Platinum Group Metals and Compounds: Article No: A21 - 075

Article No : a21_075
Platinum Group Metals and Compounds

HERMANN RENNER, Degussa AG, (retired), Hanau, Federal Republic of Germany
uNTHER SCHLAMP, Demetron GmbH, (retired), Hanau, Federal Republic of Germany
G€
€
INGO KLEINWACHTER , dmc2 Degussa Metals Catalysts Cerdec AG, Hanau, Federal
Republic of Germany
ERNST DROST, dmc2 Degussa Metals Catalysts Cerdec AG, Hanau, Federal Republic of
Germany
uSCHOW, Degussa-H€uls AG, (retired), Hanau, Federal Republic of
HANS MARTIN L€
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 KN€ oDLER, Forschungsinstitut f€ur Edelmetalle und Metallchemie, (retired),
Schw€abisch Gm€und, 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 Universit€at, Jena, Federal Republic of
Germany
RAINER SCHIELE, Klinikum der Friedrich Schiller Universit€at, Jena, Federal Republic of
Germany
1. History . . . . . . . . . . . . . . . . . . . . . . . . . 318 3.6. Reserves and Resources . . . . . . . . . . . . . 330

2. Properties . . . . . . . . . . . . . . . . . . . . . . . 321 4. Mineral Dressing and Beneficiation . . . . 331
3. Occurrence . . . . . . . . . . . . . . . . . . . . . . 323 4.1. Treatment of Alluvial Platinum Deposits 331
3.1. Abundance . . . . . . . . . . . . . . . . . . . . . . 323 4.2. Treatment of Primary Deposits . . . . . . 331
3.2. Ores and Their Origin . . . . . . . . . . . . . 325 4.3. Treatment of Nickel Ores . . . . . . . . . . . 332
3.3. Primary Deposits . . . . . . . . . . . . . . . . . 326 4.4. Treatment of Metal Scrap . . . . . . . . . . 333
3.4. Secondary Deposits . . . . . . . . . . . . . . . . 328 4.5. Treatment of Dross . . . . . . . . . . . . . . . . 333
3.5. Recovery of Secondary Platinum Group 4.6. Treatment of Supported Catalysts . . . . 334
Metals . . . . . . . . . . . . . . . . . . . . . . . . . . 328 4.7. Treatment of Solutions . . . . . . . . . . . . . 334
2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a21_075
318 Platinum Group Metals and Compounds Vol. 28
5. Dissolution Methods . . . . . . . . . . . . . . . 335 8.3. Methods of Treatment . . . . . . . . . . . . . 361

5.1. Dissolution in Aqua Regia . . . . . . . . . . . 335 9. Quality Specifications and Analysis . . . 361
5.2. Dissolution in Hydrochloric Acid – 9.1. Quality Specifications . . . . . . . . . . . . . . 361
Chlorine. . . . . . . . . . . . . . . . . . . . . . . . . 335 9.2. Qualitative Analysis . . . . . . . . . . . . . . . . 362
5.3. Dissolution in Hydrochloric Acid – 9.3. Quantitative Analysis . . . . . . . . . . . . . . 362
Bromine . . . . . . . . . . . . . . . . . . . . . . . . . 336 9.4. Purity Analysis . . . . . . . . . . . . . . . . . . . 363
5.4. Other Dissolution Processes . . . . . . . . . . 336 9.5. Trace Analysis . . . . . . . . . . . . . . . . . . . . 364
5.5. Dissolution by Salt Fusion . . . . . . . . . . 336 10. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . 364
6. Separation of Platinum Group Metals . 337 10.1. Jewelry, Coinage, Investment . . . . . . . . 364
6.1. Chemistry of Platinum Group Metal 10.2. Apparatus . . . . . . . . . . . . . . . . . . . . . . . 364
Separation . . . . . . . . . . . . . . . . . . . . . . 337 10.3. Heterogeneous Catalysts . . . . . . . . . . . . 365
6.2. Older Separation Processes . . . . . . . . . 340 10.4. Fuel Cells. . . . . . . . . . . . . . . . . . . . . . . . 368
6.3. Current Separation Processes . . . . . . . . 341 10.5. Homogeneous Catalysts . . . . . . . . . . . . 368
6.4. Processes Used in Coarse Separation . . 343 10.6. Automotive Emission Control Catalysts 369
6.5. Purification . . . . . . . . . . . . . . . . . . . . . . 346 10.7. Sensors . . . . . . . . . . . . . . . . . . . . . . . . . 369
6.6. Conversion of Salts into Metals . . . . . . 348 10.8. Electrical Technology . . . . . . . . . . . . . . 371
6.7. Partial Purification . . . . . . . . . . . . . . . . 350 10.9. Electronics . . . . . . . . . . . . . . . . . . . . . . . 372
6.8. Treatment of Internally Recycled Material 350 10.10. Coatings . . . . . . . . . . . . . . . . . . . . . . . . 374
6.9. Construction Materials . . . . . . . . . . . . . 350 10.10.1. Coatings Produced by Electrolysis . . . . . . 375
7. Platinum Group Metal Compounds . . . 351 10.10.2. Coatings Produced by Chemical Reaction 376
7.1. Inorganic Compounds . . . . . . . . . . . . . . 351 10.10.3. Coatings Produced by Physical Methods . 376
7.1.1. Platinum Compounds. . . . . . . . . . . . . . . . 351 10.11. Dental Materials . . . . . . . . . . . . . . . . . . 376
7.1.2. Palladium Compounds . . . . . . . . . . . . . . 352 11. Economic Aspects . . . . . . . . . . . . . . . . . 377
7.1.3. Rhodium Compounds . . . . . . . . . . . . . . . 353 11.1. Supply . . . . . . . . . . . . . . . . . . . . . . . . . . 377
7.1.4. Iridium Compounds . . . . . . . . . . . . . . . . . 353 11.2. Demand . . . . . . . . . . . . . . . . . . . . . . . . . 378
7.1.5. Ruthenium Compounds . . . . . . . . . . . . . . 354 11.3. Prices . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
7.1.6. Osmium Compounds . . . . . . . . . . . . . . . . 354 11.4. Commercial Aspects . . . . . . . . . . . . . . . 378
7.2. Organic Compounds . . . . . . . . . . . . . . . 354 12. Toxicology . . . . . . . . . . . . . . . . . . . . . . . 379
8. Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . 355 References . . . . . . . . . . . . . . . . . . . . . . . 380
8.1. Alloy Systems. . . . . . . . . . . . . . . . . . . . . 355
8.2. Special Alloys. . . . . . . . . . . . . . . . . . . . . 356
1. History [1–10], [166], [167] gold with a blowpipe, these methods being simi-
lar to those used in gold extraction and working.
Figure 1 gives an historical survey of important Pre-Columbian Indians were familiar with a
platinum group metal discoveries and platinum powder metallurgy technique.
group metal technology.
16th–18th Century [11], [12]. In their
Early Times. The earliest evidence of plat- search for gold in the New World, particularly
inum is provided by a gold etui covered with in the area of present-day Colombia, the Spanish
hieroglyphic inscriptions, dating from the 7th often found alluvial (‘‘placer’’) platinum. The
century B.C. Around 1900, BERTHELOT (1827 – earliest written report of the metal was made in
1907) investigated the etui, which was kept in the 1557 by J. C. SCALIGER (1484 – 1558). Howev-
Louvre, and found that some of the inlays hith- er, platinum was worked to produce jewelry and
erto thought to be silver were in fact platinum. utensils only after man had learned that the metal,
In ca. 1900, jewelry made of native platinum initially believed to be infusible, could be melted
was discovered in Ecuador, which was part of the and cast by first adding other metals to lower its
Inca empire in pre-Columbian times. This prob- melting point. Platinum was essentially regarded
ably dates from the first five centuries A.D. as a troublesome material, accompanying gold
In ancient times, the technique of washing and silver, which lowered their workability. The
river sands and fusing together the grains of Spanish named the metal platina, the diminutive
platinum was undoubtedly known, as was the form of plata (silver), as a derogatory term
making of alloys by heating alluvial platinum and because it was found only in small quantities or
Vol. 28 Platinum Group Metals and Compounds 319
Figure 1. Historical survey of important platinum group metal discoveries and platinum group metal technology
as small granules. The terms ‘‘white gold’’ and established: dissolving the raw material in aqua
‘‘heavy silver’’ were also sometimes used. When regia, purifying it by precipitation of ammonium
the metal became well known in Europe in 1748, hexachloroplatinate, (NH4)2[PtCl6], and heating
thanks to the Spanish mathematician A. DE this strongly to form platinum sponge. In 1817,
ULLOA (1716 – 1795), the demand for platinum this led to the formation of Johnson, Matthey &
increased. Its high density enabled it to be used to Co., London [13], which laid the foundation of
adulterate gold, and its introduction into Europe modern platinum technology.
was therefore prohibited. Until 1908, the price of Until the beginning of the 19th century, al-
platinum was lower than that of gold. Around most all platinum was obtained from the area
1750, the scientific investigation of platinum now known as Colombia, which from 1739 to
began, initiated largely by C. WOOD (1702 – 1819 belonged to the Spanish Crown Dependen-
1774), who learned of the metal in Jamaica in cy of New Granada. At this time, ca. 1 t/a
1741. He can be regarded as the true discoverer of of platinum was extracted. ALEXANDER VON
platinum, having presented a paper in 1750 to the HUMBOLDT was the most accomplished prospec-
Royal Society entitled ‘‘The New Semi-Metal tor and developer of noble-metal deposits in
Called Platina.’’ In this initial period, fundamen- New Granada (1819) and of the newly discovered
tal investigations into the chemistry of platinum platinum deposit in the Urals. In 1819, platinum
(solubility in aqua regia, precipitation by addi- was extracted from alluvial gold, but soon after
tion of ammonium chloride, fusion by addition of this, the main production was switched to plati-
arsenic, lead cupellation, etc.) were carried out num placers with low gold content. In 1825,
by W. WATSON (1715 – 1787), W. LEWIS Russia became the primary producer of platinum.
(1708 – 1781), and others. These workers, in- The minting of platinum coins in Russia in
cluding WOOD, often collaborated. Research at 1828 – 1845 necessitated an increase in produc-
this time had as its primary aim, distinguishing tion, which reached 3.5 t in 1843 [14–16].
and separating platinum and gold, although plat- Almost all Russian platinum ore was used for
inum was at first widely believed to consist of coinage (15 t total). Technology for the extrac-
gold contaminated with other elements. tion and treatment of placer deposits had reached
An important development in platinum tech- a high standard by this time.
nology was the technique of converting the allu- After the closing of the refinery in St. Peters-
vial (placer) deposits into platinum sponge, burg, which was associated with the local mint
which could be satisfactorily formed by heat into and produced a metal of ca. 97 % platinum, 1.2 %
compact platinum or platinum artifacts. F. C. iridium, 0.5 % ruthenium, 0.25 % palladium,
ACHARD (1753 – 1821) discovered the method 1.5 % iron, and 0.4 % copper, the refining and
of oxidizing an easily fusible platinum – arsenic working of Russian platinum ore were carried out
alloy to remove arsenic. As early as 1784, he almost exclusively in Western Europe. New
produced the first platinum crucible from plati- companies for the refining and working of plati-
num sponge made in this way. num were founded, including Desmoutis, Paris
(1822); Baker & Co., New York (from 1904:
19th Century. Around 1800, the accompa- Engelhard, Newark, New Jersey); Heraeus,
nying metals in native platinum, which generally Hanau (1851); Siebert, Hanau (1881; from
contains up to 80 % Pt, were discovered. W. H. 1930 part of Degussa, Frankfurt); J. Bishop &
WOLLASTON (1766 – 1828) discovered palladium Co., Malverne, Pennsylvania and others.
(initially also known as ‘‘new silver’’) and rho-
dium; S. TENNANT (1761 – 1815) discovered 20th Century [17–20]. The platinum indus-
iridium and osmium. At the same time, the try grew vigorously after 1880 due to increasing
existence of platinum as a true element was demands of the electrical industry, dentistry, and
established. C. CLAUS (1796 – 1864) discovered chemical technology. The primary consumer was
ruthenium in 1844. the United States. In 1913, annual production of
In 1823, J. W. DOEBREREINER (1780 – 1849) crude platinum reached 7 t. At this time, Russia
first used the catalytic action of platinum in the began to make itself less dependent on other
gas lighter named after him. In about 1810, the countries by constructing a modern platinum
process invented by W. H. WOLLASTON became refinery and smelting point at Ekaterinburg (now
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 refined 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
Figure 2. History of world platinum output (including GUS
important. Today, a large proportion of the plati- sales to Western World)
num group metals supplied by the CIS comes
from sulfidic nickel deposits. For some decades,
the Soviet Union has been one of the largest (mainly for catalysts for ammonia oxidation) and
producers of platinum and especially palladium. high prices, the result being the foundation of
Production figures are not available thus far. about 50 producing companies. The primary
Estimates are approximate and are based on platinum-bearing rock typical of South African
export figures. deposits presented the ore treatment and smelting
During World War I, the demand for nickel technologies with completely new problems.
increased, and Canada became an important Technical difficulties combined with a fall in the
producer of palladium and platinum, because price of platinum led to a slump. The largest of
nickel ores also contained platinum group me- the surviving companies formed Rustenburg
tals. Since 1890, these ores have been extracted Platinum Mines Ltd. in 1931, whose output
by the Mond Nickel Co. (since 1961, INCO, reached 3 t/a during World War II.
London), later allied with the International Nick- After World War II, the Union of South Africa
el Co. of Canada. From 1925, platinum metals (Republic of South Africa) became the main
were produced in their own refinery in Acton in producer of platinum. From 1969, all of the crude
London. Another important producer of platinum platinum produced by South Africa was refined
is Falconbridge Nickel Mines in Toronto. by Johnson Matthey in England, although
After World War I, worldwide demand could Matthey Rustenburg Refiners now refines con-
no longer be satisfied by Russia and other pro- siderable quantities of material produced in
ducers, and new sources were developed. In Rustenburg. Recently, some new producers have
South Africa, the search was particularly well appeared in South Africa [e.g., Impala Platinum,
rewarded. Platinum and osmiridium were dis- Western Platinum (a subsidiary of Lonrho and
covered at Black Reef (1888), Witwatersrand Falconbridge), and Anglo-Transvaal Consolidat-
(1892), Great Dyk (Rhodesia, 1918), and later ed Investment (Anglovaal) and its subsidiary
at Waterberg. The award of prospecting rights to Atok Platinum Mines].
private persons led to prospecting on a wide Figure 2 shows the history of world platinum
scale. A systematic geological survey of the output, and Table 1 lists the development of PGM
Bushveld by J. MERENSKY was highly successful, production according to region.
leading to the discovery of platinum in the dunite
pipes (1924) and subsequently in the stratiform
platinum deposits known as the Merensky Reef 2. Properties [166], [167]
(1925), the largest platinum deposit in the world.
This discovery brought about the greatest Atomic Properties [21], [22]. The electron-
upheaval yet seen in the platinum market. It ic structures of platinum group metals start from
occurred during a period of both high demand the inert gas structures of krypton and xenon:
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.
The other properties typical of transition metals are

