking of alkanes longer catalyst life due to fewer deposits
Pt Sn Re dehydrocyclization and aromatization of alkanes increased catalyst activity and stability
Pt Pb, Cu dehydrocyclization and aromatization of alkanes effective aromatization
Pt, Pd, Ir Au oxidative dehydrogenation of alkanes, n-butene
to butadiene, methanol to formaldehyde
better selectivity
Pd Sn, Pb selective hydrogenation of alkynes to alkenes
Pd Ni, Rh, Ag alkane deyhdrogenation and dehydrocyclization hinders coking
Pd Au, Cd ethylene and acetic acid to vinyl acetate
366 Platinum Group Metals and Compounds Vol. 28
noble metal is reduced; powdering of the
gauze takes place more slowly, and its lifetime
is increased.
In the production of hydrogen cyanide
(Andrussow process),
CH
4
NH
3
3=2 O
2
HCN3 H
2
O
platinum rhodium or platinum iridium
gauzes are used as catalysts ( Cyano Com-
pounds, Inorganic, Section 1.2.1.).
Table 8. Catalysis by platinum group metals
Noble metal catalyst
Reaction Powder Compound Support
a) Oxidation and other reactions on noble metal catalysts
Methanol formaldehyde Ag - -
Ethylene ethylene oxide - - Ag/Al
2
O
3
Ethylene acetaldehyde - PdCl
2
in solution -
Amines nitriles Ag - -
Complete oxidation of organic compounds - - Pd/Al
2
O
3
Disuldes to sulfoxides - RuO
4
in CCl
4
-
Alcohols to aldehydes, ketones - RuO
4
in CCl
4
-
Olens, oxidative cleavage - RuO
4
in CCl
4
-
Synthesis or decomposition of organic compounds
CO H
2
to methane - - Ru/Al
2
O
3
to parafn hydrocarbons - RuO
2
Ru K
2
CO
3
Addition of CO and H
2
to
olens to give alcohols - RhO
3
-
olens to give ketones - RhCl
3
-
olens to give esters - Rh oxide -
Addition of silane to olens - - Pt/carbon Al
2
O
3
Cleavage of formic acid Rh, Os Ru oxide Pt/asbestos
Leavage of formaldehyde Ru, Os OsO
4
Pd/BaSO
4
Inorganic catalysis
H
2
O
2
H
2
O 1/2 O
2
Ru, Pd - -
NO hydroxylamine - - Pt/C
PtAu5/C
PtIr1/C
Rh/C
NH
3
NO PtRh10
b) Reduction and isomerization on noble metal catalysis
H
2
addition to
acetylene and homologs Rh, Pd, Pt - Rh, Pd/Al
2
O
3
Ag/Pd70/30/Al
2
O
3
Pd and Pt/BaSO
4
ethylene and homologs - - Ru/C
aromatic hydrocarbons - - Rh/Al
2
O
3
aromatic compounds, hydrogenation of the aromatic ring - RuO
2
Rh/Al
2
O
3
heterocycles, hydrogenation of the aromatic ring - - Rh/Al
2
O
3
Reforming of crude oil
dehydration (cracking) to aromatics Pd/Al
2
O
3
isomerization/Cyclization - - Pt/Al
2
O
3
PtIr/Al
2
O
3
cleavage to alkanes - - Ru/SiO
2
Reduction
of ketones to alcohols - - Ru/C
Pd/C
Pt/C
of carboxylic acids to alcohols - RuO
2
Ru/C
Rh/C
nitrogen compounds to amines - PtO
2
Pd/C
Pt/C
of disuldes to mercaptans - RuO
2
-
of mercaptans to alcohols H
2
S - RuO
2
-
Vol. 28 Platinum Group Metals and Compounds 367
The Degussa process
CH
4
NH
3
HCN3 H
2
works with a-Al
2
O
3
tubes coated on the inside
with a platinum lm, forming a platinum alu-
minum alloy.
Finely Divided Metallic Catalysts. The so-
called platinum metal blacks are well-estab-
lished catalysts for hydrogenation, dehydroge-
nation, and oxidation, mainly on a laboratory
scale. Their high degree of dispersion is shown
by their large specic surface area (> 20 m
2
/g).
These catalysts are very active even at low tem-
perature, so reactions with labile molecules are
possible. In the production of hydrogen peroxide
by the anthraquinone process ( Hydrogen Per-
oxide, Section 4.1.2.2.), palladium black is used
to a considerable extent in suspension in a non-
aqueous medium or as a xed bed to catalyze the
reduction of alkylanthraquinone to the corre-
spondinghydroquinone. The platinumoxide PtO
2
H
2
O (Adams catalyst) is used widely as an
unsupported catalyst in the pharmaceutical indus-
try for the hydrogenation of alkenes and carbonyl
groups. Nishimuras catalyst contains rhodium
oxide in addition to platinum oxide.
Catalyst Poisoning and Regeneration
[227]. All catalysts are liable to be deactivated
(poisoned) by chemical, mechanical, and thermal
means. Typical contact poisons for platinum
group metals include sulfur, phosphorus, carbon
monoxide, hydrogen cyanide, lead, and mercury.
Reactivation is often possible, especially with
supported catalysts, by heating, steam treatment,
reaction with oxidizing or reducing gases, or
washing.
10.4. Fuel Cells
Precious metals are used as anode and cathode
catalysts in low-temperature fuel cells such as the
AFC (Alkaline Fuel Cell), PAFC (Phosphoric
Acid Fuel Cell), PEMFC (Protone Exchange
Membrane Fuel Cell) and DMFC (Direct Meth-
anol Fuel Cell). In the interesting PEMFC, which
has a signicant potential for replacing automo-
bile internal combustion engines, for the cathode
side platinum catalysts supported on carbon
black are used. For the anode side, mainly be-
cause of the required COtolerance when working
with reformed gas platinum/ruthenium catalysts
are preferred. For AFC platinum/gold associated
with nickel is applied. For PAFC quaternary
catalysts with platinum are used; platinum/rho-
dium/iron was reported as cathode catalysts; on
the anode side normally platinum is used. The
DMFC, similar to the PEM, works with platinum/
ruthenium on the anode side, sometimes addi-
tionally containing tungsten, and with platinum
on the cathode side.
10.5. Homogeneous Catalysts [30],
[88], [228230], [322]
Homogeneous catalysis by platinum group me-
tals, especially rhodium, has made a major im-
pact in industrial chemistry. Important charac-
teristics of these catalysts include high activity
and, therefore, low concentration; high selectiv-
ity leading to absence of side products; and mild
reaction conditions, enabling the use of low
temperature and pressure and facilitating the
control of reaction conditions. These factors are
of great importance and allow expensive PGMs
to be used economically. The discovery of chlor-
otris(triphenylphosphine)rhodium(I), [RhCl{P
(C
6
H
5
)
3
}
3
], a highly effective hydrogenation cat-
alyst, byWILKINSON[231] opened a newchapter in
homogeneous catalysis and in the complex chem-
istry of rhodium. Today, a number of modied
complexes of this and similar types are known.
Homogeneous catalysis by rhodium com-
plexes in oxo synthesis (hydroformylation) has
attained great importance and made possible the
synthesis of industrially important aldehydes
from alkenes (see Oxo Synthesis). This pro-
cess was formerly carried out with homogeneous
cobalt catalysts.
By using [RhH(CO){P(C
6
H
5
)
3
}
3
] as the cata-
lyst, reaction temperatures between 60 and
120

C and pressures of less than 50 bar could
be realized, in contrast to the cobalt catalysts, for
which temperatures up to 200

C and pressures
as high as 300 bar are necessary. Often other
compounds are used as precursors from which
the actual catalyst is formed during the reaction.
These include [Rh(CO)
2
(acac)] and [Rh(CO){P
(C
6
H
5
}
3
(acac)] (acac = acetylacetonate).
Another approach to oxo synthesis is to work
in a biphasic system. In this case a watersoluble
368 Platinum Group Metals and Compounds Vol. 28
ligand like P(C
6
H
4
SO
3
Na)
3
and a rhodium salt
(e.g., nitrate, acetate, or sulfate) is used as cata-
lyst precursor [325].
The Monsanto acetic acid process uses Rh
III
iodide as the catalyst precursor. In the cativa
process [323] BP uses Ir acetate as complex
precursor.
The most important application of platinumin
homogeneous catalysis is the vulcanization of
silicon rubber. In addition, the synthesis of se-
lected organofunctional silanes can be realized
by homogeneous precious metal catalysis [326].
A new era in homogeneous catalysis started
with the discovery of asymmetric hydrogenation
to produce enantiomerically pure compounds by
using metal complexes with chiral ligands [225],
[328]. Many other known reactions [322], [324]
are now also performed under asymmetric
conditions like the isomerization of allylamines
[327], [328], allylsubstitution [329] and Heck
reactions [327329]. The products are mainly
intermediates like amino acids, amines, and ster-
oids for production of pharmaceutical and agro-
chemicals. Examples of such ligands are DiAMP
[331], BINAP [332], [333], Deguphos [334],
Josiphos [335], DuPhos [336], [337]; products
include L-Dopa (drug for the treatment of
Parkinsons disease), L-Menthol (aroma), and
Metolachlor (herbizide). The catalysts are
formed in situ by reaction a precursor like [Rh
(cod)
2
]BF
a
or [Rh(cod)acac] (cod = 1,5-cy-
clooctadiene) with the chiral ligand.
10.6. Automotive Emission Control
Catalysts [32], [233236], [338345]
The use of supported noble-metal catalysts for the
treatment of exhaust gases from automobiles has
been introduced beginning in the 1970s, around
the world (see also Automobile Exhaust Con-
trol). Regulations controlling the quality of ex-
haust gases can be complied with only by the use
of such catalysts. In particular, carbon monoxide
(CO), hydrocarbons (CH
x
), and nitrogen oxides
(NO
x
) must be reduced to a small percentage of
their initial concentrations. Metals that have a
catalytic action on exhaust gases include Pt, Pd,
and Rh and all combinations thereof.
Formulations that can reduce all three harmful
components are known as three-way catalysts.
The three-way technique also includes control of
the air fuel ratio by means of a l-sensor (see
Section 10.7). Exhaust control catalysts have
their optimum activity only if the engine and the
catalytic unit are matched. The initially used
pellet catalysts have since been replaced by
monolith-type catalysts. The exhaust gas passes
through numerous parallel channels of extruded
bodies (monoliths) that are coated with a catalyt-
ically active layer, the so-called wash-coat. The
wash-coat consists of the PGM on g-Al
2
O
3
, rare
earth oxides, and other metal oxides. The oxide
mixture is designed to provide high thermal
stability and the ability to compensate uctua-
tions of the air fuel ratio through oxygen storage.
In some applications monoliths made from foils
are also used.
Each catalytic converter contains approxi-
mately 2 g of PGM. The demand for these
materials worldwide amounts to more than
one-third of the annual production of platinum
and more than four-fths of the annual pro-
duction of rhodium. In the early 1990s the use
of Pd has increased signicantly. The PGM
catalysts are the only practicable materials for
this purpose. The required lifetime of an ex-
haust-gas catalyst, as laid down by the widely
accepted U.S. standard, corresponds to 80 000
or 160 000 km.
Tighter standards in the future and the devel-
opment of engines with higher fuel efciency
(lean-burn engines, new diesel engines) have
spurred the further development of these tech-
nologies, e.g., catalysts with the ability to tem-
porarely store hydrocarbons or nitrogen oxides,
electrically heated catalysts, and catalysts that
also reduce soot emissions from diesel engines.
All these catalyst types use PGMs.
Catalysts similar to those used for the treat-
ment of automobile exhaust gases are also used to
treat emissions from thermal power plants and
industrial waste gases contaminated with harm-
ful organic materials.
10.7. Sensors [30], [88], [166], [167]
Thermocouples. Platinum metals and their
alloys are widely used in thermocouples (Table 9),
because these have longer lifetimes than those
made of base metals and can be used at higher
temperature. The most important thermocouple
element pair used in industry is Pt 90/Rh 10 Pt
Vol. 28 Platinum Group Metals and Compounds 369
(wire thickness: ca. 0.5 mm), which gives accurate
temperature measurements over the range 800
1600

C.
Pt-Pt/Rh thermocouples have improved ther-
mal stability and mechanical strength due to
dispersion hardening by alloying the platinum
with yttrium [346].
Resistance Thermometry. Platinum resis-
tance thermometers are based on the temperature
dependence of the electrical resistivity. The
temperature-coefcient of electrical resistance
(TCR) of high-purity platinum is
3.927 10
3
/K. Basic values of the changes of
resistance over temperature ranges (e.g., 200

C and 850

C) of platinum resistance ther-
mometers are specied in international standards
(DIN IEC 751).
At temperatures below about 20