Ru [Kr] 4 d7 5 s1
Os [Xe] 4 f 14 5 d6 6 s2 very marked; for example, catalytic activity due to
Rh [Kr] 4 d8 5 s1 their readiness to change valence, formation of
Ir [Xe] 4 f 14 5 d7 6 s2 intermediate compounds with different reagents,
Pd [Kr] 4 d 10
color, paramagnetism due to unpaired electrons,
Pt [Xe] 4 f 14 5 d9 6 s1
and strong tendency to form complexes.
Comparisons within the group of platinum
Two valence orbitals exist: an s shell and an metals, also including neighboring elements,
inner d shell. The small energy difference be- often give an insight into the relationship be-
tween them means that the electron shells are tween electronic configuration and chemical
filled in inconsistently, so that with some ele- properties.
ments, one or both electrons from the outer 5 s or Many properties show marked similarities
6 s shells are taken up by the 4 d or 5 d shells. along the two horizontal rows:
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 f14 electron orbitals of the Also, the tendency toward complex formation
‘‘heavy’’ elements Os, Ir, Pt (see ‘‘Lanthanide and higher oxidation states is more marked in the
contraction’’). Due to the electronic structure of row of heavy elements than in the row of light
these elements, which is also determined by elements.
relativistic phenomena, causing splitting of p- Vertical similarities between the elements
and d-orbitals to altered energy levels, they show, also occur (e.g., in their behavior toward acids;
compared to the ‘‘light’’ platinum group ele- (see Table 3):
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 Similarities also exist in the following diago-
states occur. The following oxidation states are nal sequence, sometimes with ruthenium and
known in the compounds of platinum group iridium changing places:
metals (principal oxidation states in bold print):
Ru: 2, 0, þ2, þ3, þ4, þ5, þ6, þ7, þ8

Rh: 1, 0, þ1, þ2, þ3, þ4, þ5, þ6
Pd: 0, þ2, þ3, þ4
Os: 2, 0, þ1, þ2, þ3, þ4, þ5, þ6, þ8
Ir: 1, 0, þ1, þ2, þ3, þ4, þ5, þ6
Pt: 0, þ2, þ4, þ5
The chemical properties of the platinum group
metals and the chemistry of their com-pounds fit
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 ¼ 2.701 3.803 3.887 a ¼ 2.735 3.839 3.924
c ¼ 4.275 c ¼ 4.319
c/a ¼ 1.583 c/a ¼ 1.579

Atomic radius, A 1.325 1.345 1.376 1.377 1.357 1.377
Mechanical properties
Density (20 C), g/cm3 12.45 12.41 12.02 22.59 22.56 21.45
Density liquid at melting point, g/cm3 10.90 10.70 10.49 20.1 19.39 18.91
Hardness (HV), Kg/mm2 250 – 500a 130 50 300 – 680a 200 48
Young’s modulus, GPa 485 386 124 570 538 173
Modulus of rigidity, MPa 172 153 51 220 214 67
Poisson’s ratio 0.29 0.26 0.39 0.25 0.26 0.39
Coefficient 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 m1 K1 117 150 75 87 147 73
Coeff. of linear expansion (0 – 100 C), 106 K 9.5 8.5 11.1 6.5 6.8 9.0
Electrical properties
Specific electrical resistance (0 C), mW cm 6.7 4.34 9.725 8.2 4.7 9.825
Temperature coefficient of electrical 4.0 4.6 3.8 4.2 4.3 3.92
resistance (0 – 100 C), 103 K
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
less well into such a scheme than their physical Chemical Properties [29–34]. Table 3
properties. shows the chemical behavior of platinum group
All platinum group metals have several natu- metals toward various reagents. Resemblances
rally occurring stable isotopes, with the excep- are most clear within the two groups of elements.
tion of rhodium, which has only one. The aim is to quantify the reactions, so as to
provide useful information when choosing con-
Physical Properties [22, 24–28], [167]. struction materials or dissolving platinum group
The outstanding physical properties of the plati- metals. Some combinations of reagents that can
num group metals are of great importance for be used to dissolve these metals are also detailed
their industrial use. These include high melting in Chapter 5.
point, low vapor pressure, high temperature co-
efficient of electrical resistivity, and low coeffi-
cient of thermal expansion. Table 2 lists atomic 3. Occurrence
and crystal data and physical properties of the
platinum group metals. 3.1. Abundance [10], [31], [36–39],
[166], [167]
Osmium is the densest metal known. The
density has been recalculated on the basis of The abundance of platinum group metals (PGMs),
experimental data and the atomic weight of which occupy an intermediate position based on
190.23 þ/ 0.03 to be 22.587 þ/ 0.009 g/ their atomic number and atomic weight, would be
cm3, while for iridium the corresponding values expected to be 104 ppm, based on the mode of
are 192.217 þ/ 0.003 for the atomic weight formation of atomic nuclei [40]. They are concen-
and a density of 22.562 þ/ 0.009 g/cm. trated in planetary regions, reaching ca. 30 ppm in
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 – – – .
Hydrofluoric 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/H2O2 20
Hydrochloric acid/H2O2 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 –
Table 3 (Continued)
Reagent Conditions Temperature, C Pd Pt Rh Ir Ru Os

. . .
NaOH melt þair 500
. .
KOH melt þair 500 .
.
NaOH melt þair 800 . –
.
KOH melt þair 800 .
.
KHSO4 melt þair 440 – . –
NaCN melt þair 700 . . . .
KCN melt þair 700 . . .
NaCN/KCN melt (2 : 1) þair 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 sulfide, gaseous moist 20 – – – – – –
– Mass loss <0.01 mg cm2 h1; ideal as construction material
Mass loss ca. 0.1 mg cm2 h1; limited use as construction material
.
. Mass loss ca. 1 mg cm2 h1; limited use for dissolution processes
Mass loss 10 mg cm2 h1; suitable for dissolution processes.
the earth. Considerable fractionation has taken ments of the earth’s crust, followed by the erup-
place in the earth’s interior, due mainly to the tion of magma, have led to their presence in
siderophilic chemical character of PGMs, so that regions close to the surface. Solidification pro-
virtually the entire mass of PGMs is in the earth’s cesses, differences in melting point and density,
metallic core. The siliceous lithosphere is estimat- gas emissions, convection due to heat, and the
ed to contain 0.05 – 0.5 ppm. flow and eruption of magma, have all produced
On theoretical grounds, the PGMs in the earth concentration and separation effects, mainly in
are assumed to contain ca. 20 % each of plat inum, marginal zones. Chemical interaction with high-
palladium, ruthenium, and osmium, and ca. 6 % temperature silicate layers, especially their sul-
each of rhodium, and iridium. In the case of fide, arsenide, antimonide, selenide, and telluride
ruthenium and especially osmium, these values components, has also played a major role. Al-
are not reflected in the deposits mined to date. most invariably, the platinum group elements
have separated from ultrabasic magmas. Norite
(Mg – Fe – Ca – Al silicate) contains mainly
3.2. Ores and Their Origin [10], [31], sulfidic intrusions, whereas those in dunite (Mg –
[32], [36], [41–48], [166], [167] Fe silicate) are mainly sulfide free. Platinum and
palladium (often with nickel, copper, chromium,
The PGMs in the lithosphere have been trans- etc.) sometimes undergo hydrothermal reactions
ferred from the earth’s interior. Tectonic move- with chlorides in the earth’s interior. All of these
processes have led to the formation of the prima- either as primary deposits or as material for the
ry deposits of platinum-bearing rock. Workabil- formation of secondary deposits. The only im-
ity depends on many factors–concentration of portant primary deposit is at Nishnij-Tagil,
platinum metals, accessibility, size of deposit, which is mined in many locations. It is a projec-
value and potential uses of accompanying mate- tile-like intrusion of dunite through the earth’s
rials–and is economical in only a few cases. crust, which appears to reach a depth of more
When primary deposits are altered and trans- than 100 km and has an area on the earth’s
ported by the natural action of the hydrosphere surface of 25 km2. Platinum metals are concen-
and atmosphere, secondary deposits, also known trated in dunite in the form of striae, lenses, nests,
as placers or alluvial deposits, are formed. Me- and pillars. They are present mainly as polyxene
chanical concentration of the heavy constituents (Fe – Pt), iridium-rich platinum, and osmiri-
by flowing water takes place, together with dium, and are often associated with serpentine
chemical dissolution and reprecipitation of the or chromite. Most of the platinum has been
platinum metals. Recently, hydrothermal pro- obtained from ores with a platinum metal content
cesses have been shown to be considerably more of 10 – 20 ppm. However, ores containing
important than was at first thought. Alluvial 400 ppm are found in some places. In the total
deposits usually originate from dunite. dunite body, the average platinum content is ca.
The platinum metals occur in a large number 0.1 ppm. Other dunite bodies in this region are
of minerals. Workable ore deposits contain main- not economically important either for their metal
ly sperrylite (PtAs2), cooperite (PtS), stibiopal- content or for the extent of the deposit.
ladinite (Pd3Sb), laurite (RuS2), ferroplatinum The dunite pipes at the eastern border of the
(Fe – Pt), polyxene (Fe – Pt – other platinum South African Bushveld have a similar origin to
metals), osmiridium (Os – Ir), and iridium plati- the Russian dunite bodies and are of the same
num (Ir – Pt). These minerals are associated with base material. The platinum-bearing core of this
particular carrier materials, which are often valu- narrow intrusion often has a diameter of 20 m or
able themselves (e.g., iron pyrites, nickel iron less. Veins are rarely present. The excavations at
pyrites, or chrome iron ore). Driekop and Onverwacht are the most well
The minerals are seldom present in an exact known. Mining is difficult. Since the exploitation
stoichiometric ratio. This is true of the platinum of the Merensky Reef, they can be mined eco-
group metals themselves,which are nearly always nomically only in certain cases. Platinum group
present in varying ratios, and of the accompa- metals are sometimes present in the metallic state
nying elements with which they form compounds and sometimes as sperrylite in association with
or alloys. Isomorphism opens up the possibility of chromite. Platinum concentrations are 1 –
further variations. Isomorphic intercalations 200 ppm, and locally higher.
make up a larger part of the economically work- The richest and scientifically most interesting
able reserves. Electron probe microanalysis deposits, although small in extent, are the quartz
(EPM) has enabled a large number of definite lodes of Rietfontein on the Waterberg in the
compounds and intermetallic phases to be identi- Western Cape Province. Owing to their hydro-
fied where mixtures or homogeneous solid solu- thermal origin, the platinum metals are present in
tions had formerly been assumed to be present. native form, accompanied by hematite. The PGM
Outside of true deposits, platinum group me- content of the ore often reaches almost
tals are widely distributed in very high dilution as 5000 ppm. Deposits of similar structure have not
isomorphous combinations with various metals been found elsewhere.
such as nickel, cobalt, and copper, mainly in their The largest known primary deposit of PGMs
sulfides. is the South African Bushveld Complex, with a
total extent of ca. 250 km from north to south and
480 km from east to west. This oval-shaped zone
3.3. Primary Deposits [49–65], [166], was apparently produced by an outflow of PGM-
[167] bearing norite magma into a flat basin. At the
bottom of this, the minerals sperrylite (PtAs2)
The dunite bodies in the Urals are the most and cooperite (PtS) have separated along with
important of the old Russian platinum deposits, iron pyrites, nickel pyrites, copper pyrites, and
chromite. The relatively thin PGM-bearing damental observations on the geology of the
layers at the edges of the outflow near the earth’s Bushveld. The most important areas of PGM
surface are mined. These are in both the oxidation deposits in the western and eastern part of the
and the sulfidic zones, and begin at a depth of Bushveld are known as the Merensky Reef. Not
< 100 m. The working depth extends to almost far from these deposits lie the less important
1000 m. The platinum content of the mined ore is Platreef and the UG 2 Reef (Upper Group Reef),
3 – 20 ppm. Palladium is less important than which has recently increased in importance due
platinum; all the platinum group metals are pres- to its very high rhodium content in many places.
ent. The deposit has great economic importance This metal is in great demand and therefore very
owing to its consistent quality, ease of extraction, expensive.
and large extent. The Bushveld is mined at the The UG 2 reef is a chromite layer running
western and southwestern edges (Rustenburg parallel to the Merensky Reef, but somewhat
region) and the eastern and northeastern edges deeper [66], [67].
(Lydenburg region) (Fig. 3) in two wide areas. Some examples of small deposits include the
The Bushveld is also the world’s largest chromi- Black Reef in the Bushveld and, a few hundred
um and vanadium deposit, and has large deposits kilometers north, the Great Dyk Mine in
of nickel, cobalt, copper, iron, tin, fluorspar, and Zimbabwe.
alusite, magnesite, and asbestos. The Stillwater deposit in Montana, United
These deposits were discovered in 1925 by the States is similar in origin and structure to the
geologist HANS MERENSKY (1871 – 1952) [17]. Bushveld deposit. However, PGM separation
He laid the foundations for the most important occurred at the boundary zone of a subterranean
phase in the development of platinum extraction magma intrusion resembling a sloping lens. This
by his wide-ranging prospecting work and fun- deposit extends for a length of ca. 80 km. The
Figure 3. Geology and platinum mines of the Bushveld Complex