K the TCR
of pure metals becomes too low in comparison
to the absolute value of the resistance and
cannot be measured. Alloys of rhodium with
0.5 atom% iron or alloys of gold with 1.15 at-
om% manganese show due to magnetic effects
an increasing TCR with decreasing temperature
(Kondo effect [347]) to sufcient high, measur-
able values.
Platinum wire-wound resistors, whose resis-
tance is determined by the length and cross
section of the wire, have been almost completely
displaced by so-called thin-lm resistors, man-
ufactured by thin-lm technology. A lm of
platinum ca. 1 mm thick is deposited on an
insulating ceramic substrate by vacuum deposi-
tion or cathodic sputtering. The required resis-
tance value is adjusted by laser cutting. A mean-
drous resistance path is formed in the lm of
noble metal by cutting with a laser beam or by
ionic etching through a masking coating pro-
duced by photolithography (Fig. 34). The thick-
ness of the lm and the total path length deter-
mine the resistance at 0

C. Path widths are in the
region of 20 mm. The connecting leads, which
are joined to the thin lm by special bonding
processes, also consist of noble metals or their
compounds. Modern resistance thermometers
based on thin-lm technology have the advan-
tage over wire-wound resistance thermometers
because they can be manufactured by highly
automated methods and require only small
amounts of PGM (<1 mg per device).
Iridium-layers have values of thermal expan-
sion which are comparable to those of the ce-
ramic. They are therefore applied on devices for
temperature measurements at temperatures down
to about 200

C.
Resistance thermometers are used today in a
wide range of technologies, from household
appliances to chemical equipment, and fromroad
transportation to air and space travel.
Table 9. Commonly used noble metal thermocouple pairs
Positive leg Negative leg Operating temperature,

C
Cu Au 99.4 Co 0.6 240 to 0
Pt 90 Ir 10 Au 60 Pd 40 0 to 700
Pt 90 Rh 10 Pt 850 to 1600
Pt 70 Rh 30 Pt 94 Rh 6 1000 to 1800
Rh 40 Ir 60 Ir 1000 to 2200
Figure 34. a) Platinum layer resistor element (dim 2 2.3
mm) with welded connecting wires, layer resistance adjusted
by laser cuts. b) enlarged view of platinum layer paths on the
ceramic substrate. Path width ca. 15 mm (Diehl et al. [167])
370 Platinum Group Metals and Compounds Vol. 28
Special Sensor Devices [348]. Oxygen se-
lective sensors (lambda-probes), use the high
electrical conductivity imparted to solid electro-
lytes (e.g., ZrO
2
) by the presence of oxygen ions,
compared with their normal conductivity due to
electrons. The ionic conductor is provided on
both sides with platinum electrodes and it acts as
a separator between two gas spaces. Any differ-
ence in the oxygen partial pressure can be deter-
mined by measuring the electromotive force
(Nernst electromotive force) between the elec-
trodes. Lambda probes are used in automotive
cars to maintain an accurate air/fuel ratio and to
monitor the performance of the emissions control
system (automobile exhaust-gas catalysts in
Otto-engines).
Noble-metal catalysts are also used in sensors
for detecting combustible gases in air or explo-
sive gas mixtures. Heat evolution is normally
detected by sensors known as Pellistors, which
consist of platinum wire in a small sphere of
Al
2
O
3
(diameter: 1.5 mm). The sphere is satu-
rated with a noble-metal catalyst. If a chemical
reaction takes place on the catalyst, a temperature
increase occurs that can be measured by the
change in resistance of the platinum wire. These
heat evolution sensors are used in explosion
protection equipment.
Platinum and Palladium porphyrin com-
plexes and ruthenium(II) diimines are used in
optical oxygen sensors. These sensors respond
specically to molecular oxygen by a change in
the intensity of luminescence which is emitted
from a probe molecule. The luminescence is re-
versibly quenched by molecular oxygen. Optical
sensors have been developed for oxygen detection
in hydrogen, carbon dioxide, and as biosensor for
determine the level of glucose [349].
Thin palladium layers act as hydrogen lters
in optical switching devices. These systems are
based on the hydrogen-dependent transition from
the metallic state of yttrium hydride YH
1.8
to the
transparent state YH
2.9
(Fig. 35). Thin yttrium
layers are deposited by molecular-beam epitaxy
on transparent glass plates covered with a pro-
tective niobium layer and an upper palladium
layer. The palladium layer impedes oxidation of
the yttrium hydride and provides a catalytic
surface hydrogen dissociation and diffusion into
or out of the yttriumhydride layer. Depending on
the hydrogen concentration, the cell switches
from mirror reection (YH
1.8
) to transparency
(YH
2.9
). Switching occurs in less than 0.1 s.
Applications are expected for automotive and
construction parts [351], [352]. An other hydro-
gen-concentration-dependent device consists of
an inner NbHlayer, covered on both sides by iron
plates. The system behaves ferromagnetically at
low H concentration; higher H concentration
effect the transition to the antiferromagnetic
state. The system is suited as magnetic-eld
sensor, for instance, in read and write heads of
computer hard disks.
Osmium -bipyridil-redox polymers com-
bined with a redox enzyme can be used as minia-
ture in vivo sensor for implantation into diabetes
patients for continuous monitoring of their blood
glucose levels (Wired enzyme bio-sensor,
[353]). The divalent and the trivalent complexed
osmiumions can exchange electrons at high rates.
The osmium polymer electrically connects the
redox centres of the enzymes by introducing
electron relays close to the enzyme active site.
A sol-gel based amperometric biosensor in-
corporates an osmiumredox polymer as mediator
for detection of lactate [354].
10.8. Electrical Technology [205], [237]
In low-current technology, electrical contacts of
gold, silver, palladium, rhodium, platinum, and
their alloys are used. Contacts made of bulk noble
metals are becoming less common than those
coated by electrolytic and mechanical processes.
For a long time, large numbers of so-called
reed contacts have been used in telephone relays.
These are Ag Pd-, rhodium-, or ruthenium-
coated contacts operating under a protective gas.
Such contacts must be resistant to sparking,
corrosion, and erosion, and must not become
Figure 35. Optical switching device with a palladium thin
layer [350]
Vol. 28 Platinum Group Metals and Compounds 371
welded together. During a lifetime of 30 years,
they must carry out millions of switching opera-
tions without damage. Furthermore, their contact
resistance must be low, and their nominal resis-
tance must be constant.
Platinumsealing wires are also nowused only
for specialty light bulbs and transmitter tubes.
Heating elements made of platinum metals or
their compounds are used in resistance-heated
furnaces above 1200

C. Windings of Pt 70
Rh 30 can be used up to 1500

C, and ribbon
windings of rhodium up to 1800

C. Furnace
elements made of platinum metals can be used
without a protective gas. Platinum, rhodium,
iridium, and ruthenium are used as susceptor
materials in induction furnaces.
Platinum iridiumalloys are useful for spark
plug contacts for high-power aeroplane and au-
tomobile engines.
10.9. Electronics
The platinum group metals and their alloys are
key materials in electronic devices and compo-
nents (Table 10). Those include active discrete
semiconductor devices (e.g., diodes, transistors,
semiconductor memories), single-crystal inte-
grated circuits (ICs), automotive electronic de-
vices for engine-management systems, automo-
tive oxygen sensors (lambda sensors), and safety
devices (ABS, airbag), and so-called passive
components (e.g., resistors, capacitors). The me-
tals are mainly applied as surface layers, but also
in formof bulk material (sintered frompowder) in
discrete capacitor and resistor devices.
Important applications of platinum metals in
electronics are layer arrays of conductor and
resistor paths deposited on substrate plates to
form electronic circuits. The main types of elec-
tronic circuits are printed circuits (PC) and thick-
lm and thin-lm circuits. They are usually
additionally loaded with discrete active and pas-
sive electronic components (hybrid technology).
On printed circuits boards, metallizing is pri-
marily carried out by electroplating. In thick-lm
circuity, the noble metal layers are produced by
the use of paste preparations, which consist of
noble metal powders, glass frits, and organic
binders. They are applied by screen printing onto
ceramic substrates, followed either by drying or
by ring at elevated temperatures. The glass frits
act as adhesives to the ceramic substrates.
In thin-lm circuits the noble metal layers are
precipitated on glass or special ceramic sub-
strates by sputtering, by evaporation, or by ther-
mal decomposition of noble metal resinates.
The powders used in the pastes are generally
produced by reduction of noble metal salts
[355]. The reaction conditions determine shape,
size, and specic surface area of the powder.
Bimetallic (alloyed) powders are produced by
Table 10. Main applications of platinum group metals in electronics [92, p. 557]
Form
Surface coat
Element Bulk Bimetal electroplated sputtered or evaporated pastes, lacquers solder connection
Ru reed contacts Ru O for cathodes in
special tubes
thick-lm circuits
(resistor pastes for
hybrid circuits)
Mo Ru
high-temperature
solders for electron
tubes
Rh slide contacts,
coating of Cu
disks for thyristors,
surface hardening
of Ag coatings on
pressure contacts
hard contact layers for
pressure contacts on Ag
surfaces, corrosion
protection
metallizing pastes
for sensor surfaces
Pd bonding wires
for transistors,
diodes
plug-in
contacts
plug-in contacts multilayer capacitors conductor and electrode
paste for thick-lm
circuits, multilayer
capacitors
Ag Cu Pd solders
for electron tubes
package joining
Pt test resistors test resistors, diffusion
barriers, IC technology
372 Platinum Group Metals and Compounds Vol. 28
mechanical mixing to give composite blends or
by coprecipitation, followed by thermal treat-
ment of the dried powders. Their specic sur-
face area is usually between 1.5 and 10 m
2
/g.
The particle shapes can be spheroidal, micro-
crystalline, or ake.
Platinum nds application as barrier layers
and as contact pads on semiconductor chips.
Platinum interlayers on RuO
2
electrodes of
ferroelectric capacitors (lead zirconate titanate
PZT) improve their stability and reduce leak-
age losses [356]. Platinum additions in silver-
based metallizing preparations and thick-lm
conductor pastes for screen printing of hybrid
circuits serve as stabilizing component against
silver migration. In Ag-, AgPd-, or Au-con-
taining thick-lm pastes, Pt powder increases
the resistance to scavenging during soldering
operations with Sn and Sn Pb solder alloys.
Palladium, pure or in combination with silver,
is the most important component in pastes
used for the production of the inner electrodes
of multilayer capacitors. Special ne-grain
powders are needed to obtain sufciently thin
and homogeneous layer structures (Fig. 36). It
is produced by chemical reduction of aqueous
Pd(NO
3
)
2
or PdCl
2
solution. It is used in pure
form or alloyed or mixed with silver powder
(mainly of composition Ag Pd30 wt %).
Corresponding electrode pastes are applied to
BaTiO
3
substrates and red at temperatures
depending between 1100 and 1300

C, de-
pending on grain size and substrate material.
Palladium is also used as component in silver-
based conductor pastes and for resistor ele-
ments in thick-lm circuity. As an additive in
silver metallizing pastes, Pd improves the
resistance to silver ion migration.
Electroless (by chemical reduction) deposit-
ed, thin palladium coatings form the rst met-
allization step for metallizing bare polyimide
surfaces, followed by chemical and galvanic
deposition of thicker copper layers. This proce-
dure is especially applied for the plating of holes
in the polyimide substrates to connect electrical
functions in multilayer PCs.
Ruthenium is the most important base ele-
ment of screen-printed resistor layers in thick-
lm circuits. These layers are printed with
paste preparations consisting of RuO
2
with
additions of PbO and Bi
2
O
3
. They form by
ring complex ruthenium compounds of high
thermal stability and with very low tempera-
ture coefcients of electrical resistivity. Exact
resistance values are adjusted by applying
small cuts by means of laser beam into the
resistor layer (laser trimming).
Platinumresinates are used for the production
of conductive coatings on ceramic substrates
onto which further layers can be deposited elec-
trolytically. Thin-lm cobalt platinum alloys
and multilayers play an important role as mag-
netic media on hard disks for magnetic and
magneto-optic storage and recording devices.
Various organo platinum compounds, combined
with special organic dyes, act as sensitizers to
effect the transformation of light energy into
charge separation in molecular systems. Appli-
cations are the light-induced charge transfer in
photovoltaic equipment to produce electric cur-
rent, also for the photochemical production of
hydrogen fromwater, fromhydrogen sulde, or a
nonaqueous source. Organoruthenium com-
pounds, deposited on nanocrystalline titanium
dioxide particles, serve as charge-transfer sensi-
tizers in photovoltaic devices [357]. The parti-
cles are placed as a thin transparent lm between
two glass plates which have been coated with
transparent conducting oxide layers (Fig. 37).
The sensitizer part is separated fromthe counter-
electrode by an triiodide/iodide electrolyte. A
platinum coat on the transparent conducting
oxide layer catalyzes the cathodic reduction of
triiodide to iodide. The light-induced charge
Figure 36. Fine-grain palladium powder for the production
of electrodes in multilayer ceramic capacitors [167]
Vol. 28 Platinum Group Metals and Compounds 373
transfer from the excited sensitizer to the semi-
conductor takes the route via interlocking organ-
ic groups. The charge separation is accomplished
by the fact that the forward electron transfer from
the metal via the ligand into the TiO
2
semicon-
ductor membrane is orders of magnitude faster
(< 1 ps) than the back diffusion because of the
less favorable electronic coupling between the
semiconductor and the oxidized ruthenium(III)
ion. The overall efciency for solar light conver-
sion to electricity in this arrangement reaches
10 11 %. Higher efciency is expected to be
achieved by replacing the liquid electrolyte by a
solid electron-hole conductor in which conduc-
tion does not involve mass transfer and which
allows the redox level to be matched to the
ground state oxidation potential of the sensitizer
[358]. Applications are expected in the low-
powder range (e.g., solar watches with the pho-
tovoltaic cell incorporated in the cover glass),
followed by development of interconnected
modules, and production of solar tiles.
Organometallic platinum and ruthenium(II)
compounds, anchored to a wide-band semicon-
ductor, are promising materials for performing
photoinduced hydrogen production [359363].
A tandem device that achieves the direct cleav-
age of water into hydrogen and oxygen by visible
light works byconnection of two photosystems: a
rst lm of nanocrystalline WO
3
and a second,
dye-sensitized nanocrystalline TiO
2
lm. The
blue part of the spectrum is absorbed by the rst
layer, creating by band gap excitation valence
band holes which serve to oxidize water to oxy-
gen. The second lm captures the green and red
part, transmitted through the top electrode, there-
by producing photovoltage, which enables the
formation of hydrogen by the conducting elec-
trons [359], [360].
Organic polypyridyl complexes of ruthenium
and osmium are able to effect photoinduced
electron transfer in molecular structures (mo-
lecular wires [365]). Such components are
needed to link molecular-sized electronic de-
vices (e.g., optical switches, fast recording de-
vices, miniaturized sensors) electronically to the
surrounding assembly. Their function is to pro-
vide electronic connection between spatially
remote redox-active subunits. They must main-
tain strict stereochemical integrity of the nal
assembly. Unidirectional electron ow is pro-
moted by external stimulation (e.g., absorption
of a photon, application of a potential at an
attached electrode, or by chemical means).
RuO
2
/TiN storage electrodes serve for the
production of dynamic random access memory
capacitors [366]. Surface layers of osmium and
ruthenium on dispenser cathodes lower the elec-
tronic work function [367].
10.10. Coatings [30], [31], [93], [166]
Coatings of platinum metals may be applied to a
substrate by various methods.
Figure 37. Layout of a nanocrystalline TiO
2
solar cell. The
transparent dye derivatized titanium dioxide lm is sand-
wiched between two conducting glass electrodes. It harvest
light from both front and back sides. TCO is a transparent
conducting oxide coating layer with a highly active, stable
platinum electrocatalyst [357]
(courtesy Platinum Metals Review)
374 Platinum Group Metals and Compounds Vol. 28
10.10.1. Coatings Produced by Electrolysis
[338], [368], [369]
Platinum. Lustrous thin lms for decorative
purposes are deposited from an electrolyte ob-
tained by treating potassium tetranitritoplatinate
(II), K
2
[Pt(NO
2
)
4
], with sulfuric acid. The active
complex is H
2
[Pt(NO
2
)
2
SO
4
]. This is more stable
than other platinum plating baths.
Relatively thick coatings can be deposited
from alkaline solutions of sodium hexahydroxy
platinate(IV), Na
2
[Pt(OH)
6
].
A typical bath is sodium hexahydroxoplati-
nate 20 g/L, sodium hydroxide 10 g/L, pH 13,
75

C, current density 0.8 A/dm
2
. A disadvan-
tage is the low stability due to decomposition of
the hydroxy salt. The use of the corresponding
potassium salts eliminates this difculty [370],
[371].
Platinum(II) diamminedinitrite, [Pt
(NH
3
)
2
(NO
2
)
2
] (P salt), was formerly very
widely used and today along with Na
2
[Pt(OH)
6
],
is used for coating titanium by aqueous electrol-
ysis. These coatings are of lower quality than
those produced by high-temperature electrolysis.
Also, extensive pretreatment of the substrate
metal is necessary, mainly to prevent cathodic
absorption of hydrogen.
The Q bath is based on a solution of [Pt
(NH
3
)
4
]
2
(Pt concentration 5 20 g/L) in a
dilute phosphate buffer, pH 10.3 10.5. At op-
erating temperatures above 90

C, high-quality,
thick Pt deposites are obtained which are exten-
sively used in the engineering industry when
components are subjected to high-temperature
corrosion [372], [373].
Rhodium [169], [374376]. Rhodium coat-
ings are superior to all other PGM coatings,
having better hardness, mechanical and chemi-
cal stability, and reectivity. For these reasons,
rhodium is more widely used than the other
platinum group metals (see also Electro-
chemical and Chemical Deposition, Section
8.16.).
Electrolytes consisting of rhodium sulfate
(10 20 g/L Rh) in sulfuric acid can give
comparatively thick coatings (10 12 mm).
Crack formation can be countered by addition
of sulte, selenic acid, magnesium sulfate, or
magnesium sulfamate. These baths are used to
produce rhodium coatings for heavy-duty slip
ring contacts and optical reectors, and were
at one time used for reed contacts in telephone
technology.
Rhodium sulfate or phosphate baths contain-
ing 2 g/L of rhodium are used for decorative
purposes and give strongly reective thin lms
(0.1 0.5 mm) that prevent silver or white gold
from tarnishing. They are also used for plating
eyeglass frames.
Palladium [168]. Palladium can sometimes
replace gold in coatings for electronics. The
plating baths contain palladium(II) diamminedi-
nitrite, [Pd(NH
3
)
2
(NO
2
)
2
] (palladium P-salt),
with additions of sodium and ammonium ni-
trates, or sulfamates [377], [378].
Successful results have recently been ob-
tained with plating baths based on organopalla-
dium complexes. Concentrated hydrochloric ac-
id plating baths with dissolving palladiumanodes
are rarely used now.
Palladium nickel alloys with 70 75 % Pd
can be electrodeposited from ammoniacal solu-
tions. Such deposits, overashed with gold are
used as a replacement for gold in the electronics
industry [379], [380].
Ruthenium [381383] is deposited electro-
lytically from solutions of ruthenium complexes
with a bridging nitrido ligand, for example,
nitridooctachlorodiaquodiruthenate(IV),
(NH
4
)
3
[H
2
O(Cl
4
Ru)N(RuCl
4
)H
2
O], the basis
of the so-called RuNC baths. The corresponding
complex with hydroxo ligands instead of chloro
ligands can also be used.
Ruthenium baths based on ruthenium nitro-
sylsulfamate are also used.
High-Temperature Electrolysis (HTE)
[30], [88], [239241], [384], [385]. Platinum
group metals can be deposited electrolytically
fromcyanide-containing melts in which a soluble
anode provides the noble metal that is deposited
on the cathode. The metal most widely used in
this process is platinum, although iridium is
sometimes used.
The molten salt, an eutectic mixture of
KCN and NaCN, is maintained at 500 600

C
in an electrically heated crucible. The platinum
is deposited from the melt onto the substrate,
which forms the cathode in the electric
circuit.
Vol. 28 Platinum Group Metals and Compounds 375
Process parameters are as follows:
Electrolyte K
2
[Pt(CN)
4
] in KCN NaCN
Operating temperature 500 600

C
Deposition voltage 0.1 2 V
Cathodic current density 1 5 A/dm
2
Cathodic current yield > 60 %
Mean rate of deposition 10 20 mm/h
Oxidation of the melt and of the metal is pre-
vented by a protective atmosphere of high-purity
argon. Suitable substrate materials for HTE plat-
inum deposition include refractory metals such
as titanium, niobium, tantalum, molybdenum,
tungsten, zirconium; steels; and other metals
such as copper. They must generally be pre-
treated by sandblasting and degreasing.
Advantages of HTE platinum coatings, com-
pared with those produced by aqueous electroly-
sis, include low porosity; a wide range of lm
thicknesses (1 400 mm), excellent adhesion;
good resistance to mechanical impact, thermal
shock, and sliding wear; high thermal conductiv-
ity; and high ductility.
The largest use is in producing anodes for
cathodic corrosion protection [242] (often in the
form of expanded metal) or insoluble anodes for
electrolytic technology. Platinum-coatedmolybde-
num wire is used in the construction of thermionic
tubes and for fusion with glass. High-temperature
electrolysis is also used for electroforming.
10.10.2. Coatings Produced by Chemical
Reaction [31]
Surface coatings of platinum metals can be de-
posited onto metallic or nonmetallic substrates
by chemical reduction or thermal decomposition
of PGM compounds.
Platinum acetylacetonate is used for platini-
zation of titanium. The titanium articles are
painted with a solution of this compound, dried,
and heated. Repeated application is necessary.
The process is not widely used due to allergic
reaction and the low quality of the coatings.
Platinum coatings are produced on ceramic
tubes by a new technique using a lacquer [243],
[386]. Such tubes are used as catalysts for the
synthesis of hydrogen cyanide.
Platinum metal resinates are used as ceramic
colorants [244], [245]. These can be employed to
produce conductive platinumcoatings on ceram-
ic substrates, onto which further layers can be
deposited electrolytically. Platinum coatings are
also used for decorative purposes.
Hexachlororuthenic(III) acid, H
3
[RuCl
6
],
dissolved in alcohol, is painted onto the sub-
strate, dried, and heated strongly in air to
produce an extremely adherent coating of
RuO
2
[246], [247]. Titanium sheet, coated in
this way, has outstanding electrochemical prop-
erties and is being used in chloralkali electroly-
sis as dimensionally stable anodes. The RuO
2
coatings are also used in the production of
circuit boards by screen printing.
10.10.3. Coatings Produced by Physical
Methods [88], [167]
Platinum can be deposited as a thin lm on sub-
strates by evaporating the metal in a high vacuum.
Modern thin-lm technology is based mainly on
the generation of ne particles from a cathode
(cathodic sputtering). Due to the high kinetic
energy of these metal particles, extremely good
adhesion is obtained. In the case of platinumgroup
metals, sputtering targets are used for microelec-
tronics and for resistance thermometers. Ion plat-
ing is also used to produce high-quality coatings.
Roll-bonded PGM coatings are no longer
important.
10.11. Dental Materials [88]
Platinum and palladium have major importance
in dentistry ( Dental Materials, Section 2.3.).
Up to ca. 1900, dental protheses such as gold
llings, crowns, and bridges were made mainly
of alloys with the same composition as those used
in coinage and jewelry, and later of 22-carat gold
(83.3 %). Platinum was used only to make xing
pins.
Important quality requirements such as oral
stability, biological compatibility, color, strength,
and good functional properties are achieved only
by modern dental alloys. These complex alloys,
unlike theearlier gold-containingones, have a very
ne-grained, homogeneous crystalline structure,
givingmuchbetter corrosionresistance. Also, their
hardness is controllable over a wide range and can
be adapted to particular requirements.
376 Platinum Group Metals and Compounds Vol. 28
StandardAlloys. Modern alloys for making
dentures or prostheses have compositions mainly
in the range 65 85 % gold, 1 10 % platinum,
1 4 % palladium, 10 15 % silver, 0 10 %
copper, and 0 1 % zinc.
In low-gold alloys, which are cheaper, the gold
is replaced partially by silver or palladium. These
alloys contain 40 60 %gold, 0 2 %platinum,
3 10 % palladium, 23 35 % silver, 0 12 %
copper, and 0 5 % tin, indium, and zinc.
Silver-base alloys have very lowgold content.
Adequate oral stability can be achieved by in-
cluding at least 25 % platinum group metals or
gold. Inexpensive alloys in this category contain
at least 20 25 % palladium, 0 3 % gold, ca.
55 70 % silver, and copper and zinc, and are
therefore no longer yellow, but white.
Alloys with Ceramic Veneering have been
developed in the early 1960s. With the help of these
alloys ceramics can be fused on a cast metal
framework. The main properties of the alloys nec-
essary for this task are a thermal expansion coef-
cient similar to that of the ceramic and a solidus
temperature sufciently above the fusing tempera-
ture of the ceramic. With early ceramics ring was
carried out at 980