total PGM content, with high levels of palladium lumps weighing up to several kilograms) seem to
and rhodium, is higher than that of the Merensky have been formed mainly by mechanical agglom-
Reef deposit. eration, usually involving chloridic dissolution
The nickel sulfide deposits of the Sudbury, and reprecipitation. Very old deposits that
Ontario district of Canada, yielding iron pyrites formed conglomerates by adhesive action are
(FeS), pentlandite (F – NiS), and copper pyrites termed fossil placers. The platinum metal content
(CuFeS2), are today important sources of plati- of secondary deposits varies over a wide range.
num, and more especially of palladium. These Deep alluvium and river headwater placers are
deposits are associated with noritic magma. The the most productive.
average platinum metal content of the untreated For easily washable sand, a PGM content of
ore is only ca. 0.3 ppm, with a nickel content of 0.05 ppm is economic. Before World War I, the
ca. 2 %. However, the treatment process for the PGM content of economic deposits was ca.
nickel ore concentrates the platinum metals to 2 ppm, but today it is much lower. More platinum
> 50 ppm without extra cost. metals are recovered from river placers than from
Palladium-containing sperrylite (Pt – PdAs2) alluvial deposits.
and stibiopalladinite (Pd3Sb) are present in the Secondary deposits occur mainly in the Urals,
ores, and the platinum group metals also form Siberia, Colombia, and Ethiopia. Often, the re-
isomorphic mixtures with the heavy-metal sul- covery of gold and platinum metals from such
fides. During formation of these deposits, the deposits is so interdependent that sometimes one
sulfides of nickel and copper acted as collectors. metal, and sometimes the other, is the main
The large reserves in Noril’sk in Central Siberia, product. Osmiridium is obtained mainly in Alas-
which have a high palladium content, are similar ka and in the Witwatersrand of South Africa,
to the Canadian deposits with regard to compo- along with secondary deposits of gold.
sition and ore treatment methods. Some lead –
zinc ores [e.g., in the Rammelsberg (Harz) moun-
tains], contain small amounts of platinum and 3.5. Recovery of Secondary Platinum
palladium. Group Metals [69–72]
Comparisons with other metals indicate that
PGM reserves may exist in the Antarctic [68]. Platinum metals not only are extracted from ore
The magma flow in the South African Bushveld but,due to their high value, are also recovered
occurred in an early geological epoch (Cambri- from a wide range of industrial residues. These
an – more than 2109 years ago), when the Afri- residues are of variable composition and quality,
can and Antarctic continents were still part of and recovery plants must be very flexible.
Gondwanaland. Often, the recovery operation is included in
the sales contract for semifinished and finished
goods, so materials are sent directly for recovery
3.4. Secondary Deposits [166], [167] and do not appear on the raw materials market.
For regular customers, accounts are kept of the
Alluvial deposits are typical reserves of this type. weights of noble metals involved. The supply of
They were produced in recent geological epochs material is facilitated, and risks due to price
(Quaternary – Holocene) by weathering and variation are minimized.
washing of primary deposits, mainly dunitic,
which resulted in concentration of the more Metallic Materials. Large quantities of me-
resistant and heavier components (i.e., the metallic materials in the form of used platinum –
tallic and arsenidic platinum minerals, gold, rhodium gauze catalysts result from the oxidation
magnetite, chromite, cassiterite, zircon, and of ammonia (! Nitric Acid, Nitrous Acid, and
granite) in clay and sand. These oxidation zones Nitrogen Oxides). These catalysts must be re-
are often located above the primary deposits. processed chemically after 3 – 18 months of use.
River placers are formed from the alluvial de- At present, ca. 50 t of Pt –Rh is bound up in these
posits by the erosive action of water, to yield so- gauzes. The Pd – Au gauzes used to recover
called black sands. However, typical nuggets Pt – Rh vaporized in ammonia oxidation plants
(mainly small granules but also sizable metallic are also recycled.
The glass industry generates large quantities treatment are therefore difficult. A satisfactory
of defective components for chemical recovery and economical solution to this problem has yet
(e.g., from melting vessels and other equipment). to be found. In Germany, collection logistics are
Spinnerets from textile fiber manufacture coupled to the recycling of automobiles.
must normally be replaced after about one year The chemical industry produces considerable
of operation owing to erosion of the holes. amounts of palladium catalysts on carbon car-
Defective laboratory equipment, mainly cru- riers, often in a moist state that presents sampling
cibles and dishes, makes a considerable contri- problems. Similar residues come from plati-
bution, but chemical apparatus components are num – carbon, rhodium – carbon, and PtO2 cat-
of little significance. alysts, although these are sometimes unsupport-
Considerable quantities of platinum – rhodi- ed. Platinum asbestos, which was formerly used
um scrap are provided by the electrical measure- widely in sulfuric acid production, is now of very
ment industry, mainly in thermocouple compo- little importance.
nents. Other residues from the electrical and
electronic sectors include electrical contacts, Solutions [69]. Amounts of liquid residues
heater elements, and electronic components. from homogeneous catalysts used in the oxo
Manufacture of fountain pen nibs yields re- process (hydroformylation) have increased rela-
sidues in the form of small spheres or dust that tively rapidly. The rhodium content of the organ-
can contain ruthenium, osmium, iridium, rheni- ic solvents or oily process residues is between 50
um, tungsten, molybdenum, tantalum, nickel, and 1000 ppm. Sometimes, these organic solu-
and cobalt as alloy components. Treatment of tions contain iridium, ruthenium, or p alladium.
these materials is among the most difficult of all Aqueous residues, especially homogeneous cat-
separation techniques. alysts containing rhodium, are currently being
produced in increasing quantities.
Dross. Waste materials include slag, ash, The electroplating industry yields exhausted
furnace residue, corrosion residue from equip- electrolytes that cannot be regenerated. The most
ment, and precipitation residue. Catalyst residues important of these contain tetranitroplatinate(II),
of poorly defined composition are also included. rhodium(III) sulfate, and rhodium(III) phosphate.
The PGM content of these materials is usually Finally, the processes used for separating the
low; they are extremely variable and usually platinum group metals also produce waste solu-
nonmetallic. tions that must be reclaimed (e.g., mother liquor
from crystallization). These operations form part
Supported Catalysts [70]. Large quantities of the separation process.
of platinum group metals must be recovered from
spent catalysts. The most important of these, both Radioactive Residues. An as-yet unsolved
in quantity and in value, are the heterogeneous problem is the treatment of radioactively con-
catalysts used in the petroleum industry, espe- taminated platinum equipment from chemical
cially in reforming processes, where >50 t of laboratories and processes.
platinum is bound up worldwide. The lifetime of Fission of 235U in nuclear power stations
these catalysts is 4 – 8 years. Residues usually produces considerable amounts of platinum
contain 0.3 – 0.7 % platinum on g-Al2O3, and group metals; one tonne of spent reactor fuel
usually also include palladium, rhodium, iridi- contains 1.2 kg of palladium, 0.5 kg of rhodium,
um, and rhenium, which must also be recovered. and 2.3 kg of ruthenium [72].
The other large-scale processes in the petroleum However, the radioactivity of the material has
industry–hydrofining and hydrocracking–yield not permitted the commercial use of this PGM
palladium and platinum catalysts on aluminum source until now [73]. The most important PGM
silicate carriers. isotopes in spent reactor fuel are: 107Pd (t1/2
Another source of material for recovery of 7 106 a), 102Rh (t1/2 3 a), and 106Ru (t1/2
platinum metals is spent automobile catalytic 1 a). 107Pd is a very low-energy b-emitter,
converters [69–71]. However, the PGM content which would not exclude its use in many major
is low (2 g per unit), and the units are enclosed in applications; alternatively, it may be removed
steel sheet and widely scattered. Collection and by isotope separation. The active isotopes of
Table 4. Relative proportions of platinum group metals in selected deposits, and their grades
Bushveld complex
Merensky UG 2 South Africa, Sudbury, Noril’sk, 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
rhodium and ruthenium will have decayed to World reserves of the individual metals can
background levels after intermediate storage of best be estimated from the observed composi-
ca. 30 years. 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-
3.6. Reserves and Resources curs with gold.
Natural Reserves. Data concerning re- Industrial Residues. Industrial residues

serves (discovered by prospecting and having have considerable potential for the supply of
assessable economic value) and resources platinum group metals, in addition to their ex-
(which include additional supposed deposits traction from ore. In most sectors, the possibili-
and those with no current economic value) are ties are now fully exploited. In others, recovery is
very dependent on the time prospecting was difficult because of the low PGM contents of the
carried out, and also on technical and economic waste materials (e.g., certain catalysts). Econom-
parameters. ic recovery is also difficult when small PGM-
For platinum group metals, the current esti- containing components are widely distributed
mate of workable deposits is 70 000 t [46], [75], (e.g., in electronics).
[76], 20 years ago, a figure of about one-third of In particular, no satisfactory solution has
this was assumed [77]. been found to the problem of collecting used
Figure 4. World platinum group metal reserves (total 70 000 t)

automobile exhaust catalysts. In 1991, more amount of the product itself. Losses can be
than 7 t of platinum was recovered from this reduced to some extent by recycling the lighter
source in the United States and Europe and about fraction during hydraulic classification of the
0.5 t of rhodium in the United States [248]. platinum deposits.
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, 4.2. Treatment of Primary Deposits
and some in final repositories. [46], [56], [66], [67], [86], [87], [166],
[167]
4. Mineral Dressing and Beneficiation The treatment of platinum-bearing rock, which is
always supplied in lump form from primary
4.1. Treatment of Alluvial Platinum deposits, consists of an initial size reduction by
Deposits [5], [10], [19], [30–32], [36], crushing and grinding, usually wet grinding.
[41], [43–48], [78–86], [166], [167] After discovery of the South African primary
deposits in the Merensky Reef, attempts were
Gangue materials must normally be removed initially made to treat this platinum-bearing rock
from the platinum-bearing placer deposits. Some by the methods used for alluvial deposits. Many
deposits are extracted by subsurface mining. processes were investigated including gravity
Hydraulic classification can be carried out by concentration, flotation, and metallurgical and
hand washing with simple equipment, such as chemical processes, such as chloride formation
shovels, sieves, and troughs. This was the most by calcining the powdered ore at 500 – 600 C in
common method of treating the Colombian de- the presence of sodium chloride. The results were
posits and is still used today. More modern unsatisfactory.
methods involve rotary sieves, troughs, and per- The modern process for the winning of PGMs
forated boxes with running water or water jets. from sulfide ores is shown in Figure 5. Ground
The most economical process is dredging ores from the workable oxidation zone, which
river placers. This is a simple earth-moving contain the platinum metals in native form, are
technique linked with a natural inexhaustible first subjected to gravity concentration on cor-
water supply. Large installations have capacities dyroy and James tables or by hydrocyclones, to
of several thousand tonnes of sedimentary mate- separate the metallic particles from the platinum-
rial per day, with a water consumption of ca. 10 bearing minerals and give a concentrate with a
times this figure. Aboard the dredger, deposits are high PGM content that can be processed quickly
treated mainly by gravity concentration with with low losses.
sieves and sedimentation equipment, using stir- Flotation is then carried out to remove the
rers, thickeners, washing boxes, etc. gangue from the sulfidic minerals, which are also
The last stage of concentration is often magnet- associated with arsenidic and sulfidic platinum
ic separation, with various field strengths used to metal compounds and very finely divided ele-
separate magnetite, ferroplatinum-containing mental platinum metals. This concentrates the
minerals such as chromite, and nonmagnetic com- platinum group elements by a factor of 10 – 50.
ponents into fractions. Often, a final hand washing After filtration with a rotary filter, the platinum
is carried out. In some types of deposit, gold metals in the flotation concentrate are present at a
particles or gold-containing platinum particles can total concentration of several hundred parts per
be separated as amalgam from the platinum con- million, along with a small percentage of sulfur,
centrate. Another process involves concentrating copper, nickel, and iron.
the platinum metals chemically by dissolving the This sequence of process steps is not suitable
other components in nitric acid. The concentrates for all types of deposits and production equip-
so produced can contain up to 90 % platinum group ment. Magnetic or electrostatic separation can
metals. These can be used directly by refineries. sometimes be carried out before the smelting
A problem may occur with high losses of operations.
platinum carried out as very fine metal from the The pelletized material is smelted in a shaft
gravity separation process, often exceeding the furnace to form a copper – nickel matte. Oxygen
slow-cooling matte separation process, a finely

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 sulfide 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 sulfide
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 electrorefining. A method of
this kind is apparently still used to treat sulfidic
PGM deposits in the Urals.
Problems arise during treatment of the high-
chromite ores of the UG 2 reef by the sulfidic
route; these are therefore often mixed with ore
from the Merensky deposit. A process 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 sulfide nickel ores, which

always contain copper, the platinum group me-
Figure 5. Winning of platinum group metals from sulfide
tals follow the nickel in the smelting process.
ores When the crude copper is electrorefined, the
amount of PGMs obtained in the anode slime is
very small.
is then blown into the converter to oxidize the When nickel is electrorefined, the platinum
iron sulfide selectively to iron oxide, which forms group metals remain behind in the slime formed
a slag. These two processes concentrate the at the nickel anode. The base metals and the silver
platinum metals in the copper – nickel matte to are dissolved by acid treatment, giving a concen-
> 0.1 %. The blowing operation is controlled so trate that contains ca. 70 % platinum group me-
as to give the correct sulfur content for the next tals and differs from the nickel anode slime
concentration stage. In this recently developed, obtained from platinum ores of the Merensky
reef in having an appreciably higher palladium iridium. In these cases, alloys of platinum or
content. Also, the concentration of platinum palladium, which can be dissolved more easily,
group elements in the unrefined nickel is about are preferable.
100 times lower than that in the nickel obtained Very highly dispersed noble-metal black,
from platinum ore from the Merensky or UG 2 which is often more soluble, is obtained by
reef (see Section 4.2). alloying the highly refractory platinum metals
When crude nickel is refined by the carbonyl with base metals and then dissolving the latter
process (see ! Nickel, Section 6.3.), residues out. The noble-metal black must not be heated, or
with a lower PGM content are obtained. These the optimum surface properties for the solution
are suitable for concentration by smelting under process would be adversely affected. Suitable
reducing conditions with lead(II) oxide and so- alloying elements include copper, lead, nickel,
dium carbonate. The lead is driven off, and the zinc, aluminum, bismuth, and silver.
silver is dissolved and removed. These concen- Commercial powdered rhodium and iridium
trates are of high enough quality for separation also cannot be dissolved by direct chemical
into individual metals. means, but they can be treated with chlorine at
The treatment of PGM-containing copper an- ca. 500 – 600 C to form chlorides (also insolu-
ode slime obtained from nickeliferous pyrrhotite ble), and these can be reduced at low temperature
(! Silver, Silver Compounds, and Silver Al- (e.g., by hydrogen or by hydrazine in aqueous
loys) is a long and costly process. The metals suspension) to produce finely divided blacks that
copper, selenium, tellurium, arsenic and antimo- can be dissolved in hydrochloric acid – chlorine.
ny must first be removed (e.g., by forming their Concentrates of platinum metals often contain
sulfates in a high-temperature process), followed oxides that are less soluble in oxidizing acid
by dissolution or by producing slags via smelting mixtures than the metals. In these cases, the
in the presence of potassium nitrate with an air material must first be reduced by heating in a
blast. This yields so-called Dore metal. The hydrogen atmosphere or by treating with aqueous
platinum group metals are then concentrated in hydrazine hydrate at ca. 80 C. For rhodium
the anode slime produced in the subsequent silver oxides, solutions must be highly alkaline and at
electrorefining process (! Silver, Silver Com- their boiling point.
pounds, and Silver Alloys).
Copper ores can also contain very small
amounts of platinum group metals. These appear 4.5. Treatment of Dross [88, 93–96]
in the copper anode slime during copper
electrorefining. If platinum metals cannot be separated by chem-
ical or mechanical methods from accompanying
nonmetallic materials, as is usually the case with
4.4. Treatment of Metal Scrap [166], low-grade waste, pyrometallurgical processes
[167] must be used (as in ore treatment).
The most convenient and long-established
A high proportion of the metallic waste from used pyrometallurgical process for low-grade waste
equipment and from semifinished products can is smelting with lead in a shaft furnace to produce
simply by dissolved without any prior treatment slag. Materials containing silver and gold (!
(see Chap. 5). These types of material in-clude Silver, Silver Compounds, and Silver Alloys;!
crucibles, dishes, thermocouple elements, gauze Gold, Gold Alloys, and Gold Compounds, Sec-
catalysts, and fiber spinneret nozzles. tion 6.2.) are treated in this way. The lead acts as a
Massive materials such as heavy-gauge sheets collector for the platinum group metals. The
or bars should be size reduced by crushing or presence of gold and silver also considerably
machining to produce swarf. For the highly affects the distribution equilibrium of the plati-
refractory metals of the platinum group (Rh, Ir, num group metals in the melt. In the lead shaft
Ru, and Os) and their alloys, mechanical methods furnace, some of the high-melting noble metals
are usually not sufficient to produce a surface rhodium, iridium, and ruthenium separate as so-
susceptible to dissolution. This is also true of called furnace shows. When the lead is oxidized
platinum alloys with > 30 % rhodium or 20 % and removed as litharge, most of the Rh, Ir, and
Ru (so-called bottom metals) precipitates from soda solution) leaving the noble metal as an insol-
the increasingly silver-rich alloys. Considerable uble residue. However, small, but not negligible,
amounts of rhodium and iridium pass into the amounts of noble metal also go into solution.
shaft furnace slag and are lost. Ruthenium and Moreover, sulfidic impurities in the catalyst can
particularly osmium are lost in large amounts in lead to the release of toxic hydrogen sulfide. Other
flue dust and waste gases. practical processes are dissolving the catalyst in
When the gold – silver alloy from the above sodium carbonate solution (usually at 220 C in a
process is electrorefined to obtain silver, gold and pressurized reactor), or sintering with sodium hy-
the platinum group metals remain in the anode droxide or sodium carbonate. Carbon and other
slime. If this consists mainly of gold, it is con- products of the breakdown of mineral oil in the
verted to pure gold by Wohlwill electrolysis spent catalyst must be burned off before treatment
(! Gold, Gold Alloys, and Gold Compounds, with acid or alkali, because these materials interfere
Section 5.3.), in which platinum and palladium with the filtering of the platinum metal concentrate.
are concentrated in the electrolyte, and silver Spent automobile exhaust catalysts can be
chloride and the remaining platinum group me- processed at high temperature in a plasma or a
tals in the anode slime. Alternatively, the silver submerged arc furnace. In the former, a plasma is
can be dissolved from the gold – silver alloy by produced between an electrode and the molten
nitric acid to form silver nitrate, which is purified feed material. The energy of recombination of the
by thermal decomposition of the accompanying plasma is released into the melt. In the resistance
nitrates; the platinum group metals remain in the furnace, slag serves as the electrical resistance in
water-insoluble oxide residue. which heat is produced. In both processes, the
All the concentrates mentioned above can be oxide carrier is melted with or without addition of
dissolved, and the individual platinum group a flux of lower the melting point. Iron or copper is
metals obtained from these solutions. added as a collector, forming a metallic melt that
takes up the platinum group metals. The concen-
tration of PGMs can reach 20 %.
4.6. Treatment of Supported Catalysts
[70], [71], [97–100]
4.7. Treatment of Solutions [69], [101],
Spent, inactive catalysts consisting of platinum [102]
metals supported on active carbon, or carrier-free
noble-metal catalysts that have become coated In homogeneous catalysis, high-boiling distilla-
with organic residues, are concentrated by com- tion residues are usually produced that contain no
bustion. These materials are sometimes sponta- valuable materials apart from rhodium and some-
neously flammable. When they are being burned, times ruthenium. These residues can be carefully
strong air currents are suppressed to prevent dust burned, and the ash treated by wet chemical
losses. If the resulting ash contains platinum processes. Other techniques for recovering rho-
metal oxides, these are reduced to the metal. dium have been suggested (i.e., liquid – liquid
Catalysts with incombustible carriers insolu- extraction, reductive precipitation of the metal,
ble in acid and alkali (e.g., g-Al2O3, silica gel, and pyrolytic hydrogenation). A process used in
asbestos, and zeolites) can often be treated with industry, especially for the treatment of rhodium-
oxidizing acid, but the noble metals dissolve containing oily residues from oxo synthesis, is
completely only in the absence of organic resi- precipitation of acid-soluble rhodium telluride
dues (especially tarry matter) and if the carriers by reacting the organically bound rhodium with
are very porous. Otherwise, the platinum metals tellurium. This process is notable for the high
must be concentrated by the lead shaft furnace efficiency of rhodium recovery.
process (see Section 4.5). The methods used to produce concentrates
Reforming catalysts consist of g-Al2O3 impreg- from a variety of aqueous wastes are to a large
nated with platinum, platinum – rhodium, plati- extent the same as those used for the internal
num – iridium, or platinum – rhenium. This carri- recycling of platinum metals in the solutions
er material is soluble in acid and alkali, and is produced in metal winning processes (see Sec-
dissolved (e.g., in hot sulfuric acid or hot caustic tion 6.8).
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-
dium and iridium powder, can be converted into a
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
Rh2O3 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, Figure 6. Rate of dissolution of platinum and palladium in
the choice of method is important. oxidizing acids
5.1. Dissolution in Aqua Regia To suppress side reactions, the reactants must
not be allowed to boil too violently, although
The following reaction takes place in aqua regia: maintaining them at the boiling point and use of
6 M acid offers the most convenient method of
8 HClþ2 HNO3 þPt!H2 PtCl6 þ4 H2 Oþ2 NOCl
sustaining consistent reaction conditions. To
as does the following decomposition: avoid boiling over, especially during heating,
the initial charge of nitric acid should be added
3 HClþHNO3 !Cl2 þ2 H2 OþNOCl
slowly and evenly to boiling hydrochloric acid.
This method should also be used when aqua regia
The highest rates of dissolution occur at the is added to replace spent acid.
boiling point of aqua regia. The rate depends only Finely powdered material also tends to cause
slightly on acid concentration between 6 and boiling over. To avoid a violent reaction when
12 M, and is virtually unaffected by the presence dissolving palladium-rich alloys, dilute acids
of dissolved platinum group metals. should be used.
The aqua regia method is preferred for
compact metallic platinum and high-platinum
alloys (sheet, wire, turnings, etc.). The reac- 5.2. Dissolution in Hydrochloric
tions must be carried out in a sealed apparatus Acid – Chlorine
to prevent loss of material by splashing and
mist formation. Before the next stage of treat- In the reaction between platinum and a solution
ment, nitric acid must usually be removed by of chlorine in hydrochloric acid
concentration with the addition of hydrochlo-
ric acid. Ptþ2 HClþ2 Cl2 !H2 PtCl6
the dissolution rates for platinum and platinum- or