C. Alloys for these ceramics
needed a solidus temperature above 1050

C. To
achieve this goal the content of platinum and/or
palladium in the alloy had to be increased, which
caused whitening of the alloy beside an increase of
the melting range. In recent years, low fusing
ceramics became available, which allow to use
alloys with compositions closer to the standard
alloys and alloys with a more yellow color.
Alloys for high fusing ceramics with a high
gold content have compositions in the range
75 90 % gold, 5 10 % platinum, 1 10 %
palladium, 0 3 % silver, with small additions
of iron, indium, tin, zinc, and other elements.
Attempts have been made to reduce the cost of
these alloys by replacing gold by palladium and
silver. Typical Au Pd Ag alloys have com-
positions in the following range: 42 62 %gold,
25 43 % palladium, 5 20 % silver, and 4
10 % base metals such as copper, tin, indium,
gallium, and zinc. Typical silver-free Au Pd
alloys have the following composition: 45
60 % gold, 32 40 % palladium, and 0 14 %
of the base metals tin, indium, zinc, or gallium.
Palladium-base dental alloys were introduced
in Germany in the early 1980s. These were
developed to reduce cost. Silver-free and sil-
ver-containing alloys are available. Both contain
very small amounts, if any, of gold and platinum.
The range of compositions for the silver-contain-
ing palladium-based alloys is 53 61 % palladi-
um, 28 38 %silver, 0 12 %tin, indium, zinc,
and gallium. For the silver-free palladium-based
alloys, the composition range is 73 88 % pal-
ladium, 0 2 % gold, and 12 26 % of the base
metals copper, cobalt, tin, indium, and gallium.
11. Economic Aspects [5], [10], [24],
[30], [46], [48], [5763],[76], [235],
[248255]
11.1. Supply
The most important PGM-producing mines are
located in
.
South Africa (Amplats, Lonmin Platinum, Im-
pala, Northham, Kroondal Platinum, Trojan
Platinum)
.
Russia (Norilsk Nickel, Koryak and Kondyor
mines)
.
Canada (Inco, Falconbridge, North American
Palladium)
.
USA (Stillwater)
.
Zimbabwe (Hartley PLatinum, Zimbabwe
Platinum, Anglo-American Zimbabwe).
The world total output 1998 of platinum,
palladium and rhodium is listed in Table 11 and
shown in Fig. 38.
In addition to PGMs obtained from ores, a
considerable amount of secondary material ex-
ists. The extent of this is very variable and
uctuates with time.
Averaged over all the PGMs, it amounts at
present to ca. 20 % of primary production, with
the greatest emphasis on platinum and especially
palladium. The present effort directed toward
Table 11. World supply of Pt, Pd, and Rh in 1998 by region (in 10
6
oz)
Pt Pd Rh
South Africa 3680 1820 400
Russia 1300 5800 110
North America 285 660 16
Others 135 120 4
Total 5400 8400 530
Vol. 28 Platinum Group Metals and Compounds 377
recovery from spent automobile catalysts will
considerably increase the proportional secondary
production of platinum and rhodium.
A high proportion of the PGMs is recycled by
the users or, in the case of contract suppliers of
seminished products (e.g., catalysts), by the
producers. These materials do not appear on the
market either on the supply or on the demand
side, so supply gures essentially reect only
mined products.
11.2. Demand
Table 12 and Figure 39 show the demand for
platinum, palladium, rhodium, iridium and ru-
thenium by application.
11.3. Prices
The prices of the PGMs are strongly inuenced
by factors of demand for new technical applica-
tions, by availability of supply, and by specula-
tive stock building, leading to considerable dif-
ferences between monthly and yearly high and
low price notations (see Table 13). Rising de-
mand for technical applications, especially in the
autocatalyst sector has caused strongly rising
prices for platinum, palladium, and rhodium.
11.4. Commercial Aspects
Since 1975, a so-called London free market price
for platinum is calculated and published twice
daily. Since 1976, a London palladiumquotation
has also been available. Both of these were only
price indications, not to be compared with the
xed quotations for gold and silver. The London
Platinum and Palladium Market (LPPM) has
since been established and publishes xed quota-
tions twice daily.
Platinum and palladium are also traded on the
New York Mercantile exchange (NYMEX) and
on the TOCOM in Tokyo.
Trading in platinum on the New York
exchange is in the form of contracts for units
of 50 troy ounces. The purity of platinum
supplied in fulllment of such a contract must
be at least 99.9 %, and the platinum must
originate from a producer or assayer registered
with the exchange. For palladium, the contract
amount is 100 troy ounces, and the purity must
be 99.9 %.
Spot transactions (immediate delivery and
payment) are guided by the London quotation
and the New York exchange quotation.
Palladium in recent years has found increas-
ing utilization in the production of automotive
catalysts. Due to very unstable supply from the
Table 12. PGM demand in 1998 by application (in 10
6
oz)
Pt Pd Rh Ir Ru
Autocatalyst 1830 4470 490 36
Chemical 265 230 31
Dental 1230
Electrical 320 8
Electronics 2070 184
Electrochemical 30 74
Glass 220 34
Investment 315
Jewelry 2370 250
Petrochemistry 130
Process catalysts 3 87
Others 305 115 10 36 30
Total 5755 8365 573 105 375
Figure 38. World palladium, rhodium, and platinum supply
in 1998 by region (in 10
6
oz) a) palladium (total 8400);
b) rhodium (total 530); c) platinum (total 5400)
378 Platinum Group Metals and Compounds Vol. 28
main palladium producer of the world, Russia,
palladiumprices increased more than threefold in
the period from December 1996 to May 1998.
12. Toxicology
Platinum is used in therapy; cisplatin is currently
used for cancer treatment. Known side-effects
are sickness, vomiting, hypersensitivity reac-
tions, ototoxicity and nephrotoxicity [387].
The tetroxides of osmium and ruthenium
strongly irritate and corrode the conjunctiva
and cornea of the eye and the mucous mem-
branes of the respiratory tract. Temporary toxic
effects can occur in bone marrow, liver, and
kidneys. The salts of hexachloroplatinic acid
H
2
[PtCl
6
] [16941-12-1] have a strong allergenic
potential (see below); platinum metal is not
allergenic.
The MAK value for platinum compounds has
been set as lowas 2 mg/m
3
(as Pt), not because of
their toxicity but due to allergenic potential. For
osmium tetroxide [20816-12-0] the MAK value
is even lower because of its strong irritating
effect: 0.2 mg/m
3
. In the United States, TLVs
for water-soluble rhodium salts are 1 10 mg/
m
3
. For other platinum group metals toxicologi-
cal limits have not yet been established.
Table 13. PGM price lows and highs (1996 1998, in $/oz)
1996 1997 1998
low high low high low high
Pt 367 433 342 497 334 429
Pd 114 143 117 245 201 417
Rh 320 345 200 370 370 780
Ir 60 10 110 290 270 575
Ru 29 55 38 41 39 65
Figure 39. World PGM demand in 1998 by application (in 10
6
oz). Total quantities include recycled material (PA
405 10
6
oz, Pd 175 10
6
oz, Rh 57 10
6
oz) a) platinum (total 5755); b) palladium (total 8365); c) rhodium (total
573); d) iridium (total 105); e) ruthenium (total 375)
Vol. 28 Platinum Group Metals and Compounds 379
The median concentrations of platinum in
blood, plasma/serum, and urine are about 1 ng/L
[388]. The limit for platinum and osmium in
industrial efuents is 3 mg/L[389]. In the United
States, most platinum group metals are classied
as poisonous or very poisonous in waste-
water treatment plants [390].
Automotive Emission Control Catalysts.
Toxicological effects of platinum-group metals
have been studied increasingly because of their
widespread use as automotive emission control
catalysts. According to a recent investigation, an
engine that is equipped with a modern three-way
catalyst emits approximately 15 ng of platinum
per cubic meter of exhaust gas in an automobile
travelling at a constant speed of 100 km/h; plati-
num metal is emitted, as well as platinum com-
pounds that are yet to be analyzed [391]. The
study could not detect any health risk arising
from the use of automotive emission control
catalysts, but they undoubtedly have an environ-
mental benet because they decrease the emis-
sion of nitrous oxides, hydrocarbons, and carbon
monoxide. Even the most sensitive methods
could not detect a correlation between the uptake
of platinum from the environment and trafc
density [392].
Hexachloroplatinate Allergy. Salts of hex-
achloroplatinic acid H
2
[PtCl
6
] are among the
strongest synthetic allergens. Symptoms range
fromirritation of skin and mucous membranes to
life-threatening attacks of asthma. Cigarette
smokers run a higher risk of sensitization to
platinum salts. The symptoms of allergy usually
start after several weeks of exposure.
Hypersensitivity to hexachloroplatinate is ir-
reversible, and further exposure must be avoided
immediately.
For prophylaxis, exposure to dust and aerosols
must be avoided by use of appropriate equip-
ment. Special workplace hygiene is required
when hot solutions of hexachloroplatinates, hex-
achloroplatinic acid, or the products of their
thermal decomposition are handled. Exposed
persons must undertake skin tests (prick test) at
regular intervals. In this way, sensitization is
detected at an early phase and appropriate mea-
sures can be taken.
Other platinum and platinum group metal
compounds are not known to have an allergenic
potential. Recently, skin allergies to the plati-
num-base alloys used in dental materials have
been reported but are still under discussion. The
German government has recommended to test
the corrosion resistance and biocompatibility of
palladium copper alloys prior to their use in
dental restoration [393].
References
1 D. McDonald: A History of Platinum, J. Matthey Co.,
London, 1960.
2 D. McDonald, L. B. Hunt: A History of Platinum and its
Allied Metals, J. Matthey Co., London 1982.
3 PlatinumMetals Review, vol. 1 (1957) vol. 44 (2000),
J. Matthey Co., London.
4 A. Binz: Edelmetalle Ihr Fluch und Segen, W. Lim-
pert-Verlag, Berlin 1943.
5 Fonds der Chemischen Industrie: Edelmetalle Ge-
winnung, Verarbeitung, Anwendung, Folienserie,
no. 12, Frankfurt 1989.
6 R ompp Lexikon Chemie, 10th ed., Thieme, Stuttgart
1996 1999.
7 H. Rompp: Chemie der Metalle, Franckhsche Verlag-
shandlung, Stuttgart 1941.
8 P. Walden: Chronologische ubersichtstabellen zur
Geschichte der Chemie (Altertum bis 1950), Spring-
er-Verlag, Berlin 1952.
9 S. Neufeld: Chronologie Chemie 1800 1980, VCH,
Weinheim, Germany 1987.
10 H. Quiring: Platinmetalle, Die metallischen Roh-
stoffe, vol. 16, Enke Verlag, Stuttgart 1962.
11 J. Morin: La Platine, lOr Blanc ou le Huitieme M etal,
Paris 1758.
12 A. Galan, R. Moreno: Platinum in Eighteenth Centu-
ry A Further Spanish Contribution to an Understand-
ing of Its Discovery and early Metallurgy, Platinum
Met. Rev. 36 (1992) 40 47.
13 D. McDonald: One Hundred and Fifty Years An
Anniversary Review of Johnson Mattheys Role in the
Economic History of Platinum, Plat. Met. Rev. 11
(1967) 18 29.
14 H. M. Severin: Gold and Platinum Coinage of Imperial
Russia from 1701 1911, Crown and Taler Publ. Co.,
New York 1958.
15 H.-G. Bachmann, H. Renner: Nineteenth Century Plat-
inum Coins, Platinum Met. Rev. 28 (1984) 126 131.
16 A. L. von Erengreuth: Allgemeine M unzkunde und
Geldgeschichte des Mittelalters und der neueren Zeit,
R. Oldenbourg, Munchen 1971.
17 L. B. Hunt: Dr. Hans Merensky Centenary of the
Discoverer of the PlatinumReef, PlatinumMet. Rev. 15
(1971) 102 107.
18 J. Levin: The Story of Mintek 1934 1984, Council for
Mineral Technology (Mintek), Randburg 1985.
380 Platinum Group Metals and Compounds Vol. 28
19 A. M. Edwards, M. H. Silk: Platinum in South Africa,
Council for Mineral Technology (Mintek), Randburg
1987.
20 H. Houben: Festschrift zum f unfzigj ahrigen Bestehen
der Platinschmelze G. Siebert GmbH, Hanau, Albertis
Hofbuchhandlung, Hanau 1931.
21 D. G. Cooper: Das Periodensystemder Elemente, VCH,
Weinheim, Germany 1972.
22 E. Fluck, K. G. Heumann, Periodensystemder Elemente,
IUPAC-Empfehlungen, VCH, Weinheim, Germany
1985.
23 G. C. Bond, Plat. Met. Rev. 44 (2000) 146 155.
24 H. P. Munster, Taschenbuch des Metallhandels, 8th ed.,
Metallverlag, Berlin 1989.
25 G. H. Aylward, I. J Findlay: Datensammlung Chemie,
VCH, Weinheim, Germany 1975.
26 National Bureau of Standards Circulars.
27 R. W. Douglass, F. C. Holden, R. J. Jaffee: High-
Temperature Properties and Alloying Behavior of the
Refractory Platinum-group Metals, Battelle Memorial
Institute, Columbus 1959.
28 E. M. Savitskii, V. P. Polyakova, M. A. Tylkina: Palla-
dium Alloys, Primary Sources/Publ., New York 1968.
29 Doduco: Datenbuch Handbuch f ur Techniker und
Kaueute, 2nd ed., Pforzheim 1977.
30 The Platinum Asociation: Platinum, Production, Prop-
erties and Applications, a Short Course, Hill & Knowl-
ten, Frankfurt 1989.
31 Ullmann 5th ed., A21, 75 ff.
32 Kirk-Othmer, 4th ed., 19, 349.
33 Degussa: Platinger ate Best andigkeit und Handha-
bung, Hanau 1976.
34 R. Bock: Aufschlumethoden der anorganischen und
organischen Chemie, VCH, Weinheim, Germany
1972.
35 M. Fieberg, H. Renner, G. Schlamp in G. L. Trigg, E. H.
Immergut (eds.): Encyclopedia of Applied Physics,
vol. 18, Wiley VCH, Weinheim, Germany 1997,
pp. 235 279.
36 Gmelin 8th ed., System no. 68 (Platin), 65 (Palladium),
64 (Rhodium), 67 (Iridium), 63 (Ruthenium), 66
(Osmium).
37 E. Merian: Metals and their Compounds in the Environ-
ment Occurrence, Analysis, and Biological Rele-
vance, 2nd ed., VCH, Weinheim, Germany 1991.
38 E. Merian (ed.): Metalle in der Umwelt, VCH, Wein-
heim, Germany 1984.
39 R. G. Schwab, Was wissen wir uber die tieferen
Schichten der Erde ?, Angew. Chem. 86 (1974)
612 624.
40 C. Bresch, Zwischenstufe Leben, Piper-Verlag,
Munchen 1977.
41 W. Schreiter: Seltene Metalle, vol. 2, Dtsch. Verlag f.
Grundstofnd., Leipzig 1961.
42 H. Schneiderhohn: Erzlagerst atten, Fischer Verlag,
Stuttgart 1962.
43 V. Tafel: Lehrbuch der Metallh uttenkunde, vol. 1, Hir-
zel Vlg., Leipzig 1951.
44 A. Cissarz: Verbreitung der Platinmetalle, ihre la-
gerstattenkundliche Stellung und ihre Anteile an der
Weltproduktion, Erzmetall 25 (1972) 7 16.
45 Gesellschaft Deutscher Metallhutten- und Bergleute
(ed.): Edelmetalle Exploration und Gewinnung,
Schriftreihe der GDMB, no. 44, VCH, Weinheim,
Germany 1986.
46 W. Gocht: Handbuch der Metallm arkte-Erzvorkommen,
Metallgewinnung, Metallverwendung, Preisbildung,
Handelsregelungen, 2nd ed., Springer-Verlag, Berlin
1985.
47 F. Pawlek, Metallh uttenkunde, Walter de Gruyter Ver-
lag, Berlin 1983.
48 Winnacker-K uchler, 4th ed., 4, pp. 541 572.
49 R. L. Bates, J. A. Jackson (eds.): Glossary of Geology,
2nd ed., American Geological Institute, 1980.
50 J. R. Loebenstein: Mineral Commodity Proles, 1984,
Bureau of Mines, US Department of the Interior, Wa-
shington, annually.
51 V. I. Smirnov (ed.): Ore Deposits of the USSR, vol. II,
Pitman Publishing, 1977.
52 C. B. Coetzee: Mineral Resources of the Republic of
South Africa, Department of Mines, Pretoria 1976.
53 J. Lurie: South African Geology for Mining, Metallur-
gical, Hydrological and Civil Engineering, McGraw-
Hill, Johannesburg 1981.
54 W. Herzberg: Der Bergbau Sudafrikas, Metall 37
(1984) 407 411.
55 R. C. Hochreiter, D. C. Kennedy, W. Muir, A. I.
Woods: Platinum in South Africa, J. S. Afr. Inst. Min
& Metall. 85 (1985) no. 6, 165.
56 A. M. Edwards, M. H. Silk: Platinumin South Africa,
Mintek Special Publication, no. 12, Randburg 1987.
57 H. Renner, U. Trobs: Rohstoffprol Ruthenium, Me-
tall 42 (1988) 714 716.
58 H. Renner, U. Trobs: Rohstoffprol Osmium, Metall
44 (1990) 687690.
59 H. Renner, U. Trobs: Rohstoffprol Iridium, Metall
40 (1986) 726 730.
60 H. Renner, U. Trobs: Rohstoffprol Rhodium, Metall
38 (1984) 1002 1005.
61 O. Stoppinski: Platinum Group Metals, National Re-
search Council, Washington 1977.
62 Hargreaves, Williamson (eds.): The Platinum Industry,
Prospects in Recovery, Shearson/American Express,
London 1984.
63 L. B. Cabril: Platinum-Group Elements, The Canadian
Institute of Mining and Metallurgy, Ottawa 1981.
64 Metalle aus dem Meteoritenkrater Nickel, Kupfer,
und Platin in Sudburry, Neue Z urcher Zeitung 1990,
no. 258, Nov. 7.
65 T. P. Mohide: Platinum Group Metals Ontario and
the World, Ministry of Natural Resources, Ontario
1979.
66 Mintek: The Sucessful Development of an Industrial
Process for the Recovery of Platinum-group Metals from
the UG-2 Reef, Application Report, no. 1, Randburg,
1987.
Vol. 28 Platinum Group Metals and Compounds 381
67 Mintek: Recovery of PGMs from the UG-2 Reef,
Research Digest, no. 29, Randburg, 1988.
68 G. Hempel: Wozu Polarforschung ?, Erzmetall 37
(1984) 577 584.
69 H. Renner: Behandlung und Verwertung von verbrauch-
ten edelmetallhaltigen Katalysatoren, Mull- und Ab-
fallbeseitigung (Mullhandbuch), 2nd ed., no. 8595, E.
Schmidt-Verlag, Berlin 1987.
70 W. Hasenpusch: Aufarbeitung von Autoabgaskataly-
satoren Die oberirdische Platin-Mine, EFCE Publ.
Ser. 10 (1989) no. 79.
71 H. Giegerich, C. Hensel: Autokat-Recycling ein Bei-
trag zur kunftigen Edelmetallversorgung, Metall 44
(1990) 684 687.
72 G. A. Jensen: Platinum-group Metals as a Possible
Byproduct of Nuclear Reactions, Precious Met. Proc.
Int. Precious Met. Inst. Conf., 9th Meeting, Allentown,
Pa. 1985, 235 252.
73 G. Buckow et al.: Verwertung von Reststoffen aus einer
Wiederaufbereitungsanlage, Gesellschaft fur Reaktor-
sicherheit (GRS), Koln 1986.
74 H. Rothemeyer: Endlagerung radioaktiver Abf alle,
VCH-Verlagsges., Weinheim, Germany 1991.
75 R. Saager: Metallische Rohstoffe von Antimon bis Zir-
konium, Bank Vontobel, Zurich 1984.
76 V. E. McKelvey, E. N. Cameron: The Mineral Potential
of United States 1975 2000, University Wisconsin
Press, Madison 1973.
77 D. Meadows, E. Zahn, P. Milling: Die Grenzen des
Wachstums, 15th ed., Deutsche Verlagsanstalt, Stuttgart
1990.
78 L. Trueb: Das Platin und seine funf Geschwister einer
Geschichte der Platinmetalle, Neue Z urcher Zeitung
1989, no. 298 (Dec. 21).
79 L. Trueb: Platinmetalle Vom Bergwerk zum Kata-
lysator, Neue Z urcher Zeitung 1989, no. 194
(Jun. 14).
80 O. S. North: Mineral Exploration, Mining and Proces-
sing Patents, McGraw Hill, New York, annually.
81 E. Henglein: Lexikon Chemische Technik, VCH, Wein-
heim, Germany 1988.
82 G. Agricola: VomBerg- undH uttenwesen, DTV-Verlag,
Munchen 1980.
83 W. Truthe: Hundert Jahre Gold- und Silber-Scheidung
nebst Gewinnung der Platinmetalle, Degussa 1943,
unpublished.
84 E. Jackson: Hydrometallurgical Extraction and Recla-
mation, Ellis Horwood, Chichester 1986.
85 E. M. Savitskii: Handbook of precious metals, Hemi-
sphere Publishing Corp., New York 1989.
86 J. C. Mostert, P. N. Roberts: Electric Smelting at
Rustenburg PlatinumMines Ltd. of Nickel-Copper Con-
centrates containing Platinum Group Metals, J. S. Afr.
Inst. Min. Metall. 73 (1973) no. 9, 290.
87 C. F. Brugman, D. G. Kerfoot, Treatment of Nickel-
Copper Matte at Western Platinum by the Sherritt
Acid Leach Process, International Nickel Conference,
Toronto, Canada, 1985.
88 Degussa: Metall Forschung und Entwicklung im
Degussa-Forschungszentrum Wolfgang, Frankfurt
1991.
89 G. Schlamp: Noble Metals and Their Alloys, in R.
Cahn (ed.): Materials Science and Technology, vols.
8/9, Structure and Properties of Nonferrous Metals,
VCH, Weinheim, Germany 1995, pp. 467 587.
90 T. B. Massalski (ed.): Binary Alloys Phase Diagrams,
vols. 1 and 2, ASM Metals Park, OH 1986.
91 T. B. Massalski (ed.): et al. Noble Metal Alloys Phase
Diagrams, The Metallurgical Soc. USAWarrendale, PA
1986.
92 G. Petzow, G. Effenberg: Ternary Alloys, VCH, Wein-
heim, Germany 1988.
93 J. E. Hoffmann, J. Met. 40 (1988) no. 6, 40 44.
94 E. J. Kohlmeyer, K. von Sprenger, Z. Anorg. Chem. 257
(1948) 199 214.
95 V. Jung, J. Met. 33 (1981) no. 10, 42 44.
96 Degussa, DE 2 059 235, 1970 (V. Jung).
97 V. Jung: The Treatment of Automotive Exhaust Cat-
alysts, TMS/GDMB-Conference, Productivity and
Technology in the Metallurgical Industries, Koln, Sept.
1989.
98 D. Meredith et al., Stahl Eisen 17 (1988) 796
800.
99 S. E. Stenkvist, Steel Times, 1985, no. 10, 480 483.
100 Iron and Steel Society, Plasma Technology in Metallur-
gical Processing, Grand Junction, CO/USA, 1987.
101 Degussa, DE 3 223 501, 1983 (H. Renner, K. Kleis,
R. Schlodder).
102 W. C. Heraeus GmbH, DE 2 911 193, 1979.
103 International Precious Metals Institute (ed.): Current
Publications and Proceedings of Conferences and Semi-
nars, Dave Schneller, Boulder 1979, pp. 92 ff.
104 F. A. Cotton, G. Wilkinson: Advanced Inorganic Chem-
istry, 4th ed., John Wiley & Sons, New York 1980,
pp. 950 966.
105 F. A. Cotton, G. Wilkinson: Anorganische Chemie, 4th
ed., VCH, Weinheim, Germany 1985.
106 G. Wilkinson, R. D. Gillard, J. A. McCleaverty: Com-
prehensive Coordination Chemistry, vol. 5, Pergamon
Press, Oxford 1987.
107 F. R. Hartley: The Chemistry of PlatinumandPalladium,
John Wiley & Sons, New York 1973.
108 S. E. Livingstone, in J. C. Bailar et al. (eds.): Compre-
hensive Inorganic Chemistry, vol. III. Pergamon Press,
New York 1973, pp. 163 1370.
109 N. N. Greenwood, A. Earnshaw: Chemie der Elemente,
VCH, Weinheim, Germany 1988.
110 S. Daamach, G. Cote, D. Bauer: Separation of Plati-
num-group Metals in Hydrochloric media: Solvent Ex-
traction of Palladium(II) with Dialkyl Suldes, IPMI
1977, No. 22.
111 D. W. Agers, E. R. de Ment: The Evaluation of New
LIX Reagents for the Extraction of Copper and Sugges-
tions for the Design of Commercial Mixer-Settler
Plants, The Metallurgical Society of AIME, Paper
no. A 72 82, 1972.
382 Platinum Group Metals and Compounds Vol. 28
112 Matthey Rustenburg Ref., GB 2 013 644, 1978 1979
(K. J. Shanton, R. A. Grant).
113 Matthey Rustenburg Ref., DE-OS2 459 099, 1973 1975
(J. B. Payne).
114 L. Manziek (ed.): Precious Metals Recovery and Re-
ning, Proceedings of the Precious Metals Recovery
and Rening Seminar, Nov. 12 14, 1989, Scottsdale,
Arizona.
115 V. H. Apprahamian, G. P. Demopoulos, G. B. Harris:
The Behavior of Impurities during the Solvent Extrac-
tion of Platinum Metals with TN 1911 Extractants in
Precious Metals 1991, IPMI, Allentown, Pa. 1991,
p. 143.
116 W. Hasenpusch: Die Trennung der Platinmetalle,
CLB, Chem. Labor Betr. 38 (1987) 454.
117 Ch. Baes, R. E. Mesmer: The Hydrolysis of Cations, J.
Wiley and Sons, New York 1976.
118 M. Knothe: Untersuchungen zum Verhalten des Rh,
Pd, Ir und Pt im Chloridmedium an Anionenaus-
tauschern, Z. Anorg. Allgem. Chem. 463 (1980)
204 212.
119 A. P. Evers, R. J. Edwards, M. Fieberg, DE
27 26 558 B 2, 1976/1981.
120 G. Schmuckler, US 4 885 143, 1989.
121 W. Prodinger: Organische F allungsmittel in der quan-
titativen Analyse, Enke Verlag, Stuttgart 1954.
122 J. Fries, H. Getrost, Organische Reagentien f ur die
Spurenanalyse, E. Merck, Darmstadt 1977.
123 D. A. Boyd: A Novel Approach to PGMRening, IPMI,
1992.
124 R. Marr, H.-J. Bart: Metallsalz-Extraktion, Chem.-
Ing.-Tech. 54 (1979) 119 129.
125 L. Alders: Liquid-Liquid Extraction Theory and Lab-
oratory Practice, Elsevier Publishing, Amsterdam
1959.
126 G. M. Ritcey, A. W. Ashbrook: Solvent Extraction:
Principles and Application to Process Metallurgy, Else-
vier, New York 1984.
127 F. Habashi: Hydrometallurgy, Principles of Extrac-
tive Metallurgy, vol. 2, Gordon and Breach, New York
1970.
128 G. H. Morrison, H. Freiser: Solvent Extraction in
Analytical Chemistry, J. Wiley & Sons, New York
1957.
129 E. J. Barnes, J. D. Edwards: Solvent Extractions at
Incos Acton Precious Metal Renery, Chem. & Ind.
(London) 1982 no. 3, 151 164.
130 R. J. Edwards: Rening of the Platinum-group Me-
tals, J. Met. 28 (1976) no. 8, 4 9.
131 R. J. Edwards: Selective Solvent Extractants for the
Rening of Platinum Metals, Proceedings of the Inter-
national Solvent Extraction Conference ISEC 7, Vol. 1,
CIM, Special Vol. 21, 24 (1979).
132 D. S. Flett: Solvent Extraction in Precious Metal Re-
ning, IMPT Seminar, London 1982.
133 E. M. Elkin, P. W. Bennett: A new Technique for the
Recovery of Palladium and Platinum from Gold Elec-
trolyte, J. Met. 17 (1965) no. 3, 252 254.
134 G. Brauer: Handbuch der pr aparativen anorganischen
Chemie, vol. 3, Enke, Stuttgart 1980.
135 R. Gilchrist: The Platinum Metals, Chem. Rev. 32
(1943) 277 372.
136 Matthey Rustenburg Ref., GB 2 065 092, 1980 (R. A.
Grant).
137 Matthey Rustenburg Reners: The Separation Chem-
istry of Rhodiumand Iridium, Proceeding of a Seminar
of the International Precious Metals Institute, IMPI,
Scottsdale, Arizona, 1989.
138 P. Charlesworth: Separating the Platinum Group Me-
tals by Liquid-Liquid Extraction, Platinum Met. Rev.
25 (1981) 106 112.
139 L. R. P. Reavill, P. Charlesworth: The Application of
Solvent Extraction to PlatinumGroup Metals Rening,
Proceedings of the International Solvent Extraction
Conference, ISEC 80 vol. 3, Liege 1980.
140 M. J. Clearne, P. Charlesworth, D. J. Bryson: Solent
Extraction in Platinum Group Metal Processing, J.
Chem. Technol. Biotechnol. 29 (1979) 210 214.
141 Matthey Rustenburg Ref., US 3 979 207, 1974 (J. J.
McGregor).
142 INCO, US 4 390 366, 1983 (R. K. Lea, J. D. Edwards,
D. F. Colton).
143 M. Fieberg, R. J. Edwards: The Extraction of Gold
from Chloride Solutions, Rep. Natl. Inst. Metall. (S.
Afr.) 1978, no. 1996.
144 A. S. Myerson, K. Toyokura (eds.): Crystallisation as a
Separations Process, ACS Symp. Ser. 438 (1990)
145 W. Gosele et al.: Feststoffbildung durch Kristallisa-
tion und Fallung, Chem.-Ing.-Tech. 62 (1990) 544
552.
146 W. Hasenpusch, K. Bonin: Kristallisation von Ammo-
nium-Hexachloroplatinat(IV), Chem.-Ztg. 1991, no. 5,
129 133.
147 M. Knothe, W. Hosenpusch, Inorg. Chem. 35 (1996)
4529 4530.
148 R. B. Wilson, W. D. Jacobs: Separation of Iridium
from Rhodium by Extraction with Tributyl Phosphate,
Anal. Chem. 33 (1961) 1650 1652.
149 S. J. Tanaka: The Recovery and Purication of Rhodi-
um using Superlig
TM
Technology from a Platinum-
group Metals Stream, IPMI 1992.
150 Matthey Rustenburg Ref., US 4 382 067, 1982 1983
(R. A. Grant).
151 Matthey Rustenburg Ref., DE-OS 2 457 672, GB
5 682 673, 1973 1979 (J. J. McGregor).
152 PGMIndustries, DE-OS 27 26 390, 1977 1979 (J. Baltz,
E. Coltrinari).
153 National Institute for Metallurgy (NIM), GB 1 490 815,
1974 1977 (R. J. Edwards).
154 AT & TTechnologies, US 4 479 922, 1983 (R. Haynes,
A. Jackson).
155 H. Renner: The Selective Solvent Extraction of Palla-
dium by the Use of Di-Normal-Hexylsulde, Rep.-
MINTEK, 1985, no. 217.
156 G. P. Demopoulos: Solvent Extraction in Precious
Metals Rening, J. Met. 1986 no. 6, 13 17.
Vol. 28 Platinum Group Metals and Compounds 383
157 G. P. Demopoulos: A Radically New Solvent Extrac-
tion Process for Rhodium Recovery, in Precious Me-
tals 1992, IPMI, 1992.
158 M. Grote, U. Huppe, A. Kettrop: Solvent Extraction of
Noble Metals by Formazons(II), Hydrometallurgy 19
(1987) 51 68.
159 K.-H. Konig: Zur Solventextraktion von Platinmetal-
len, Achema, Frankfurt 1985.
160 M. Knothe: Die Fallung des Pd
II
als Pd(NH
3
)
2
Cl
2
sowie
des Verhaltens verschiedener Begleitelemente, Z. An-
org. Allg. Chem. 503 (1983) 213 223.
161 A. P. Evers, R. J. Edwards, M. M. Fieberg, SA
7 63 681, 1976.
162 R. J. Edwards, M. M. Fieberg, W. te Riele, B. C. Want,
US 4 155 750, 1979.
163 A. Prior, K. H. Ohrbach, A. Kettrup, G. Matuschek:
Calcination of Platinum Group Metal Complexes to
Form Pure Metals, IPMI Seminar, 1988.
164 A. Prior, B. Lerwill: Cost Management Strategies in
Reneries in the 1990s, IPMI Seminar, Tempe, Ari-
zona, 1991.
165 V. S. Khain, E. V. Fomina: Reduction of OsO
4
by
Sodium Tetrahydroborate in Acidic Medium, Russ.
J. Inorg. Chem. (Engl. Transl.) 25 (1980) 307 308.
166 Degussa: Edelmetall-Taschenbuch, Frankfurt 1967.
167 Degussa: Edelmetall-Taschenbuch, 2. Au., Huthig-
Verlag, Heidelberg 1995.
168 E. M. Wise: Palladium, Academic Press, New York
1968.
169 J. A. Federov: Rhodium, Nauka Vlg., Moskau 1966.
170 A. F. Hollemann, E. Wiberg, N. Wiberg: Lehrbuch der
Anorganischen Chemie, 101. Au., W. de Gruyter,
Berlin New York 1995, pp. 1546 (Ru, Os), 1572 (Rh,
Ir), 1602 (Pd, Pt), 1628 1716 (Carbonyle).
171 J. Huheey, E. Keiter, R. Keiter (eds.): Anorganische
Chemie, 2. Au., W. de Gruyter, Berlin New York
1995, pp. 735 864.
172 A. S. Darling: Some Properties and Applications of the
Platinum Group Metals, Int. Met. Rev. 18 (1973) 91
122.
173 E. Raub: DieEdelmetalleundihreLegierungen, Springer-
Verlag, Berlin 1940.
174 E. Janeke: Kurzgefates Handbuch aller Legierungen,
C. Winter Verlag, Heidelberg 1949.
175 J. L. Haughton, A. Prince: The Constitution Diagrams of
Alloys, ABibliography, Institute of Metals, London1956.
176 A. Prince: Multicomponent Alloy Constitution, Bibliog-
raphy 1955 1973, Metals Society, London 1978.
177 A. Prince: Multicomponent Alloy Constitution, Bibliog-
raphy 1974 1977, Metals Society, London 1981.
178 W. Home-Rothery, G. V. Raynor: The Structure of
Metals and Alloys, Institute of Metals, London 1954.
179 M. Hansen: Der Aufbau der Zweistoff-Legierungen,
Springer-Verlag, Berlin 1936.
180 M. Hansen, K. Anderko: Constitution of Binary Alloys,
2nd ed., McGraw-Hill, New York 1958.
181 R. P. Eliott: Constitution of Binary Alloys, 1st suppl.,
McGraw-Hill, New York 1965.
182 F. A. Shunk: Constitution of Binary Alloys, 2nd suppl.,
McGraw-Hill, New York 1969.
183 W. G. Moffatt: The Handbook of Binary Phase Dia-
grams, General Electric Company, Schenectady, N.Y.,
1976 1977.
184 G. Petzow, G. Effenberg: Ternary Alloys, VCH, Wein-
heim, Germany 1988 onwards.
185 J. C. Chaston: The Purity of Platinum, Platinum Met.
Rev. 15 (1971) 122 128.
186 A. Wogrinz: Analytische Chemie der Edelmetalle, Enke
Verlag, Stuttgart 1936.
187 F. Ensslin: Edelmetall-Analyse, Springer-Verlag, Berlin
1964.
188 Chemikerausschu der GDMB (ed.): Analyse der Me-
talle, 2nd ed., Springer-Verlag, Berlin 1961.
189 F. E. Beamish, J. C. van Loon: Analysis of Noble Metals,
Academic Press, New York 1977.
190 S. Kallmann: A Survey of the Determination of the
Platinum Group Elements, Talanta 34 (1987) no. 8,
677 698.
191 H. G. Sigel, A. Sigel (eds.): Handbook on Toxicity of
Inorganic Compounds, Marcel Dekker, New York
1988.
192 E. D. Goldberg et al.: Determination of Platinum
Sediments, Anal. Chem. 58 (1986) 616 620.
193 H.-M. Luschow: Probenahme, Theorie und Praxis,
Schriftenreihe der GDMB, VCH, Weinheim 1980.
194 H.-M. Luschow: Zur Probenahme von Edelmetallen,
Teil 1: Probenahme von metallischen Materialien,
Erzmetall 42 (1989) 153 159.
195 H.-G. Bachmann, E. Koberstein, R. Straub: Chemie-
Technik 7 (1978) 441 446.
196 J. Suchomel, Fresenius Z. Anal. Chem. 300 (1980)
257 266; Fresenius Z. Anal. Chem. 307 (1981)
14 18.
197 B. Welz: Atomic Absorption Spectrometry, VCH, Wein-
heim, Germany 1985.
198 G. Jager: U