rich alloys have a maximum in the range 80 –
H2 PtBr6 þ3 Cl2 !H2 PtCl6 þ3 Br2
90 C (see Fig. 6). As the boiling point of hydro-
chloric acid (110 C) is approached, the rate of can take place in parallel with the dissolution
reaction decreases rapidly, increasing again at process, bromine can be present in substoichio-
higher temperature. For palladium, the rate of metric amounts.
dissolution is considerably higher. Platinum and its alloys with rhodium or iridi-
For these dissolution reactions, 6 – 8 M hy- um are more resistant to hydrochloric acid –
drochloric acid is preferred since, in this con- bromine than to hydrochloric acid – chlorine.
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- 5.4. Other Dissolution Processes
ed hydrochloric acid is used. The presence of
dissolved platinum metals does not decrease the Concentrated nitric acid is suitable for dissolving
rate of dissolution. By careful control of addi- palladium (see Fig. 6).
tion rates, a very slight excess of chlorine can be Concentrated sulfuric acid dissolves finely
used, so that this method leads to lower levels of divided rhodium at ca. 300 C, but strongly
waste gas contamination than the aqua regia heated rhodium powder is largely insoluble in
method. However, the rates of dissolution de- sulfuric acid.
crease considerably in the absence of agitation, Concentrated hydrobromic acid is the only
and the process is most suitable for easily stirred reagent that can directly dissolve oxides of the
powders, slurries, or concentrates and unsuit- platinum group metals such as PdO, PtO2,
able for bulk material. Rh2O3, and IrO2. Platinum can be dissolved in
Metal dissolves more slowly in the vapor a mixture of hydrobromic acid and bromine
phase or in refluxing hydrochloric acid contain- above 100 C in a pressurized reactor. Metallic
ing dissolved chlorine (see Fig. 6). rhodium is quite soluble in concentrated hydro-
Hydrogen peroxide can be used in place of bromic acid near its boiling point.
chlorine as oxidizing agent. Optimum concen- Powdered ruthenium or osmium can be trea-
trations are difficult to maintain owing to the ted with an alkaline solution of potassium per-
decomposition of hydrogen peroxide into oxygen oxodisulfate (K2S2O8) to form solutions of ruthe-
and water; therefore, reaction rates are very low nate or osmate. In acidic media, osmium is oxi-
compared with those for HCl – Cl2. The HCl – dized by peroxodisulfate or chromic acid to form
H2O2 system has some limited use for palladium. OsO4.
Perchloric acid has been reported to be a
solvent for platinum and its alloys, ruthenium,
5.3. Dissolution in Hydrochloric and osmium.
Acid – Bromine
Palladium dissolves more rapidly in hydrochloric 5.5. Dissolution by Salt Fusion [34]
acid – bromine mixtures than in hydrochloric
acid – chlorine (see Fig. 6). Bromine is more Aqueous dissolution processes are not successful
soluble than chlorine in hydrochloric acid, en- for all types of concentrates and raw materials.
abling high halogen concentrations to be used. If Often, reactions in molten salts are more effec-
the temperature is kept well below the boiling tive. For many raw materials, molten salt meth-
point of bromine (59 C), losses in the waste ods are selective and therefore also suitable for
gases become very small. Bromide formed in the separation.
dissolution reaction can be oxidized to bromine Rhodium can be converted into water-soluble
by chlorine in an easily controllable reaction, rhodium(III) sulfate at ca. 600 C by melting
recovered by distillation, and recycled. Since the with potassium or sodium hydrogensulfate,
conversion of bromide to bromine which is converted to the pyrosulfate with loss
of water. Platinum, iridium, and ruthenium are
2 Br þCl2 !Br2 þ2 Cl not attacked.
Ruthenium is converted into water-soluble In general, coarse separation is followed by a

K2[RuO4] when reacted with KOH – KNO3. purification stage. The process used for coarse
Osmium reacts similarly. This reaction can be separation is determined largely by the compo-
used to treat finely divided osmiridium, especial- sition of the starting solution, and the purification
ly after preliminary treatment with molten zinc, process depends on the particular PGM. The
in which the iridium remains undissolved (see purification stage is necessary because, with few
also Section 4.4). Potassium salts are more ef- exceptions, an individual platinum group metal
fective than sodium salts. Alkali-metal carbo- of commercially acceptable purity cannot be
nates can be used instead of alkali-metal isolated from complex solutions in a single step.
hydroxides. In practice, the composition of the raw mate-
Ruthenium and osmium are very readily at- rial changes frequently and profoundly, especial-
tacked by molten Na2O2. The reaction can be ly in the recovery of secondary metal. Here, the
prevented from becoming too violent by addition crude separation process must be very flexible. In
of NaOH or Na2CO3 to reduce the melt tempera- separation plants that are parts of mining opera-
ture. Iridium can be oxidized to acid-soluble tions, the raw material is usually fairly consistent
iridate by fusion with Na2O2. over a long period of time.
Iridium can also be converted to acid-soluble The most important separation processes to-
iridate by treatment with fused BaO2 or BaO2 – day make use of various combinations of precip-
Ba(NO3)2. This has the advantage of enabling the itation, crystallization, solvent extraction, and
cation to subsequently be removed simply by distillation.
precipitation as BaSO4. The process is also used To achieve the necessary performance eco-
to treat osmiridium, although osmium is con- nomically, a high selectivity, a good yield of
verted to OsO4 and must be recovered from the noble metal, and (to minimize loss of the interest-
waste gas. earning potential of high-value materials) a short
When mixtures of powdered platinum group treatment time are required.
metals are heated at 700 C in a chlorine atmo-
sphere, acid-soluble chlorides of palladium and
platinum, and acid-insoluble RhCl3, are formed. 6.1. Chemistry of Platinum Group
Chlorination of iridium and ruthenium produces Metal Separation [104–115]
substoichiometric acid-insoluble products.
All of the platinum group metals form water- Of the many known reactions in PGM chemistry,
soluble complex chlorides when treated with certain ones have been developed to separate the
sodium chloride in a chlorine atmosphere. metals or have been shown to be especially useful
for this purpose. This is true both for crude
separation and for purification; in many cases
6. Separation of Platinum Group the same reaction is equally important in both
Metals [31], [103], [263] stages.
After the platinum group metals have been dis- Dissolution Properties. Differences in re-
solved, the individual metals must be recovered. activity toward chemical reagents, especially
Depending on the raw material, the solution may oxidizing acids and molten salts, can often be
contain all or some of the PGMs, together with utilized for coarse separation of platinum group
gold, silver, and base metals. metals. Good separation is possible only if plati-
Over the past 200 years, numerous separation num and palladium do not form mixed crystals
processes have been developed and used [31], with the refractory PGMs.
[32], [36], [41]. Many of the individual steps are
still very important in modern processes. Others Solution Equilibria. In the crystallization
are of historical interest, but may be used in process (by either evaporation or precipitation),
special cases to treat very small quantities. In the solubilities of chloro complexes of the plati-
addition to the large-scale separations carried out num group metals are very important, as is the
by mining companies and refineries a number of possibility of altering these solubilities. The
small companies exist. temperature dependence of these solubilities is
generally quite large and can be utilized or must

be considered, in many stages of the process. In
the range between room temperature 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 H2PtCl6.
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-
Figure 8. Dependence of the solubility of platinum group

metal chloro complexes on the concentration of NH4Cl and
HCl at 20 C
. . . . unstable solution equilibrium; —– stable solution
equilibrium
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
[RhCl6]3 to [Rh(H2O)6]3þ, and of [PtCl6]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-
Figure 7. Solubility of platinum group metal chloro com- sion of (NH4)2[PtCl6] is heated, the concentra-
plexes in water as a function of temperature
. . . . unstable solution equilibrium; —– stable solution tion of dissolved platinum (after being cooled to
equilibrium 20 C) increases in 24 h from 2.2 g/L to twice
Table 5. Stability of platinum group metal chloro complexes
Metal Oxidation state Complex Redox stability Kinetic stability Thermal stability
2
Pt IV [PtCl6] stable very stable very stable
Pt II [PtCl4]2 unstable unstable
Pd IV [PdCl6]2 unstable stable unstable
Pd II [PdCl4]2 stable very stable
Ir IV [IrCl6]2 stable stable
Ir III [IrCl6]3 stable stable
Rh III [RhCl6]3 stable stable unstable
Ru IV [RuCl6]2 unstable unstable
this amount, and after 96 h it increases fourfold. aqueous solution by zinc was often an important
This is due to partial hydrolysis to give soluble step, both for separation and for the recovery of
compounds. The reverse reaction, brought about PGMs from recycled solutions. However, the use
by heating with hydrochloric acid at its azeotro- of zinc as a cementation agent is now ruled out for
pic concentration, occurs at similar rates. environmental reasons. Where cementation can-
not be avoided, iron, aluminum, or Fe – Al alloys
Ion Exchange Chromatography. The use can be used instead. In aqueous media, hydra-
of ion exchange is limited mainly to the separa- zine, formate, or boranate can be used to reduc-
tion of PGMs from base metals [118]. For exam- tively precipitate elemental PGMs.
ple, selective adsorption of [PtCl6]2 on strongly
basic anion-exchange resins is possible, followed Solvent Extraction [124–133]. Many liq-
by elution with sodium hydroxide solution, yield- uid – liquid extraction systems have been de-
ing [Pt(OH)6]2. The separation of a PGM mix- scribed that can be used for solvent extraction
ture into individual PGMs by chromatography is of metals. Much research into the platinum group
described in [119], [120]. metals has been carried out, mainly aimed at their
separation. The extraction processes do not usu-
Organic Precipitation Agents [121], [122]. ally involve a true Nernst distribution of the
Palladium can be selectively precipitated by di- extractable compounds between the organic and
methylglyoxime, but the precipitate is difficult to the aqueous phases. More often, the extractable
filter. Separation systems have also been reported compounds (generally organometallic) are
that depend on the formation of complexes of the formed in the extraction system itself. The re-
PGM with substituted formazanes and substituted actants are dissolved in an inert organic phase or,
benzoylthiourea. Precipitable organometallic if they are themselves liquids, can be used as
compounds can often be recovered by solvent such. The system is generally diluted with an
extraction instead of precipitation. inert solvent to lower the viscosity.
The extractants and extraction mechanisms
Distillation and Sublimation. The only in- are classified in the following groups:
dustrial use of distillation or sublimation at pres-
ent is the separation of RuO4 and OsO4, usually 1. Compound formation
by steam distillation. These substances have high 2. Anion exchange
vapor pressures even at room temperature, so a 3. Cation exchange
noncondensable carrier gas cannot be used be- 4. Solvation
cause of the high carryover of material. A possi- 5. Solvent extraction without reaction
ble future process is the separation of PGM by
using sublimation of PGM fluorides [123]. Of the many systems investigated, very few
are of practical use.
Reduction to Metal. Since the PGMs are all The organic phase often increases significant-
electrochemically noble metals, selective reduc- ly in viscosity as metal content increases and is
tion and cementation by base metals are not usually diluted by a hydrocarbon mixture in the
possible. In the past, collective cementation from 150 – 200 C bp range.
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. Modifications of these
Figure 10. Older separation process B (Siebert)
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 refinery
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-
Figure 9. Older separation process A lective dissolution of Pt – Pd can be achieved
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 – Cl2. An advantage of
the process was the efficient 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 difficulty 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 efficiency,
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 beneficial. The
process is very flexible, which is an advantage,
particularly for the recovery of secondary metal
when the ratio of PGMs changes continuously. If
the ruthenium content is high, RuO4 should be
Figure 11. Older separation process C (Gilchrist) removed by distillation as the first step of the
separation process.
since the refractory PGMs are concentrated in
separate particles. Some special process steps are Separation Process E (Fig. 13). Solvent
used, including alloying with lead, and selective extraction with dialkyl sulfide is used. Unlike
dissolution of rhodium, ruthenium and iridium by process D, this provides a practically quantitative
salt fusion. and sharp separation of palladium, which yields
favorable conditions for the purification of pal-
Separation Process B (Fig. 10). A process ladium and platinum. Solvent extraction of iridi-
formerly used by the platinum smelting company um can be carried out almost quantitatively and is
Siebert/Degussa is characterized by the recycling very useful when iridium content is low. Under
of unacceptably large amounts of platinum due to these conditions, use of precipitation crystalliza-
the relatively high solubility of sodium chloro- tion would result in excessive amounts of iridium
Figure 12. Modern separation process D