ber die Platinbestimmung in Platforming-


Katalysatoren, Dissertation, Mainz 1957.
199 W. Diehl: Die quantitative Bestimmung der Verunrei-
nigungen der AG, Au, Pt und Rh mit einem 3,4-m-
Gitterspektrographen, Metall (Berlin) 23 (1969)
587 589.
200 F. Mylius: Reinheitsgrade von Metallen des Handels,
Z. Anorg. Chem. 74 (1912) 407.
201 F. Mylius, A. Mazzuchelli: uber die Platinanalyse, Z.
Anorg. Allg. Chem. 89 (1914) 1 38.
202 DIN 43 760, 1968.
203 DIN 43 710, 1977.
204 Gmelin, Platin, suppl. vol. A 1, 8.
205 H. Wolf: Die Edelmetalle in Forschung und Industrie,
Metall 12 (1958) no. 7, 3 16.
206 J. Sagoschen: Platin-Laborgerate, Chem. Ztg. 88
(1964) 420 429.
207 G. Reinacher: Platin-Gerate im Labor, Chem. Anla-
gen Verfahren 1970, no. 1/2, 61 63.
208 Degussa: Platin-Ger ate f ur Labor und Praxis, no. 1 ff.,
Frankfurt 1977 ff.
384 Platinum Group Metals and Compounds Vol. 28
209 G. Reinacher: U