Figure 13. Modern separation process E
remaining as soluble (NH4)2[IrCl6] in the mother extraction; the higher rate of complex formation
liquor. enables column technology to be used. Also, the
separation process can be set up as an integrated
Separation Process F (Fig. 14) [136]. A unit. Ion exchange, which is also carried out on
process used mainly in mining operations (i.e., columns, results only in separation of base
with primary raw materials) has, as its most metals.
notable feature, solvent extraction of platinum, Similar separation processes based on solvent
which is the metal present in highest concentra- extraction are in industrial use or development
tion. Oximes are better than thioethers for solvent [129–133], [137–143].
solution due to H[AgCl2] 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 filtration are improved
by flocculating 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. Sodium nitrite,
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-

Figure 14. Modern separation process F (Matthey Rusten- ladium by Precipitation Crystallization
burg refiners) [144–146]. The same basic process has been used
for the separation of the largest quantities of plati-
6.4. Processes Used in Coarse num group metals since the beginning of separation
Separation [31] technology–precipitation crystallization of ammo-
nium hexachloro complexes (NH4)2[MCl6]. This
Separation of Silver. Insoluble silver chlo- process can be optimized in many ways by influ-
ride is formed in the dissolution process and is encing solubilities (e.g., by valence changes, addi-
removed by careful filtration from the starting tion of a common ion, or changing the temperature
solution in concentrated hydrochloric acid. How- and rate of precipitation).
ever, this acid at its usual concentration leads to The first step in separation is usually to pre-
unacceptably high levels of silver remaining in cipitate platinum as (NH4)2[PtCl6]. If the
dissolved platinum is present as PtII, it must first but must be avoided to prevent the following
be oxidized to PtIV (e.g., by chlorine). Excess reaction from occurring:
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 A virtually quantitative yield is obtained if the
selectively reduced to iridium(III), for example, crystals are isolated quickly and washed with a
with iron(II) salts or ascorbic acid. The ammo- cold concentration NH4Cl solution saturated
nium hexachloroplatinate(IV) is precipitated with Cl2.
preferably by slow addition of concentrated The same basic separation process can be
ammonium chloride solution at room tempera- carried out by using potassium chloride instead
ture with stirring. The hydrochloric acid con- of ammonium chloride. Using potassium chlo-
centration should be 1 M, and the platinum ride has advantages and disadvantages:
content should be 50 – 200 g/L. After precipi-
tation, the excess of NH4Cl in the solution . As the solubilities of potassium hexa chloro
should be at least 0.5 mol/L. The mother liquor salts are lower than those of corresponding
is removed from the salt by washing with semi- ammonium salts, separation yields are better
saturated cold ammonium chloride solution. . Precipitation of (NH4)2 [PdCl6] by passing
The deep-yellow ammonium hexachloroplati- chlorine through an NHþ 4 -containing solution
nate(IV) is recovered with a purity of 99.0 – is dangerous, because explosive nitrogen
99.5 % in > 99 % yield. trichloride is formed. This can be oxided by
Attempts have been made to precipitate the using potassium chloride [147]
(NH4)2[PtCl6] slowly by gradual formation of . Potassium ions are introduced into the purifi-
NHþ 4 ions in the reaction medium (e.g., by cation processes (see below) and are more
hydrolysis of urea or hexamethylenetetramine). difficult to remove than immonium ions
In this way, an almost ideally homogeneous
precipitation medium is produced. However, Separation of Rhodium. Ammonium hex-
the purities and yields achieved do not justify achlororhodate, (NH4)3[RhCl6], can be isolated
the cost. from rhodium solutions in hydrochloric acid such
To precipitate iridium as (NH4)2[IrCl6], iridi- as those obtained after removal of the other
um(III) is converted to iridium(IV) by treatment platinum group metals. Ammonium chloride is
with an oxidizing agent at ca. 100 C, while added, followed by concentration and crystalli-
palladium remains in the divalent state at this zation. Much of the remaining (NH4)2[PtCl6] and
temperature. Black (NH4)2[IrCl6] is filtered (NH4)2[IrCl6] is precipitated at the same time.
off from the cold solution. It is more readily Chlorides of the base metals mostly remain in
soluble than the corresponding platinum salt, and solution. The (NH4)3[RhCl6] can be selectively
therefore sufficient excess of NH4Cl (0.5 – redissolved in water at room temperature to form
1.0 mol/L) and good cooling (20 C) must be an almost saturated solution. This gives a purified
used, and the minimum amount of concentrated solution of rhodium. Both (NH4)2[PtCl6] and
NH4Cl solution must be used for washing. (NH4)2[IrCl6] are recovered by filtration.
Chlorine is then passed into the solution at room The rhodium can also be isolated as chloro-
temperature, the excess NH4Cl in solution being pentamminerhodium(III) chloride, [RhCl
> 1 mol/L, and palladium is precipitated in the (NH3)5]Cl2, or potassium hexanitrorhodate(III),
pure state in the form of the sparingly soluble, K3 [Rh(NO2)6], but the precipitations must be
brick-red ammonium hexachloropalladate(IV), carried out in weakly alkaline solution. These
(NH4)2[PdCl6]. The separation from rhodium methods are unsuitable for solutions that contain
(III) is, however, not sharp. large quantities of base metals because, under
The main problem encountered in this precip- reaction conditions, these form insoluble hydro-
itation is the difficulty of producing sufficiently xides that are difficult to filter.
large crystals for filtration, which can be favored Cementation of rhodium by other metals (see
by adding the palladium solution to the NH4Cl Section 6.3) can also be carried out. However, all
solution. High temperature favors crystal growth of the noble metals and the copper remain with
the rhodium. An advantage is that precipitation of atmosphere must be prevented by use of the best
rhodium is complete in this process. possible absorption equipment. No danger of
explosion exists.
Distillation of Ruthenium(VIII) Oxide. Also, OsO4 can be formed and distilled off by
The most important industrial process for the heating fine osmium powder in a stream of
isolation of ruthenium is distillation of the very oxygen.
volatile ruthenium(VIII) oxide, RuO4, from
aqueous solution. This compound is formed in Solvent Extraction. Liquid – liquid extrac-
solutions of potassium ruthenate(VI), K2[RuO4], tion is often characterized by distribution coeffi-
and hexachlororuthenate(III), K3 [RuCl6], by cients that vary greatly from element to element.
oxidation with chlorine at around neutral pH or These can usually be modified by chemical meth-
with sodium chlorate at pH 0 – 3. Oxidation can ods to give conditions favorable for the separation
also be carried out in dilute sulfuric acid solution of PGMs. However, the separation factors result-
with potassium permanganate, or with potassium ing from the ratios of the distribution coefficients
chlorate in sulfuric acid solution, but these meth- rarely enable a single separation stage to provide
ods are less satisfactory for safety reasons. The purities that fulfill modern requirements for metal
volatile RuO4 is absorbed by dilute hydrochloric quality. Although separations are generally better
acid, and is converted into water-soluble chlor- than those effected by precipitation crystalliza-
oruthenate complexes. tion, coarse separation by solvent extraction must
Even in the absence of potassium permanga- be followed by purification.
nate, chlorate, or their reaction products, the In practical industrial separation processes,
distillation of RuO4 is hazardous. The presence mainly four extractants are used [109],
of NHþ 4 salts can lead to the formation of [130–133], [143–146]. The most long-standing
explosive chlorides of nitrogen. Therefore, re- process is the separation of Pt (IV) and
moving ruthenium at the start of a separation Ir (IV) from Rh (III) with tributyl phosphate
process is often preferable. The formation of (TBP) [148], [149]. The extraction of H2[PtCl6]
chlorine dioxide, chlorate, and perchlorate is and H2[IrCl6] must be carried out in 4 – 6 M HCl
also possible. Moreover, RuO4 can explode by (Fig. 15). If the usual mixture of 1 part TBP with
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, osmium is present in only a few primary and
secondary raw materials. Osmium should, if
possible, be isolated as the first step of a separa-
tion process, so that later operations will not lead
to loss of volatile OsO4.
Solutions obtained from digestion of ores
normally contain osmates. Treatment of solu-
tions in dilute sulfuric acid with oxidizing agents
such as CrO3, K2S2O8, or HNO3 causes osmium
(VIII) oxide to be formed and to distill off. From
this distillate, OsO4 can be isolated directly as a
water-insoluble oil (mp 40 C). Alternatively, it
can be absorbed in potassium hydroxide solution,
forming K2OsO4, or can be converted to metallic
osmium by reaction with formaldehyde solution. Figure 15. Extraction of platinum group metal chloro com-
Owing to the toxicity of OsO4, its escape into the plexes by tributyl phosphate
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 refinery
feed solutions).
Trioctylamine is used widely for the sol-
vent extraction of large amounts of platinum
from refinery solutions [150–152]. 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 Figure 17. Extraction of palladium(II) and platinum(IV)
of the metal. Diluent solvents are also em- chloro complexes by an aldoxime (LIX TN 1911) a) Plati-
ployed when carrying out solvent extraction num(IV); b) Palladium(II)
with amines.
For the solvent extraction of palladium, thioe- aqueous ammonia produces [Pd(NH3)4]Cl2; this
sters are currently used (e.g., di-n-hexyl sulfide or can be converted easily to [Pd(NH3)2Cl2], which
di-n-octyl sulfide) [110], [151–155]. They pro- is then purified.
duce good separation from other PGMs and have The method used for high-tonnage production
a high capacity for the metal. A disadvantage is of copper by solvent extraction with oximes is
the poor kinetics of complex formation, the also successfully used for palladium (Fig. 17).
reaction times required being 30 mins or more. However, high concentrations of palladium in
Hence, mixer – settler equipment must be used the organic phase cannot be achieved.
rather than column equipment. Stripping with Numerous other solvent extraction systems
have been investigated, some of which are un-
dergoing industrial development [114], [115],
[149], [156–159].
6.5. Purification
Methods used for purification of the products

from the separation process employ the same
principles (i.e., valence change, temperature
change, addition of common ions, and modifica-
tion of complexes by chemical reaction).
Purification of Platinum. Recrystalliza-

tion of sodium hexachloroplatinate(IV),
Na2[PtCl6], from hot water is effective, but large
amounts of platinum must be recycled.
Very effective purification 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.
Figure 16. Extraction of platinum group metal and gold The yield of platinum therefore depends on the
chloro complexes by trioctylamine purity of the feed material.
The classical method of purification is by ½PdðNH3 Þ4 Cl2 þ2 HCl!½PdCl2 ðNH3 Þ2 þ2 NH4 Cl
repeated precipitation of (NH4)2[PtCl6] or
The impure salt should be dissolved quickly at
K2[PtCl6]. The crude salt is converted into me-
room temperature with agitation to prevent ap-
tallic platinum, dissolved to form H2[PtCl6] (see
preciable quantities of the (NH4)2[PtCl6] present
Chap. 5), and reprecipitated. By repeating this
as an impurity from dissolving. Undissolved ma-
many times, very high purities are obtained,
terial, mainly hydroxides and (NH4)2[PdCl6], is
although the cost is also high. Also,
filtered off. Hydrochloric acid is added to the
(NH4)2[PtCl6] can be converted directly to
solution until a pH of 1 is reached, causing
H2PtCl6 by oxidation of the NHþ 4 or by cation [PdCl2(NH3)2] to precipitate as easily filterable
exchange. In the oxidative decomposition of
crystals. Possible causes of poor purification are
NHþ 4 (e.g., by heating the aqueous solution with too high a concentration of (NH4)2[PdCl6] in the
addition of Cl2 or HNO3), care must be taken to
impure material, too prolonged a reaction with
use a carrier gas or distillative conditions to
ammonia, too high a concentration of ammonia,
prevent accumulation of explosive nitrogen –
or problems with filtration of the hydroxidic
halogen compounds.
precipitate before precipitating [PdCl2(NH3)2].
Conventional crystallizations from water are
High temperature is also detrimental. If the acid
possible, but the solubility of (NH4)2[PtCl6] is
concentration is too high, the yield is reduced due
relatively low, so that despite favorable temper-
to further reaction to form soluble (NH4)2[PdCl4].
ature coefficients (see Fig. 7), large volumes
Other possible methods for dissolving
must be used. Modified crystallization methods
(NH4)2[PdCl6] are
are more economic (e.g., utilization of the con-
siderably higher solubilities in water above 2 ðNH4 Þ2 ½PdCl6 þN2 H4 !2 ðNH4 Þ2 ½PdCl4 þ4 HClþN2
100 C at higher pressure). The purification ef-
fected by crystallization is enhanced by hydro- or
lysis. In neutral or very slightly acidic media ðNH4 Þ2 ½PdCl6 !ðNH4 Þ2 ½PdCl4 þCl2
above 90 C, the conversion of the chloro com-
plexes of the platinum group metals (especially Pure (NH4)2[PdCl6] can be obtained in almost
metals other than platinum) into hydroxo com- quantitative yield by passing chlorine through the
plexes and oxide hydrates begins. These cannot solution and adding NH4Cl.
form mixed crystals with (NH4)2[PtCl6]. The The purification of (NH4)2[PdCl6] by repre-
extent of hydrolysis of hexachloroplatinate(IV) cipitation is useful in the presence of silver and
increases with increasing temperature and reac- most base metals. In the presence of rhodium,
tion time. Therefore, high temperature and long platinum, iridium, and copper, however, better
reaction time lead to a lower yield of crystalline purification is achieved by precipitating
product. The reaction is reversible in the presence [PdCl2(NH3)2], although higher losses of palla-
of hydrochloric acid. dium to the mother liquor must be tolerated.
When the products of solvent extraction by Dichlorodiamminepalladium(II),
substituted amines are stripped, solutions of plat- [PdCl2(NH3)2], can be produced by direct
inum compounds in hydrochloric acid are ob- precipitation from an impure solution of palladi-
tained. From these, pure (NH4)2[PtCl6] is pre- um resulting from crude separation or inadequate
cipitated by addition of NH4Cl. purification. It is dissolved in aqueous ammonia
solution to form [Pd(NH3)4]Cl2 and reprecipi-
Purification of Palladium [160]. Impure am- tated by hydrochloric acid.
monium hexachloropalladate(IV), (NH4)2[PdCl6], An ammoniacal stripping solution is used
can be dissolved directly for purification. This is after solvent extraction of palladium by dialkyl
achieved by the following reaction: sulfide. Palladium can be precipitated from this
by acidifying to pH 1, thus producing [Pd
3 ðNH4 Þ2 ½PdCl6 þ20 NH3 !3½PdðNH3 Þ4 Cl2 þ12 NH4 ClþN2
(NH3)2Cl2] directly in a highly pure form.
Acidification of a solution of [Pd(NH3)4]Cl2 Purification of Iridium. The purification

precipitates the sparingly soluble, pale yellow of crude ammonium hexachloroiridate(IV),
trans-diamminedichloropalladium(II): (NH4)2[IrCl6], is carried out by precipitation of
the unwanted elements as sulfides; 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 (NH4)2[IrCl6]. The sulfides
are precipitated from slightly acidic solution by
hydrogen sulfide. To ensure optimum precipitation
conditions for all elements present, the sulfide
precipitation must usually be carried out repeated-
ly. Iridium can be purified 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 Fe2þ, As3þ, or ascorbic
acid at room temperature causes selective reduc-
tion of Ir (IV) or Ir (III); Pt (IV) is unaffected.
Purification of Rhodium [162]. Ammoni-

um hexachlororhodate(III), (NH4)3[RhCl6], can
be crystallized from water or hydrochloric
acid. However, the yields are poor, as is the
degree of separation from platinum and iridium.
Precipitation of [Rh(NH3)5Cl]Cl2 or (NH4)3[Rh
(NO2)6] is more effective, although yields are
not good, and treatment of the mother liquor is
problematic. Figure 18. Thermal decomposition of platinum group metal
Good results are obtained when H2[PtCl6] and complexes
H2[IrCl6] are removed by liquid – liquid extrac-
tion, and base metal cations by strongly acidic chloro complexes (calcination). These com-
ion-exchange resins. At one time, treatment of pounds have decomposition temperatures
crude rhodium with chlorine at 700 C was an (Fig. 18), of 200 – 500 C. The size and geom-
important process. The reaction product con- etry of the charge affect the reaction course. The
sisted mainly of insoluble RhCl3 from which the low thermal conductivity of the charge means
chlorides of platinum, palladium, and base me- that the reaction proceeds slowly, but smooth
tals were dissolved by treatment with hydrochlo- production of the desired decomposition pro-
ric acid. Satisfactory purification could usually ducts is ensured. Also, the negative heat of
be obtained only by repeating the process. reaction of the decomposition tends to slow down
Crude potassium hexanitritorhodate(III), the process. In practice, favorable conditions are
K3[Rh(NO2)6], can be converted to hexachlor- achieved by external heating at 900 – 1000 C.
orhodate(III) by heating with hydrochloric acid. In earlier days, the thermal decomposition of
This can be followed by reprecipitating K3[Rh PGM compounds was carried out in gas-heated
(NO2)6] or precipitating [RhCl(NH3)5]Cl2. muffle furnaces that were not very leaktight. The
best of these were provided with a collection
chamber for NH4Cl (sublimation temperature
6.6. Conversion of Salts into Metals 340 C) and included a waste gas system [43].
[31], [36], [41], [108], [118] Today, tubular fused silica reactors, enclosed in
an electrically heated furnace, are used. A stream
The end products of PGM separation are metal of inert gas can be passed through at a controlled
compounds, but all platinum group metals are rate, and absorption equipment is present for
marketed almost exclusively in the form of me- NH4C and HCl. Automated plants are in opera-
tallic sponge or powder. tion [163], [164].
Conversion to the metals is carried out mainly Thermal treatment of PGM compounds can also
by thermal decomposition of the ammonium be carried out in the presence of hydrogen. For
safety reasons, a mixture of hydrogen and nitrogen hexachlorometallates are present, because their
below the ignition temperature is preferable. decomposition products cannot be sublimed.
Another possibility to convert PGM compounds
into metals is chemical reduction with, e.g., hydra- Palladium. The thermal decomposition of
zine in aqueous media. This process must be used if dichlorodiaminepalladium(II), [Pd(NH3)2Cl2],
the final products of purification are salts other than begins at ca. 290 C in an inert atmosphere.
the ammonium salts (e.g., K2[PtCl6]). Process conditions are the same as for
(NH4)2[PtCl6]. The reaction is
Platinum. The compound (NH4)2PtCl6 can
3½PdðNH3 Þ2 Cl2 !3 Pdþ4 NH4 Clþ2 HClþN2
be converted to platinum sponge by thermal
decomposition at 800 C, according to
For the calcination of ammonium hexachlor-
3 ðNH4 Þ2 ½PtCl6 !3 Ptþ2 NH4 Clþ16 HClþ2 N2 opalladate(IV), which loses chlorine at ca.
280 C, the temperature should be increased
extremely slowly over the range 100 – 300 C.
Excessive carryover of platinum can be
If calcination is carried out in air, the palladium
avoided by introducing ammonium hexachloro-
sponge formed contains large amounts of PdO,
platinate(IV) into the reaction zone at ca. 300 C
which must be reduced by strong heating in a
and heating it rapidly. Waste gas is washed with
hydrogen atmosphere.
water to extract ammonium chloride, both for
The wet chemical reduction
environmental reasons and to prevent the loss of
traces of platinum. 2½PdðNH3 Þ2 Cl2 þN2 H4 !2 Pdþ4 NH4 ClþN2
If the reaction is carried out in a hydrogen
atmosphere, elemental platinum is formed below and the reduction of (NH4)2[PdCl6] proceed
the sublimation temperature of NH4Cl (ca. quantitatively in strongly ammoniacal solution
350 C). Platinum carryover is then appreciably above 50 C. Sodium formate in alkaline solu-
less, and more ammonium chloride is formed: tion can also be used as reducing agent. A nitro-
gen atmosphere must be used in both cases to
ðNH4 Þ2 ½PtCl6 þ2 H2 !Ptþ2 NH4 Clþ4 HCl
prevent formation of explosive gas mixtures.
Chemical reduction often produces pyrophoric
If NH4Cl is not sublimed but is removed by palladium black, which must be dried in an inert
dissolving in water, finely divided platinum pow- gas atmosphere.
der can be produced by this process. Calcination
of the hexachloroplatinate(IV) of an alkali metal Iridium. The best method of producing irid-
is not recommended, because the alkali metal ium is to reduce ammonium hexachloroiridate
chloride produced is difficult to remove by aque- (IV), (NH4)2[IrCl6], in a hydrogen atmosphere
ous dissolution from the platinum sponge. ca. 800 C, yielding the metal powder. Calcina-
Hexachloroplatinates can usually be reduced tion in air gives an oxide-containing material.
in aqueous solution or suspension according to Wet chemical reduction with hydrazine is possi-
ble only in strongly alkaline sodium hydroxide
ðNH4 Þ2 ½PtCl6 þN2 H4 þ6 NaOH!Ptþ6 NaClþ2 NH3 solution and does not always go to completion.
þN2 þ6 H2 O
Rhodium. Ammonium hexachlororhodate
The reaction proceeds best above 80 C, with (III) is subjected to the same process of thermal
excess NaOH maintained at 2 M and the reaction reduction as used for (NH4)2[IrCl6].
controlled by adjusting the rate of addition of Wet chemical reduction with hydrazine ac-
N2H4. The reaction must be flushed with nitro- cording to
gen, because hydrogen can be formed in a side 4 ðNH4 Þ3 RhCl6 þ3 N2 H4 þ24 NaOH!4 Rhþ3 N2 þ12 NH3
reaction. The platinum black formed is washed to
þ24 NaClþ24 H2 O
remove salts, and either dried to produce powder
or heated strongly to produce sponge. Overall, must be carried out with a large excess of hydra-
wet chemical reduction is more expensive than zine and NaOH at ca. 100 C to ensure complete
calcination but should be used if alkali metal reaction.
Ruthenium. Ammonium hexachlororuthe- The quantity or recycled noble metals should

nate(III – IV) is reduced, preferably in a hydro- normally not exceed 1 % of the metal in the starting
gen atmosphere, at ca. 800 C. Aqueous solutions material. The extent of recycle must be limited,
of ruthenates(IV) (e.g., produced by adding RuO4 because losses are relatively high when noble
to an alkali-metal hydroxide solution) are treated metals are recovered from this type of material.
with ethanol to precipitate hydrated RuO2, which Solutions containing platinum metals with
is reduced in a hydrogen atmosphere at 800 C. only small amounts of other materials should be
concentrated by evaporation in the presence of
Osmium. Osmium tetroxide that has been hydrochloric acid. They can be combined with
absorbed in potassium hydroxide solution is fresh raw material for separation.
precipitated as potassium osmate(IV) by adding If the solutions contain only ammonium chlo-
ethanol. This is reduced by strong heating in a ride and platinum group metals, they can often be
hydrogen atmosphere or reacted with NaBH4 in reused directly as a precipitating agent after
aqueous solution [165]. The product must be concentration in acid conditions.
washed with water in both cases. If the solutions contain large amounts of salts
of alkali metals, alkaline earths, or other metals
6.7. Partial Purification along with platinum and palladium residues, it is
advantageous to separate the ions [PtCl6]2 and
Platinum – Rhodium Mixtures. For in- [PdCl4]2 from the other materials by using
strongly basic ion exchangers. Good separation
dustrial use, platinum and rhodium are often
alloyed together, and separating these elements is achieved if only the two chloro complexes are
during the recovery process may be unnecessary. present. For rhodium and iridium this condition is
often not achieved, because of hydrolysis to give
The solutions obtained by dissolving metallic
platinum – rhodium scrap can be used. The neu- hydroxo complexes, so this method cannot be
tral solutions are treated with a sodium-loaded used unless special precautions are taken.
ion exchanger to replace all unwanted cations In earlier times, noble metals were recovered
with sodium. Sometimes, Naþ is replaced by Hþ, from such solutions by cementation with zinc in a
giving a solution of H2[PtCl6] and H3[RhCl6] hydrochloric acid solution. Aluminum is now the
suitable for further treatment (e.g., reduction by preferred reducing agent because of the high cost
hydrazine to give Pt – Rh powder). of zinc, which must be present in large excess,
Similar processes can be used for treating and the resultant environmental problems. Noble
some single metal catalysts (e.g., material from metals can also be recovered with sodium boro-
the calcination of carbon – palladium). hydride. Alternatively, they can be reduced by
hydrazine in alkaline solution. If no precautions
Surface Cleaning. Some returned metallic are taken, hydroxides of base metals are also
materials with only surface contamination reprecipitated, but these can easily be redissolved.
quire merely surface cleaning, thereby avoiding Copper is also precipitated in this reduction
a wet separation process. They can be treated process. After redissolving the metals, the latter
with acids, such as hydrofluoric acid, or with can be reprecipitated as copper(II) oxalate or
fused salt (e.g., NaHSO4), although some of the another copper(I) or copper(II) salt that is spar-
outer layer of platinum dissolves. ingly soluble in slightly acidic solution.
All materials from which noble metals have
been recovered must be monitored carefully for
6.8. Treatment of Internally Recycled possible noble-metal content before disposal, so
Material that no irrevocable losses occur.
A buildup of base metals occurs in recycled mate-

rial such as mother liquor from precipitation and 6.9. Construction Materials
crystallization. These base metals originate from
the raw materials and from salts formed in the Many of the operations described above pose
reactions, and also include small quantities of special problems in the choice of materials for
platinum group metals from the separation process. equipment and vessels.
Plastics resistant to mineral acids can often be chloric acid saturated with chlorine in a stirred
used. Vessels and reactors lined with hard rubber vessel at ca. 80 C. The solution obtained is
are resistant to acids and saturated chlorine solu- evaporated until it reaches 150 C. When cooled,
tions at 90 C. Unsuitable metals for commonly it changes into solid H2PtCl6 4.5 H2O, which
occurring solutions of platinum and other plati- contains ca. 40 % platinum, no mother liquor is
num group metals include stainless steel, titani- produced. If the platinum is dissolved in aqua
um, zirconium, the Hastelloys, and silver, regia instead of hydrochloric acid – chlorine, the
because these materials cause cementation of nitric acid and NOCl formed must be removed
platinum group metals. Tantalum is an exception. completely, preferably by repeated evaporation
It is resistant to dissolved halogens and does not to a syrupy consistency and redissolution in
cement platinum group metals from solution. It is hydrochloric acid.
a suitable material for steam-heated heat exchan-
gers. Equipment constructed of borosilicate glass Uses. Hexachloroplatinic(IV) acid is the
and glass-lined steel reactors are chemically most industrially important platinum compound.
resistant to all of these materials. For solutions It is used in the production of most other platinum
containing large amounts of ruthenium or osmi- compounds and preparations. It is used primarily
um, other construction materials are recom- to make catalysts by impregnating support ma-
mended, including graphite for some items. terials and as a precursor hydrosilylation
For treating raw materials with acidic molten catalysts.
salts or salts that have a chlorinating action, and
for calcination, the use of fused silica equipment Hexachloroplatinates(IV). Ammonium
is best. Treatment with molten oxidizing alkaline hexachloroplatinate(IV), (NH4)2[PtCl6], and, to
salts is carried out in silver or nickel crucibles. a limited extent, the orange-red salt sodium
hexachloroplatinate(IV), Na2[PtCl6], are impor-
tant in platinum separation processes (see
7. Platinum Group Metal Chap. 6).
Compounds [5], [6], [30], [32], [36],
[41], [88], [105–107], [166], [263–270] Platinum Chlorides. Platinum(IV) chlo-
ride, PtCl4, is produced by careful dehydration
Because of the many possible oxidation states of of H2PtCl6 6 H2O at ca. 300 C in a stream of
platinum group metals and their tendency to form chlorine. It is a red-brown, crystalline, hygro-
complexes, the range of compounds is extremely scopic powder with a relatively narrow range of
wide. thermal stability.
Above 380 C, PtCl4 liberates chlorine and
forms platinum(II) chloride, PtCl2, which is sta-
7.1. Inorganic Compounds ble between 435 and 580 C. Platinum(III) chlo-
ride, PtCl3, is probably formed as an intermediate
7.1.1. Platinum Compounds in this reaction. Above 580 C, further decom-
position occurs to yield metallic platinum. Plati-
Hexachloroplatinic(IV) acid, H2[PtCl6] num(IV) chloride is the only chloride of platinum
6 H2O, Mr 517.92, theoretical platinum content that is soluble in water.
37.68 %, platinum content of commercial prod- Platinum(II) chloride can also be obtained
uct ca. 40 % [commercial names: chloroplatinic from a solution of H2[PtCl4] by careful evap-
acid, hydrogen hexachloroplatinate(IV)], forms oration under vacuum. Chlorides of platinum
reddish brown crystals (mp ca. 150 C), which can be produced by reacting chlorine with
deliquesce in moist air and are readily soluble in finely divided platinum. The chloride obtained
water or alcohol. The usual commercial product will be the one that is stable at the reaction
is an aqueous solution with a platinum content of temperature.
25 %.
Oxides of Platinum. The most industrially
Production (see Chap. 5). Platinum sponge important oxide of platinum is platinum(IV)
is treated with moderately concentrated hydro- oxide hydrate, PtO2 H2O, a hydrogenation
catalyst. To prepare this substance, a solution in hydrochloric acid contain 20 % palladium and
of 9 parts sodium nitrate and 1 part platinum are dark brown.
as H2[PtCl6] is evaporated to dryness. The
product mixture is finely powdered and added Production. The method of producing
to molten NaNO3 (10 parts) at 520 C with H2[PdCl4] solution is similar to that for H2[PtCl4]
agitation. The product is dissolved in water, solution. The metal is dissolved in HCl – Cl2 or
washed, and carefully dried to give a brown HCl – HNO3, the rate of dissolution being higher
powder, insoluble in aqua regia, with poorly than with platinum (see Fig. 6). If dissolution
defined stoichiometry. occurs below ca. 50 C, hexachloropalladic(IV)
Platinum(II) oxide, PtO, and platinum(II) ox- acid is formed first.
ide hydrate, PtO H2O, are also known, but have
little or no industrial importance. Uses. The solution of tetrachloropalladic(II)
acid is the most industrially important palladium
Other Platinum Compounds. The follow- preparation. It is the starting material for almost
ing compounds are used in aqueous electrochem- all other palladium compounds, particularly
istry: potassium tetranitroplatinate(II), K2[Pt catalysts.
(NO2)4]; dinitrodiammineplatinum(II), [Pt
(NH3)2(NO2)2]; and sodium hexahydroxoplati- Palladium(II) Chloride, PdCl2, Mr 177.31,
nate(IV), Na2[Pt(OH)6]. theoretical palladium content 60.0 %, palladium
Potassium tetracyanoplatinate(II),K2[Pt content of commercial product 59.9 %, is a
(CN)4], can be used in electroplating by molten brown to brownish violet powder, insoluble in
salt electrolysis. Barium tetracyanoplatinate(II), water, but readily soluble in hydrochloric acid
Ba[Pt(CN)4], is used in the manufacture of fluo- and solutions of alkali-metal chlorides. It sub-
rescent screens. Many other cyano complexes are limes at 590 C. Decomposition begins at
known. Simple cyanides such as Pt(CN)2 and Pd 600 C and is complete at 740 C.
(CN)2 also exist.
Potassium tetrachloroplatinate(II),K2[PtCl4], Production. The best method of production
is a starting material for the synthesis of most of PdCl2 is careful evaporation of a solution of
Pt (II) compounds. Platinum(II) acetylacetonate H2[PdCl4] in hydrochloric acid, preferably in a
is used in the pyrolytic production of platinum rotary evaporator.
surface coatings (see Section 10.10.2) and is
superior to other platinum compounds in this Uses. Anhydrous PdCl2 is the starting mate-
application. rial for a number of palladium compounds.
Dichlorodiammineplatinum(II), [PtCl2
(NH3)2], is of historical interest and was Palladium Oxides. Poorly defined oxide
known in two forms: ‘‘Peyrone’s chloride’’ hydrates are obtained by adding alkali to aqueous
and ‘‘Reiset’s second chloride.’’ In 1893, solutions of Pd (II) compounds. The Pd (IV)
WERNER recognized that these were cis and oxide hydrates obtained from Pd (IV) solutions
trans isomers. cis-Diammine dichloroplati- release oxygen. A catalytically active palladium
num, also known as cisplatin or cis-platinum, preparation analogous to PtO2 x H2O can be
is used in cancer therapy. Carboplatin (cis- obtained by evaporating a solution of H2[PdCl4]
diammine-1,1-cyclobutanedicarboxylatoplati- and NaNO3, and fusing the product.
num), a second-generation cancer drug shows Stoichiometric palladium(II) oxide, PdO,
fewer side effects than cis-Platinum. Drugs for which is crystallographically well defined, is
oral application like JM 216 are still in clinical obtained by reaction of palladium black with
trials [271]. oxygen or air at 750 C. Decomposition occurs
at 850 C.
7.1.2. Palladium Compounds [168] Ammine Complexes of Palladium. The