ber die Gewichtskonstanz von Geraten


aus der Legierung Platin/3 % Iridium bei analytischen
Operationen, Werkst. Korros. 1964, no. 1, 84 88.
210 G. Reinacher, H. Roters: Neuere Anwendungen von
Platinwerkstoffen in Chemie und Glasindustrie, Metall
23 (1969), 570 575.
211 G. Reinacher: Anwendung von Platin-Werkstoffen in
Glashutten, Chem. Anlagen Verfahren 1975, no. 10,
27 34.
212 D. Bottger: The Use of Platinumin the Glass Industry,
Glass 62 (1985) no. 5, 177 178; Metall 39 (1985)
748 750.
213 M. Rowe: Noble Metals in the Glass Industry, Ceram.
Eng. Sci. Proc. 6 (1985) 256 268.
214 W. Funk, R. Schumm: Spinndusen Bauteile fur die
Chemiefaserindustrie, Chemiefasern Text. Anwen-
dungstech./Text.-Ind. 22 (1972) 518 521.
215 J. R. Anderson, M. Baudart: Catalysis, Science and
Technology, vols. 12, Springer-Verlag, Berlin 1981.
216 Fonds der Chemischen Industrie: Katalyse, Foliens-
erie, no. 19, Frankfurt 1986.
217 K. Weissermel, H. J. Arpe: Industrial Organic Chemis-
try, VCH, Weinheim, Germany 1978.
218 P. N. Rylander: Catalysis Hydrogenation over Platinum
Metals, Academic Press, New York, 1967.
219 W. Holderich, M. Schearzmann, W. D. Mross: Hetero-
gene Katalysatoren in der chemischen Industrie, Erz-
metall 39 (1986) 292 298.
220 A. J. Bird, A. B. Stiles: Catalyst Supports and Supported
Catalysts, Butterworth, London 1987.
221 J. Falbe, U. Haserodt: Katalysatoren, Tenside und
Mineral oladditive, Thieme Verlag, Stuttgart 1978.
222 D. M. Little: Catalytic Reforming, Pennwall Pub., Tulsa
1985.
223 W. Ostwald, E. Brauer, in H. Huben (ed.): Festschrift
zum f unfzigj ahrigen Bestehen der Platinschmelze G.
Siebert GmbH, Hanau, Hanau 1931, pp. 240 256.
224 H. Holzmann: uber die katalytische Oxidation von
Ammoniak bei der industriellen Salpetersaure-Herstel-
lung, Chem.-Ing.-Tech. 39 (1967) 89 95.
225 F. Sperner, W. Hohmann: Rhodium-Platinum Gauzes
for Ammonia Oxidation, PlatinumMet. Rev. 20 (1976)
12 20.
226 H. Connor: The Role of PlatinumAlloys Gauzes in the
Ammonia Oxidation Process, Platinum Met. Rev. 11
(1967) 2 9, 60 69.
227 E. G. Schlosser: Die Katalysator-Desaktivierung und
-Vergiftung in verfahrenstechnischer Sicht, Chem.-
Ing.-Tech. 47 (1975) 997 1005.
228 R. Ugo: Aspects of Homogeneous Catalysis, D. Re-
ibel Publ, Dordrecht 1970.
229 F. J. Smith: New Technology for Industrial Hydrofor-
mulation, Platinum Met. Rev. 19 (1975) 93 95.
230 K.-H. Schmidt: Neuentwicklungen in der homogenen
Katalyse, Chem. Ind. 37 (1985) 762 765.
231 J. Osborn, G. Wilkinson, Chem. Commun. 1965, 131.
232 H. Brunner: Rhodium-Katalysatoren fur die enantio-
selektive Hydrosylierung ein neues Konzept zur
Entwicklung asymmetrischer Katalysatoren, Angew.
Chem. 95 (1985) 921 931.
233 G. J. K. Acres, B. J. Cooper: Automobile Emission
Control Systems, PlatinumMet. Rev. 16 (1972) 74 86.
234 W. Weigert, E. Koberstein, E. Lakatos: Katalysatoren
zur Reinigung von Autoabgasen, Chem.-Ztg. 97 (1973)
469 478.
235 O. Stopinski: Platinum-group Metals, National Re-
search Council, Washington 1977.
236 E. Koberstein: Katalysatoren zur Reinigung von Auto-
abgasen, Chemie in unserer Zeit 18 (1984) no. 2, 37
45.
237 A. Keil: Werkstoffe f ur elektrische Kontakte, Springer,
Berlin 1960.
238 A. von Krusenstjern: Edelmetall-Galvanotechnik,
Leuze-Vlg., Saulgau 1970.
239 D. Schlain et al.: Elektrodesposition of Platinum Me-
tals from Molten Cyanides, Platinum Met. Rev. 21
(1977) 38 42.
240 J. H. Notton: Fused Salt Platinum Plating for Industrial
Applications, Platinum Met. Rev. 21 (1977) 122 128.
241 H.-H. Beyer, F. Simon, Metall 34 (1980) 1016 1018.
242 J. Wurm, S. Sari: Verchromen mit platinierten Titana-
noden, Ober ache-Surf. 1989 no. 12, 19 21.
243 F. Endter: Die technische Synthese von Cyanwasserst-
off aus Methanund Ammoniakohne Zusatz vonSauerst-
off, Chem.-Ing.-Tech. 30 (1958) 305 310.
244 L. B. Hunt: The Platinum in the Decoration of Porce-
lain and Pottery, Platinum Met. Rev. 22 (1978) 138
148.
245 Degussa: Glanzgoldbel, Frankfurt 1979.
246 V. de Nora, J.-W. Kuhn-von Burgsdorff: Der Beitrag
der dimensionsstabilen Anoden (DSA) zur Chlortech-
nologie, Chem.-Ing.-Tech. 47 (1975) 125 128.
247 J.-W. Kuhn-von Burgsdorff: Anwendung dimensions-
stabiler Elektroden in der Elektrochemie, Chem. Ind.
(D usseldorf) 28 (1976) 406 408.
248 Johnson Mattey: Platinum, London, anually.
249 IMPT (ed.): Precious Metals New and Review, vol. 1
ff, Allentown, 1976 ff.
250 Degussa, Gesch aftsbericht, Frankfurt, annually.
251 Knies: Die Marktsituation der Edelmetalle, Metall,
annually.
252 J. H. Jolly: Platinum-group Metals, US Dep. of the
Interior, Bureau of Mines, Washington 1968 ff.
253 K. Bolz, U. Harms, P. Pissulla, H. Schmidt: Gold,
Platinmetalle und Diamanten in der sowjetischen Han-
delspolitik, Verlag Weltarchiv, Hamburg 1985.
254 H. Kutzer: Metalle zwischen Mangel und U

beru,
Handelsblatt-Schriftreihe, Dusseldorf, 1981.
255 F. H. Kemper: Metalle Belastung fur den
Menschen? Erzmetall 40 (1987) 541 549.
256 J. Pepys, C. A. C. Pickering, E. G. Hughes: Asthma due
to Inhaled Chemical Agents Complex Salts of Plati-
num, Clin. Allergy 2 (1972) 391 396.
257 M. C. Cleare, E. Hughes, B. Jacoby, J. Pepys: Imme-
diate (typ I) Allergic Responses to Platinum Com-
pounds, Clin. Allergy 6 (1976) 183 195.
Vol. 28 Platinum Group Metals and Compounds 385
258 Bundesverband der Pharmazeutischen Industrie: Rote
Liste Verzeichnis von Fertigarzneimitteln, Edition
Cantor, Aulendorf, annually.
259 A. I. G. McLaughlin et al.: Toxic Manifestations of
Osmium Tetroxide, Brit. J. Ind. Med. 2 (1946) 183.
260 G. Rosner, R. F. Hertel: Gefahrdungspotential von
Platinemissionen aus Autoabgas-Katalysatoren,
Staub-Reinhalt. Luft 46 (1986) 281 285.
261 A. Bartsch, C. Schlatter: Platinemissionen aus Auto-
mobil-Katalysatoren, Schriftenreihe Umweltschutz,
no. 55, Bundesamt fur Umweltschutz, Bern 1988.
262 W. Hasenpusch: Explosive Reactions with Platinum-
group metals, Chem.-Ztg. 111 (1987) 57 60.
263 W. Beck, W. Weigand: Chemistry of Platinum Me-
tals, Prax. Naturwiss. Chem. 40 (1991) 9 14.
264 S. D. Robinson, Annu. Rep. Prog. Chem., Sect. A: Inorg.
Chem. 85 (1988) 209 44.
265 S. D. Robinson, Annu. Rep. Prog. Chem., Sect. A: Inorg.
Chem. 87 (1990) 105 29.
266 S. D. Robinson, Annu. Rep. Prog. Chem., Sect. A: Inorg.
Chem. 88 (1991) 183 209.
267 D. T. Thompson, Annu. Rep. Prog. Chem., Sect. A:
Inorg. Chem. 89 (1992) 209 42.
268 G. Reid, Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.
90 (1993) 227 49.
269 M. A. Halcrow, Annu. Rep. Prog. Chem., Sect. A: Inorg.
Chem. 93 (1996) 241 267.
270 G. Reid, Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.
91 (1994) 261 94.
271 T. J. Ohara, Plat. Met. Rev. 39 (1995) 54 62.
272 T.-M. Park et al., Talanta 44 (1197) no. 6, 973 978.
273 M. J. Abrams, Plat. Met. Rev. 39 (1995) 14 18.
274 S. P. Fricker (ed.): Metal compounds in Cancer Therapy;
Metals in Health and Diseases Series, vol. 1, Chapman
and Hall, London 1994.
275 S. P. Fricker, Ruthenium, Nitric Oxide and Disease, Plat.
Met. Rev. 39 (1995) no. 4, 150 154.
276 M. J. Moss, Plat. Met. Rev. 39 (1995) 33 36.
277 G. R. Newcome et al., J. Chem. Soc., Chem. Commun.
(1993) 925.
278 G. R. Newcome et al., Macromol. Symp. 98 (1995)
467.
279 G. R. Newcome et al., Angew. Chem. Int. Ed. Engl. 34
(1995) 2023.
280 D. T. Thompson, Plat. Met. Rev. 40 (1996) 23 25.
281 D. T. Thompson, Plat. Met. Rev. 39 (1995) 108 11.
282 V. I. Sokolov, V. Bashilov, Plat. Met. Rev. 42 (1998)
18 24.
283 T. Lizhen, G. Jinxing, Plat. Met. Rev. 38 (1994) 98
108.
284 G. L. Selman, J. G. Day, A. A. Bourne, Plat. Met. Rev. 18
(1974) no. 2, 46 75.
285 Q. Zhang, D. Zhang, S. Jia, Plat. Met. Rev. 39 (1995)
167 171.
286 J. H. Kim, S.-C. Shin, Jpn. J. Appl. Phys. 35 (1996)
342 345.
287 Y. Tanaka et al., J. Magn. Magn. Mater. 170 (1997)
289 297.
288 T. N. Nguyen, P. A. Lee, H.-C. zur Loye, Science 271
(1996) 489 491.
289 G. Demazeau et al., J. Magn. Magn. Mater. 140 144
(1995) 165 166.
290 E. A. Franco-Ferreira, Plat. Met. Rev. 41 (1997) no. 4,
154 163.
291 R. W. Schutz, Plat. Met. Rev. 40 (1996) 54 61.
292 E. L. Semenova, N. Yu. Rusetskaya, V. M. Petyukh, V.
Ye. Listovnichiy, Plat. Met. Rev. 39 (1995) 174 179.
293 D. Goldberg, Y. Xu et al., Mater. Lett. 22 (1995) nos. 5,
6, 241 248.
294 E. Herda, R. Higuchi-Rusli, Parangtopo, Mater. Lett. 30
(1997) nos. 5, 6, pp. 347 350.
295 G. A. Moore, Trans. Electrochem. Soc. 75 (1939) 237
269.
296 F. A. Lewis: The Palladium Hydrogen System, Aca-
demic Press, New York 1967.
297 F. A. Lewis, Plat. Met. Rev. 38 (1994) 112 118.
298 G. Nelin, Phys. Stat. Solidi 45 (1971) no. 2, 527 536.
299 F. A. Lewis, Plat. Met. Rev. 26 (1982) 20 27, 70 78,
121 128.
300 J. B. Hunter, Plat. Met. Rev. 4 (1960) no. 4, 130
131.
301 A. G. Knapton, Plat. Met. Rev. 21 (1977) 44 50.
302 J. C. S. Booth, 11th World Hydrogen Energy Confer-
ence, Stuttgart, Germany, June 23 28, 1996.
303 E. Wicke, G. H. Nernst, Ber. Bunsenges. (1964) 224
235.
304 G. Sicking, Dissertation, Munster, Germany, 1970.
305 K. U. Neumann et al., J. Magn. Magn. Mat. 137 (1994)
no. 3, 264 268.
306 A. Freund et al., Catalysis Today 27 (1996) 279 283.
307 K.-A. Starz, Third European Precious Metals Confer-
ence, Florence, Sept. 17 19, 1997.
308 M. Watanabe, K. Tsurumi, T. Mizukami, T. Nakamura,
P. Stonehart, J. Electrochem. Soc. 141 (1994) no. 10,
pp. 2659 2668.
309 T. R. Ralph, Plat. Met. Rev. 41 (1997) 102 113.
310 M. P. Hoghart, G. A. Hards, Plat. Met. Rev. 40 (1996)
150 159.
311 M.-L. Tercier, N. Parthasarathy, J. Bufe, Electroanal-
ysis 7 (1995) no. 1, 55 63.
312 I. M. Wolff, P. J. Hill, Plat. Met. Rev. 44 (2000) 158
166.
313 H.-M. Luschow: Edelmetallanalytik, Eine U