addition of ammonia to solutions of palladium
Tetrachloropalladic(II) acid, H2[PdCl4], chloride first causes the formation of a pink
is stable only in solution. Commercial solutions precipitate of the binuclear complex
[Pd(NH3)4PdCl4], known as Vauquelin’s salt, uble in water and mineral acids, is obtained by
which is converted to soluble tetramminepalla- heating rhodium powder to 700 C in a chlorine
dium(II) chloride, [Pd(NH3)4]Cl2, by further ad- atmosphere.
dition of NH3. Acidification of this solution So-called soluble rhodium chloride, with the
yields the sparingly soluble light-yellow trans- approximate composition RhCl3 2.5 H2O, is
diamminedichloropalladium(II), [PdCl2(NH3)2]. obtained by evaporating a solution of H3[RhCl6]
These compounds and reactions are important in in hydrochloric acid, preferably in a rotary evap-
the industrial separation of palladium (see orator. This compound is the most important
Chap. 6) and in electroplating processes. commercial rhodium product, and is used as the
starting material for other rhodium compounds
Other Palladium Compounds. Ammoni- and catalysts.
um hexachloropalladate(IV), (NH4)2[PdCl6], is
important in separation technology. It is an oxi- Rhodium Sulfate. Rhodium(III) sulfate,
dation product of tetrachloropalladate(II) (see Rh2(SO4)3, can crystallize with varying
Chap. 6). Palladium(II) sulfate, palladium(II) amounts of water; it can be obtained by dissol-
nitrate, and palladium(II) acetate are of some ving Rh(OH)3 x H2O in sulfuric acid or by the
importance in preparative chemistry. The ready action of hot sulfuric acid on freshly precipitat-
formation of palladium hydride is exploited in- ed rhodium black. It is used in rhodium plating
dustrially for example for the purification of baths.
hydrogen.
Chlorotris(triphenylphosphine)Rhodium(I),
RhCl[P(C6H5)3]3, is formed by the reaction of
7.1.3. Rhodium Compounds [169] triphenylphosphine with soluble rhodium(III) chlo-
ride in ethanol solution under reflux. It separates as
Hexachlororhodic(III) Acid, H3RhCl6. deep-red crystals.
Wet separation processes and molten salt disso- This complex, and rhodium compounds with
lution usually produce (NH4)3[RhCl6] or similar structures, are important homogeneous
Na3[RhCl6] 12 H2O in crystalline form. Both catalysts (see Section 8.1).
compounds form deep-red crystals, which are
very soluble in water. Free hexachlororhodic
(III) acid, H3[RhCl6], can be obtained by cation 7.1.4. Iridium Compounds
exchange, by oxidative decomposition of the
cation in the case of the NHþ 4 salt (see Section Hexachloroiridic(IV) Acid, H2[IrCl6], is
6.2) or by dissolution of finely divided rhodium produced in aqueous solution by the methods
powder in hydrochlorine acid and chlorine gas. used to obtain H3[RhCl6] (i.e., from the ammo-
The composition of the chloro complexes of nium or sodium salts). It is by far the most
rhodium depends strongly on the concentration important iridium compound. The oxidation state
of hydrochloric acid, the temperature, the dura- is relatively easily changed (in either direction),
tion of reaction, and the previous treatment the very intense dark brown [IrIVCl6]2 changing
of the solution. By starting with a strongly to the lighter colored [IrIIICl6]3 or vice versa.
acidic medium, the following transformations The compounds are used as precursors in the
are possible: preparation of coated anodes for the production
of chlorine and sodium hydoxide. The ammoni-
½RhCl6 3
½RhCl5 ðH2 OÞ2
um salts of both anions are important in separa-
½RhCl4 ðH2 OÞ2
½RhCl3 ðH2 OÞ3
tion technology (see Chap. 6).

½RhCl2 ðH2 O4 Þþ
½RhClðH2 OÞ5 2þ
½RhðH2 OÞ6 3þ

Iridium(III) Chloride, IrCl3. A product
stoichiometrically deficient in chlorine is ob-
The color varies from raspberry red to brown. tained by heating iridium powder in a stream
of chlorine at 650 C. The chlorination reac-
Rhodium Chlorides. Anhydrous, brownish tion is assisted by the presence of carbon
red rhodium(III) chloride, RhCl3, which is insol- monoxide.
7.1.5. Ruthenium Compounds electron-transfer mechanisms in molecular struc-

tures and also serve as sensitizer materials for
Ruthenium(VIII) Oxide, RuO4 is formed photoinduced hydrogen production (see
by the oxidation of aqueous solutions of ruthe- Section 10.9).
nates. It has a melting point of 25.5 C and is Osmium bipyridyl redox polymers com-
therefore a liquid at room temperature. It is both bined with a redox enzyme can be used as
toxic and explosive (see Section 10.1). miniature in vivo sensors for implantation into
diabetes patients for continuous monitoring of
Soluble Ruthenium(IV) Chloride. So- their blood glucose levels (wired enzyme bio-
called soluble ruthenium chloride consists main- sensor, [271]). The divalent and trivalent com-
ly of Ru(OH)Cl3 with some RuCl3 H2O, and is plexed osmium ions can exchange electrons at
prepared by reacting RuO4 with hydrochloric high rates. The osmium polymer connects
acid and evaporating the solution. The compound electrically the redox centres of the enzymes
(NH4)2[RuCl6] can be precipitated by adding by introducing electron relays close to the
NH4Cl. Solutions of ruthenium chloride in hy- enzyme active site. A sol – gel based ampero-
drochloric acid are used in the production of metric biosensor incorporates an osmium re-
coated anodes. dox polymer as mediator for detection of
lactate [272].
Potassium Ruthenate(VI), K2[RuO4], is Ruthenium phthalocyanine complex com-
formed by fusing ruthenium with KOH – KNO3 pounds have proven effective as drugs for pho-
or by dissolving RuO4 in potassium hydroxide todynamic cancer therapy. It is administered
solution. intraperitoneally, followed by laser irradiation
of the tumor tissue. The compound acts in the
presence of light as sensitizer to induce the
7.1.6. Osmium Compounds photochemical destruction of the unwanted
tissue [273].
Osmium(VIII) Oxide, OsO4, 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. OsO4
used as an oxidation catalyst or as an aqueous
solution to stain organic tissue for microscopic
analysis.
Potassium osmate(VI), K2[OsO2(OH)4], is Ruthenium complexes with polyaminocar-

formed by the reaction of OsO4 with potassium boxylate ligands act as effective nitric oxide
hydroxide solution and alcohol. scavengers. The binding property for nitric oxide
enables macrophage cells to kill tumor cells and
may also form the base for drugs against other
7.2. Organic Compounds [170], [171] nitric oxide influenced diseases including hyper-
tension, epilepsy, diabetes, arthritis, and septic
The PGMs form numerous compounds with shock [274].
direct metal-carbon links both as carbonyls and Giant, dendritic organic coordination com-
as organometallic compounds. Many of these are plexes of ruthenium and osmium (dendrimers,
of industrial importance in homogeneous cataly- [276–279]) with up to 22 ruthenium atoms have
sis (see Section 10.5). Complex organic com- been synthesized, which may be used for the
pounds of ruthenium and osmium can facilitate production of thin films.
Ruthenium forms catalytic active complex 8. Alloys [28], [30–32], [88–91], [166],
compounds with C60 molecules [280–282]. [167], [172–184]
8.1. Alloy Systems
All the platinum group metals are infinitely

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.
Figure 21. Phase diagram of binary platinum group metal

Figure 19. Phase diagram of binary platinum group metal alloys: Fe – Pt
alloys: Ag – Pt
Some phase diagrams of the binary alloys of temperature resistance, electrical conductivity,
platinum according to Massalski [90] are shown thermoelectric power, and magnetic behavior.
in Figures 19–33; of industrial importance are Platinum – palladium alloys are used in
mainly the binary alloys Pt – Rh, Pt – Ir, Pt – jewelry, for electrical contacts, and for equip-
Pd, Pt – Au, but Pt alloyed with base metals (Ni, ment parts for glass production and construction
Co, W) and a few ternary or higher alloys are also elements in highly corrosive environments.
used. 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
8.2. Special Alloys [283]. Pt alloys are used in spark plugs for
automotive engines.
Platinum and palladium are the most important Dispersion-strengthened platinum and plat-
base components of industrially utilized PGM inum alloys are produced by coprecipitation of the
alloys. Special properties of interest concern metals and refractory oxides, for instance, with
corrosion resistance, mechanical strength, high ZrO2 (zirconium oxide grain-stabilized platinum,
Figure 20. Phase diagram of binary platinum group metal Figure 22. Phase diagram of binary platinum group metal
alloys: Au – Pt alloys: Co – Pt
alloys: Pt – Rh alloys: Fe – Pd