bersicht
uber bew ahrte klassische und moderne Methoden, Heft
69 der Schriftenreihe der GDMB, Clausthal-Zellerfeld,
1993.
314 ISOStandard No. 11210, Determination of Platinumin
Platinum Jewellery Alloys Gravimetric method after
precipitation of diammonium hexachlorolatinate.
315 ISOStandard No. 11489, Determination of Platinumin
Platinum Jewellery Alloys Gravimetric Method after
Reduction with Mercury(I) Chloride.
316 ISO Standard No. 11494, Determination of Palladium
in Palladium Jewellery Alloys ICP-Solution-Spectro-
metric Method using Yttrium as Internal Standard
Element.
386 Platinum Group Metals and Compounds Vol. 28
317 ISOStandard No. 11495, Determination of Platinumin
Platinum Jewellery Alloys ICP-Solution-Spectromet-
ric Method using Yttrium as Internal Standard
Element.
318 J. Roberts et al.: Detection limits for trace elements in
high purity gold using a DC arc spectrograph with solid
state CIDdetection, Appl. Note No. 60, Thermo Jarrell
Ash Corp. Franklin, MA 1995.
319 G. Ertl, H. Knozinger, J. Weitkamp (eds.): Handbook
of Heterogeneous Catalysis, VCH, Weinheim,
Germany 1997. E. Drost et al., Platinwerkstoffe fur
Hochtemperatur-Einsatz, Metall 50 (1996) nos. 7/8,
492.
320 E. Auer, A. Freund, J. Pietsch, T. Tacke, Applied Catal-
ysis A 173 (1998) 259 271.
321 H. Lindlar, Helvetica Chimica Acta 35 (1952) 446
450.
322 B. Cornils, W. A. Hermann (eds.): Applied Homoge-
neous Catalysis with Organometallic Compounds,
VCH, Weinheim, Germany 1996.
323 J. H. Jones, Plat. Met. Rev. 44 (2000) 94 105.
324 G. W. Parshall, S. D. Ittel: Homogeneous Catalysis,
Wiley Interscience, New York 1992.
325 B. Cornils, W. A. Hermann (eds.): Aqueous-Phase Or-
ganometallic Catalysis, Wiley-VCH, Weinheim, Ger-
many 1998.
326 B. Marciniec (ed.): Comprehensive Handbook on Hy-
drosilylation, Pergamon Press, Oxford 1992.
327 I. Ojima (ed.): Catalytic Asymmetric Synthesis, Wiley,
New York 1993.
328 R. Noyori (ed.): Asymmetric Catalysis in Organic Syn-
thesis, Wiley, New York 1994.
329 B. M. Trost, D. L. van Vranken, Angew. Chem. Int. Ed.
Engl. 31 (1992) 228.
330 O. Loiseleur, M. Hayashi, N. Schmees, A. Pfaltz, Syn-
thesis (1997) 1338.
331 D. B. Vineyard, W. S. Knowles, M. J. Sabacky, G. L.
Bachmann, D. J. Weinkauf, J. Am. Chem. Soc. 99 (1977)
5946.
332 A. Miyashita et al., J. Am. Chem. Soc. 102 (1980) 7932.
333 H. Takaya et al., J. Org. Chem. 51 (1986) 629.
334 U. Nagel, E. Kinzle, J. Andrade, G. Prescher, Chem. Ber.
119 (1986) 3326.
335 A. Togni, Angew. Chem. 108 (1996) 1581.
336 M. Burk, J. E. Feaster, R. L. Harlow, Organometallics 9
(1990) 2653.
337 M. J. Burk, J. Am. Chem. Soc. 113 (1991) 8518.
338 E. Lox, K. Ostgathe, P. Zelenka: Reduction of Diesel
Exhaust Emission by Using Oxidation Catalysis, SAE
Tech. Pap. Ser. 1990, 902 111.
339 B. H. Engler, E. Lox, K. Ostgathe, W. Cartellieri, P.
Zelenka: Diesel Oxidation with LowSulfate Formation
for HD-Diesel Engine Application, SAE Tech. Pap.
Ser. 1991, 910 607.
340 B. H. Engler, E. Lox, K. Osthgathe, T. Ohata, K.
Tsuchitani, S. Ichihara, G. Garr, D. Psaras: Recent
Trends in the Application of Tri-Metal Emission Control
Catalysts, SAE Tech. Pap. Ser. 1994, 940928.
341 J. Leyrer, E. Lox, W. Strehlau: Design Aspects of Lean
NO
x
-Catalysts for gasoline and Diesel Engine Applica-
tions, SAE Tech. Pap. Ser. 1995, 952 495.
342 D. Lindner, E. Lox, R. v. Yperen, K. Ostgathe, T.
Kreuzer: Reduction for Exhaust Gas Emissions by
Using Pd-based Three-way Catalysts, SAE Tech. Pap.
Ser. 1996, 960 802.
343 W. Strehlau, J. Leyrer, E. Lox, T. Kreuzer, M. Hori, M.
Hoffmann: NewDevelopments in Lean-NO
x
Catalysis
for Gasoline Fueled Passenger Cars in Europe, SAE
Tech. Pap. Ser. 1996, 962 047.
344 W. Strehlau, J. v. d. Tillaart, J. Leyrer, E. Lox, W.
Muller: Evaluation of NO
x
-Storage Catalysis for Lean
Burn Gasoline Fueled Passenger Cars, SAE Tech Pap.
Ser. 1997, 970 465.
345 L. Mumann, D. Lindner, E. Lox, R. v. Yperen, T.
Kreuzer, I. Mitsushima: The Role of Zirconium in
Novel Three-way Catalysts, SAE Tech. Pap. Ser.
1997, 970 746.
346 B. Wu, G. Liu, Plat. Met. Rev. 41 (1997) 81 85.
347 J. Kondo, Progr. Theor. Physics 34 (1965) 372 382.
348 W. Diehl, Degussa Edelmetalltaschenbuch, Huthig
Verlag, Heidelberg 1995, p. 468.
349 A. Mills, Plat. Met. Rev. 41 (1997) 115 127.
350 J. N. Huiberts et al., Nature 380 (1996) 231 234.
351 R. Giessen, Phys. Bl. 53 (1997) 1207 1212.
352 A. Remhof, Phys. Rev. 56 (1997) 2897 2899.
353 T. J. Ohara, Plat. Met. Rev. 39 (1995) 54 62.
354 T.-M. Park et al., Talanta 44 (1997) no. 6, 973 978.
355 K. Lutz, Hagener Symp. Pulvermet. November 19th/
20th Hagen, 1998.
356 H. N. Shareef, K. R. Bellur, A. I. Kingon, O. Auciello,
Appl. Phys. Lett. 66 (1995) 239 241.
357 M. Gratzel, Plat. Met. Rev. 38 (1994) 151 159.
358 M. Gratzel in R. D. McDonell (ed.): AIP Conf. Proc.
404: Future GenerationPhotovoltaic Technologies: First
NREL Conference, Colorado October 1997, 156396
7049, pp. 119 126.
359 K. Sayama, H. Arakawa, J. Chem. Soc. Faraday Trans.
93 (1997) no. 8, 1647 1654.
360 K. Gurunathan, P. Maruthamuthu, M. V. C. Sastri, Int. J.
Hydrogen Energy 22 (1997) no. 1, 57 62.
361 M. Misara, R. N. Pandey, O. N. Srivastava, Int. J.
Hydrogen Energy 22 (1997) no. 5, 501 508.
362 L. Shivalingappa, J. Sheng, T. Fukami, Vacuum 48
(1997) no. 5, 413 416.
363 T. Maruyama, T. Yamamoto, J. Phys. Chem. B. 101
(1997) no. 19, 3806.
364 R. Argazzi et al., J. Phys. Chem. B 101 (1997) no. 14,
2591 2597.
365 V. Grosshenny, A. Harriman, M. Hissler, R. Ziessel,
Plat. Met. Rev. 40 (1996) 26 35, 72 77.
366 K. Takemura et al., Jpn. J. Appl. Phys. 34 (1995) 5224
5229.
367 P. Zalm, J. A. van Stratum, Philips techn. Rev. 27 (1966)
nos. 3/4, 69 75.
368 F. H. Reid: Electrodeposition of the Platinum Group
Metals, Metallurg. Rev. 8 (1963) 167.
Vol. 28 Platinum Group Metals and Compounds 387
369 F. H. Reid: Platinum Metal Plating A Process and
Application Survey, Trans. Inst. Met. Finish. 48 (1970)
115.
370 Johnson Matthey & Co., GB 363 569, 1931 (A. R.
Powell, A. W. Scott).
371 Engelhard Ind. Inc., FR 1 273 663, 1960 (H. W.
Robinson).
372 Johnson Matthey, EP 358 375, 1996 (J. M. Albon, W. J.
Davis, P. E. Skinner, S. G. Warren).
373 P. E. Skinner: Platinum Met. Rev. 33 (1989) 102.
374 F. H. Reid: Some Experimental and Practical Aspects
of Heavy Rhodium PLating, Trans. Inst. Met. Finish.
33 (1956) 105.
375 M. Danemark, Y. Rusconi: Rhodium Eigenschaften
und elektrolytische Abscheidung, Galvanotechn.
Ober achensch. 3 (1062) 287.
376 M. Branik, F. Kummer: Die galvanische Rhodiu-
mabscheidung, Galvanotechnik 72 (1981) 1175.
377 F. H. Reid: PalladiumPlating Processes and Applica-
tions in the United Kingdom, Plating 52 (1965) 531.
378 J. A. Abys: Palladium Plating, Plat. Surf. Finish. 82
(1995) no. 8, 67.
379 P.Wilkinson: The Replacement of Gold by Palladi-
um Nickel on Connectors, Trans. Inst. Met. Finish.
65 (1987) 33.
380 K. J. Whitlaw: Gold-Flashed Palladium Nickel for
Electronic Contacts, Trans. Inst. Met. Finish. 64 (1986)
62.
381 F. H. Reid, J. C. Blake: Electrodeposition of Rutheni-
um, Trans. Inst. Met. Finish. 38 (1961) 45.
382 G. S. Reddy, P. Taimsalu: Electrodeposition of Ruthe-
nium, Trans. Inst. Met. Finish. 47 (1969) 187; US 3
576 724, 1971.
383 A. F. Bogenschutz, J. L. Jostan, W. Mussinger: Galva-
nische Abscheidungen von Rutheniumschichten, Gal-
vanotechnik 67 (1976) 98.
384 G.-B. Dick: Galvanische Abscheidungen von Platin
durch Hochtemperaturelektrolyse, Galvanotechnik 79
(1988) 4066.
385 G.-B. Dick: Galvanische Abscheidungen von Platin,
Tantal und Iridium durch Hochtemperaturelektrolyse,
Galvanotechnik 86 (1995) 1427.
386 Degussa, DE 196 17 040, 1998 (L. van Hippel, C. Bus-
sek, J. Sauer, M. Sauer, D. Arntz).
387 H. Marquardt, G. Schafer (eds.): Lehrbuch der Toxiko-
logie, Wiss.-Verl., Mannheim 1994.
388 J. Messerschmidt et al., Fresenius J. Anal. Chem. 343
(1992) 391.
389 E. Merian (ed.): Metals and Their Compounds in the
Environment, VCH, Weinheim, Germany 1991.
390 U. Forstner: Umweltschutztechnik, 4. Au., Springer
Verlag, Berlin 1993.
391 Gesellschaft fur Strahlen- und Umweltforschung (GSF)
und Forschungszentrum Julich (eds.): Edelmetallemis-
sionen, Zwischenbericht GSF, Munchen 1990.
392 J. Angerer, J. Schaller: Akute und chronische Toxizitat
von Spurenelementen, Schriftenreihe der Gesellschaft
fur Mineralstoffe und Spurenelemente e.V., XIV, Wis-
senschaftliche Verlagsgesellschaft, Stuttgart 1993,
p. 214.
393 Bundesgesundheitsamt (BGA; ed.): Legierungen in der
zahnarztlichen Praxis, Informationsschrift des Bundes-
gesundheitsamtes, BGA Berlin 1993.
Further Reading
A. Bonetti, R. Leone, F. Muggia, S. B. Howell (eds.): Plati-
num and Other Heavy Metal Compounds in Cancer
Chemotherapy, Humana Press, New York, NY 2009.
C. M. Giandomenico: Platinum-Group Metals, Compounds,
Kirk Othmer Encyclopedia of Chemical Technology,
5th edition, vol. 19, p. 635667, John Wiley & Sons,
Hoboken, NJ, 2006, online: DOI: 10.1002/
0471238961.1612012007090114.a01.
R. J. Seymour, J. I. OFarrelly: Platinum-Group Metals,
Kirk Othmer Encyclopedia of Chemical Technology,
5th edition, vol. 19, p. 596635, John Wiley & Sons,
Hoboken, NJ, 2006, online: DOI: 10.1002/
0471238961.1612012019052513.a01.pub2.
F. Zereini, F. Alt (eds.): PalladiumEmissions in the Environ-
ment, Springer, Berlin 2006.
388 Platinum Group Metals and Compounds Vol. 28

You might also like