Figure 24. Phase diagram of binary platinum group metal alloys: Ni – Pd
alloys: Ag – Pd
alloys: Au – Pd alloys: Cu – Pd
alloys: Pd – H alloys: Ir – Rh
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 –
alloys: Ag – Rh rhodium alloys have higher strength than pure
alloys: Fe – Rh alloys: Ir – Pt
platinum at 1000 C, finer grain structure, and netic Sr3CuPtO6 and the ferromagnetic
better resistance to wetting by molten glass. Sr3CuIrO6. The platinum : iridium ratio deter-
Platinum – iridium alloys find different ap- mines the magnetic behavior of the solid solution
plications in electrochemistry, chemical technol- [288]. Alloys of the type Cr1xIrxO2 (0 < x
ogy, medicine, and jewelry. Iridium contents (in < 0.3) are ferromagnetic materials with high
wt %) are for laboratory ware 0.4 – 0.6 %, jew- coercivity [289].
elry 5 – 15 %, medical applications 10 %, elec- Platinum – nickel alloys have been proven
trical contacts 10 – 25 %, electrodes 10 %, pens, in electrical switches and as high-strength and
needles, springs 25 – 30 %. Maximum hardness highly temperature resistant construction mate-
(ca. 360 HB) is reached with 30 % iridium. rials in the chemical industry. Compositions
W – Th – Al-doped platinum – 26 wt % range from trace amounts up to 20 % nickel with
iridium and platinum – 30 wt % rhodium are maximum tensile strength of about 1725 MPa
used to encapsulate plutonia fuel pellets for after 90 % cold reduction.
spacecraft heat sources [290]. Platinum – tungsten alloys, commonly used
Platinum – rhodium alloys with 10 % rho- in compositions with 5 – 8 wt % Co, have ex-
dium are used as catalyst for the oxidation of cellent wear resistance. They are used for poten-
NH3, as the standard element in thermocouples tiometers, glow wires in copiers, diode switches,
(Pt – Rh of different compositions or Pt), and as heater elements and cladding on rods for fuel
heater elements in electrically heated high-tem- elements in nuclear reactors.
perature furnace. Pt – Rh alloys with additions of Platinum electrodes are hardened with iridi-
Au are especially resistant to wetting by molten um for use in spark plugs and as corrosion
glass. They are used in machine parts for the resistant electrodes.
production of high-tech glasses for computer In equiatomic Ti – Ni alloys, (known for the
monitors, cathode ray tubes, television screens, shape-memory effect), substitution of nickel by
liquid crystal displays, and plasma panels; glass 2 atom % ruthenium stabilizes the high temper-
fibers for telecommunication; and for use in ature B2-type phase at room temperature [292].
glass-reinforced construction materials. Partial replacement of Ni by palladium in the
Platinum – ruthenium alloys. Ruthenium equiatomic TiNi alloy improves the shape mem-
strengthens platinum very effectively; 10 % ru- ory properties [293].
thenium increases the hardness to 168 HV. The Platinum alloys are components in catheters
alloy PtRu5 has the same strength, hardness, and for pacemakers, in dental gold alloys, in marker
corrosion resistance as the alloy PtIr10 (‘‘hard bands, in guidewires and in temporary and per-
platinum’’). Applications are jewelry items, elec- manent implants.
trodes for electrochemistry, spark plug electro- Palladium – gold alloys are the basis of pre-
des, electrical contacts, and wear-resistant wires cision resistance alloys. Addition of iron accent-
in potentiometers. Higher alloy compositions up uates the formation of long range ordering. The
to 14 % ruthenium and ternary types with 15 % alloy Au50Pd45Mo5 has a resistivity of
rhodium and 6 % ruthenium are used for electri- 100 mWcm and a temperature coefficient of re-
cal contacts and potentiometer wires for heavy- sistance (TCR) of 0.00012 K1 between 0 and
duty applications. 100 C.
Platinum – cobalt multilayers on various The tensile strength reaches values of about
substrates are used for ultrahigh-capacity hard 1060 N/mm2.
disks, for magneto-optical storage, and perpen- Palladium – silver alloys are used as capac-
dicular recording applications. Special proces- itor electrode layers, as silver conductor paths,
sing enhances domain wall pinning effects and and as resistor elements in thick-film circuits.
leads to higher coercivity [286]. Pt – Fe alloys The palladium – silver alloy with 40 atom % Ag
have maximum coercivity at 39.5 wt % platinum has the highest electrical resistivity at room
[287]. temperature. It finds use for precision resistors
A new class of magnetic behavior, random in electrical technology. The resistivity between
quantum spin chain paramagnetism, is exhibited 20 and 100 C is nearly constant and amounts to
in one-dimensional compound Sr3CuPt1xIrxO6 42.5 mW cm; between 20 C and 800 C the
prepared as solid solution of the antiferromag- resistivity changes from 42.5 to 44 mW cm.
Ternary alloys containing silver and copper pure palladium and are resistant to thermal cy-
with up to 10 to 25 % palladium are hard solders cling [299]. Pd – Ag23 exhibits extremely high
for high-strength. hydrogen permeability and is used for semiper-
Palladium – ruthenium with 4.5 wt % ru- meable membranes for the extraction and purifi-
thenium is a standard jewelry alloy in the United cation of hydrogen up to 99.99999 % purity.
States. Alloys with ruthenium contents up to Palladium – silver permeation membranes are
12 % serve as material for electrical contacts provided in the form of bundled tubes with
and as catalysts for the reduction of nitric oxide. wall thickness of ca. 75 mm, sealed at one
Palladium alloys with 60 – 80 wt % Pd for end. Hydrogen is pressed from outside through
use in dentistry contain copper and gallium as the tubes, dissociating and diffusing through
hardening elements and tin to lower the melting the alloy to the inner side of the tubes, leaving
temperature. Best corrosion resistance is attained most impurities outside the membrane [300],
with a single-phase structure in the composition [301].
range of Cu 4 – 6 wt %, Ga 5 – 7 wt %, and Sn The solubilities of the hydrogen isotopes in
6 wt %. Addition of 1 wt % palladium to silver – palladium and palladium – silver alloys differ
tin – copper amalgam alloys improves hetero- to an appreciable degree. Diffusion membranes
geneous phase formation and the thermal stabil- of palladium or palladium – silver alloys can
ity [294]. therefore be used for separation and concentra-
Palladium alloys with iron and with cobalt tion processes of different hydrogen isotopes
show ferromagnetism. [302]. The equilibrium hydrogen/deuterium
By alloying palladium with 0.1 wt % cobalt, separation factors vary from ca. 2.4 at 25 C to
the palladium atoms surrounding a cobalt atom, 3.7 at 80 C [303]. For the hydrogen/tritium
are strongly magnetized to magnetic moments in ratio, a value of 2.8 was measured at 25 C
the order of 10 mB, which is about six times [304].
larger than that of a single cobalt atom. The ternary alloy Pd – Ti – Al is ferromag-
Palladium and certain palladium alloys are netic, in contrast to the antiferromagnetic alloy
unique in their capability to dissolve large Pd – Ti [25].
amounts of hydrogen up to about 2800 times Pt and Pt alloys are electrocatalysts in low-
their own volume [295–297]. Hydrogen enters temperature fuel cells. The phosphoric acid fuel
palladium interstitially. The hydrogen atoms are cell (PAFC) contains a Pt – Co – Cr alloy on
located in the octahedral holes of the fcc lattice. the cathode side and straight platinum on carbon
Above 295 C, palladium and hydrogen form a as the anode. The higher activity of alloys
continuous serious of solid solutions with fcc compared to pure platinum on the cathode side
structure. Below that temperature, the phase is due to the fact that the non-noble metal
splits into a fcc palladium-rich phase and an fcc components are leached from the alloy crystal-
hydrogen-rich phase, and the result is a miscibil- lite surfaces, leaving a highly reticulated and
ity gap which broadens with decreasing temper- active surface [306], [307]. The catalytic activi-
ature. The occupation of interstitial sites by ty is effected by the preparation method and the
hydrogen atoms causes expansion of the palladi- crystal structure of the three-component alloy
um lattice. The lattice parameters increase with [308]. The proton exchange membrane fuel cell
increasing hydrogen content from 3.891 A for (PEMFC) contains a platinum – ruthenium-
pure palladium up to 4.06 A at 75 atom % hy- loaded graphite anode and pure-platinum-load-
drogen [298]. Thermal cycling of Pd – H alloys ed graphite cathode [309]. The ruthenium alloy
in the duplex phase region causes high mechani- protects the catalyst against poisoning by the
cal stresses due to changes of the lattice dimen- carbon monoxide which may be present in the
sions with changing amounts of dissolved hydro- hydrogen supply. Platinum – ruthenium alloys
gen. Pure palladium, when repeatedly heated and are also used as the anode catalyst in the direct
cooled in hydrogen-containing atmosphere, be- methanol fuel cell (DMFC [310]). They prevent
comes brittle and cracks. the formation of linearly bonded carbon mon-
Palladium – silver alloys with 20 – 25 wt % oxide (Pt–CO) during the electrosorption of
silver dissolve larger amounts of hydrogen than methanol on the platinum.
Iridium alloys are used in microelectrodes for tant method of treating iridium. This melting
testing water quality by square-wave anodic process causes selective evaporation of trace
stripping voltammetry [311]. elements and impurities at ca. 2700 C.
Alloying of titanium and high-strength titani- Platinum, palladium, and most of their alloys
um alloys (e.g., Ti – 6Al – 4V) with 0.1 % ru- can be mechanically shaped by forging, rolling,
thenium effects improvements in the corrosion drawing, and by deep drawing, etc., at room
resistance against hydrochloric acid solutions temperature, with intermittent heating. Form-
and can supersede corresponding Ti-Pd alloys. ability decreases with increasing proportions of
Selective dissolution generates on the surface the other platinum group metals in the ascending
cathodic sites of low hydrogen overvoltage. This series palladium, rhodium, iridium, ruthenium,
accelerates hydrogen ion reduction and thus and osmium. Special techniques are used for
causes a substantial shift in the corrosion poten- weaving and knitting Pt – Rh catalyst gauzes
tial towards higher nobity, where the protective and for drilling extremely small holes in the
surface oxide film is stable. Applications are platinum alloy spinneret nozzles used in the
apparatus parts for processing corrosive chemi- production of fibers.
cals [291]. Platinum and the other metals can also be
Platinum metals based intermetallics in al- processed by powder metallurgy. The process of
loyed or composite microstructures show inter- inert gas spraying is used to produce powders.
esting properties in high temperature strength Particle sizes are around 50 mm.
and oxidation resistance as needed for materials Platinum and palladium can be fusion welded
in high temperature service. Prototypes are Ir – without special precautions by TIG, plasma,
IrN-composites with refractory metals. Pt – Al – and laser welding. Platinum metal can also be
Ru-alloys, ferritic alloys with Ru, and eutectic diffusion welded by hammering at red heat. A
Ru – RuAl and Ir – IrAl alloys [312]. protective gas must be used with rhodium and
iridium.
8.3. Methods of Treatment [88], [107],

[166], [167] 9. Quality Specifications and Analysis
[5], [36], [185–198]
The starting material for the manufacture of
PGM alloys from platinum and palladium is 9.1. Quality Specifications [185], [200],
generally metal sponge. The remaining ele- [201]
ments – rhodium, iridium, ruthenium, and osmi-
um – are supplied as powders. Platinum and pal- In industry, the purity and fineness of platinum
ladium are also available in ingot form. and platinum metals are even today often de-
Owing to their high melting points, the plati- scribed by the classifications ‘‘technically pure’’
num group metals are almost invariably melted in (99 %), ‘‘chemically pure’’ (99.9 %), ‘‘physically
an induction furnace, either under vacuum or pure’’ (99.99 %), and ‘‘spectroscopically pure’’
with argon as a protective gas. The vigorous (99.999 %). These are taken from the recommen-
mixing action produced by inductive heating is dations of the Physikalisch-Technische Reich-
an additional advantage in producing alloys. sanstalt [29].
Crucible materials can be aluminum oxide; zir- Present practice is to use the following
conium oxide; or magnesium oxide. Pure cal- qualities:
cined calcium oxide was also used in the past.
The molten metal is poured into water-cooled
99 % (now hardly used)
copper molds. The refractory platinum group 99.9 %
metals, ruthenium and osmium, are seldom need- 99.95 %
ed as pure, solid metals, but may be compacted by 99.98 %
sintering. Electric-arc melting and electron- 99.99 %
99.999 %
beam melting are sometimes used. Electron- 99.9999 % (only in exceptional cases)
beam purification has recently become an impor-
Table 6. ASTM standard specifications for platinum group metals chloride solution, no precipitation occurs at
Metal Standard Grades
first; the brown hydroxide precipitates only
when ethanol is added. This distinguishes
Pt B 561 - 94 99.95, 99.99 between Rh and other PGMs.
Pd B 589 - 94 99.95
Rh B 616 - 96 99.80, 99.90, 99.95
Iridium can be detected by heating a solution
Ir B 671 - 81 (Reappr. 1993) 99.80, 99.90 in concentrated sulfuric acid to fuming and, after
Ru B 717 - 96 99.80, 99.90 cooling, adding ammonium nitrate. Renewed
warming of the solution produces an intense blue
color by formation of anionic complexes of IrIV.
Other specifications are used for particular Chemically, even microgram quantities of ruthe-
applications (e.g., physical properties if used in nium can be detected in hydrochloric acid solu-
sensors or microelectronics [202], [203]). tion by the formation of a blue complex of RuIII
Apart from osmium ASTM standard specifi- with thiourea.
cations are available for the chemical composi- Osmium interferes with Ru detection with
tion of some grades of the other refined PGMs thiourea by formation of a red complex of OsIII,
(Table 6). which can be used for identification of Os. It can
Most commercially available platinum and be separated from Ru by distillation from nitric
palladium have purities of 99.95 – 99.98 %. acid solution. The stinging odor of (the toxic)
Higher purities usually sell at higher prices. Plati- osmium tetroxide is also characteristic.
num and palladium are generally supplied as In the PGM industry spectrochemical meth-
ingots or bares (stamped with the purity). Other ods are used almost exclusively for qualitative
platinum metals are supplied mainly as powder. analysis. The detection sensitivity for platinum in
Platinum and palladium ingots of 500 – solutions by using the 265.85 nm emission line is
1000 g are preferred for investment purposes in only slightly higher with inductively coupled
Japan [1]. plasma optical emission spectroscopy (ICP-
OES) than with flame atomic absorption spec-
troscopy (FAAS). X-ray fluorescence (XRF) of-
9.2. Qualitative Analysis fers quick detection or identification facilities for
PGMs in metallic or nonmetallic materials. The
The older wet chemical qualitative reactions 244.8 nm, 340.46 nm, and 363.47 nm lines are
have not entirely lost their usefulness. used amongst others for the spectro-analytical
Platinum can be identified by the precipitation detection of palladium by classical spectrogra-
of PtIV as yellow crystalline K2[PtCl6] or phy, FAAS, or ICP-OES. The surest way of
(NH4)2[PtCl6] from dilute hydrochloric acid so- detecting rhodium spectroanalytically is by using
lution by the addition of a KCl or NH4Cl solution. the 343.49 nm line with the above-mentioned
Other quadrivalent platinum group ions interfere. methods. Frequently used lines of Ir are at
Analogous to Cassius gold purple, platinum 212.68 nm, at 215.27 nm, and at 224.27 nm. For
forms platinum purple in weakly acid solutions Ir, the detection limit of ICP-OES is two orders of
by reduction with SnCl2, Zn, or Al. The detection magnitude better than with FAAS. The spectro-
limit is ca. 1 mg/L, but Pd, Rh and Au can analytical detection or identification of Ru by
interfere. means of FAAS or ICP-OES offers no problems,
The chemical detection of palladium uses as a series of lines, e.g., at 240.27 nm or
precipitation of PdII as the yellow, ammonia- 349.89 nm, are available. Among all PGMs, Os
soluble dimethyldioxime complex. In contrast has the lowest detection limit when ICP is used.
to the corresponding PtII compound, the Pd com-
plex precipitates at low temperatures.
There is no simple specific detection reac- 9.3. Quantitative Analysis [313]
tion for the mainly trivalent rhodium. If other
colored ions are absent, it can be recognized The methods of analysis used for economic
by its raspberry pink color in solutions of control reasons when buying and selling crude
rhodium(III) chloride or hexachlororhodate products, alloys, compounds, etc., must reflect
(III) complexes. If KOH is added to a RhIII the high value of PGMs.
Chemical Assay Methods. For commonly Platinum – Iridium Alloys. Platinum – irid-
occurring combinations of elements, mandatory ium alloys are converted into a finely divided
methods of analysis and sampling have been state by fusion with zinc, and removing the zinc
developed. The classical methods of separation with HCl, and the platinum is dissolved with aqua
and gravimetrical determination outlined briefly regia. Iridium remains undissolved and, after
below are today of minor importance. PGMs reduction with hydrogen, is weighed.
present in concentrations from mg/g to a few The classical dissolution for alloys like Pt – Ir
percent are often subjected to preliminary con- and Pt – Rh beginning with a fusion with zinc
centration by fire assay with lead (see ! Gold, can be replaced advantageously by dissolving the
Gold Alloys, and Gold Compounds, Section alloys in a mixture of HCl and HNO3 under
9.3.), nickel sulfide, or copper as collector prior pressure in a sealed glass tube which is heated
to the determination. in a drying furnace, or by dissolution in a PFA or
quartz vessel by using a microwave furnace.
Platinum – Base Metal Alloys. Platinum is The PGM content of commercial compounds
precipitated as (NH4)2[PtCl6] from a nitrate-free and preparations is usually determined gravi-
solution of H2[PtCl6] by addition of NH4Cl, the metrically by reduction in solution with hydra-
precipitate is heated strongly, which converts it to zine or by reduction of the solid sample with
platinum, and then weighed [314]. Another pos- hydrogen. Reductive precipitation from solu-
sibility to determine platinum gravimetrically is tion in strong hydrochloric acid by treatment
the reduction with mercury(I) chloride [315]. For with zinc turnings is an exact method if carefully
Pt on a-Al2O3 catalysts used in the petroleum carried out.
industry, the possible method of determining
platinum is by the coloration produced with tin Physical Methods. Physical methods, espe-
(II) chloride, which is determined photometrical- cially spectroscopic ones, are increasingly being
ly after extraction with ethyl acetate or after used, because they are inexpensive and, with
preliminary separation of platinum by reduction improvements in the equipment, have sufficient
with formic acid. accuracy for economic purposes. If brought into
solution by suitable acid treatment and/or fusion,
Platinum – Rhodium Alloys. A finely divid- such as Na2O2 fusion, and after separation from
ed black metal is obtained by fusion with zinc interfering base metals, the PGMs can be deter-
followed by treatment with hydrochloric acid. mined simultaneously by X-ray fluorescence, or
Platinum is dissolved in aqua regia, ICP-OES. Application of the principle of internal
(NH4)2[PtCl4] is precipitated and heated strongly standardization (! Gold, Gold Alloys, and Gold
to yield platinum. The remaining noble metal is Compounds, Chap. 9.) is mandatory for precise
reductively precipitated from the mother liquor, work. The measurement procedures outlined in
combined with the residue remaining after aqua [316] for Pt and in [317] for Pd can be applied also
regia treatment, and treated with chlorine at to the ICP-OES of Rh, Ir, and Ru. The difficult and
650 – 700 C. The RhCl3 obtained, which is time-consuming separation of the PGMs from one
insoluble in aqua regia, is heated strongly in a another is no longer necessary. Therefore, analy-
hydrogen atmosphere to produce the metal, sis of complex materials containing precious
which is weighed. metals, such as PGM ore concentrates containing
gold, offers no problems. XRF can also be used
Platinum – Palladium Alloys. Palladium is for direct anlysis of metallic materials with suffi-
quantitatively precipitated with dimethylglyox- cient accuracy for production control in the
ime from a dilute solution in aqua regia. It is manufacturing of defined alloys. Calibration of
filtered off, washed thoroughly, calcined, re- this method may however be difficult.
duced to the metal by hydrogen, and weighed.
The dimethylglyoxime in solution is decom-
posed by aqua regia, and platinum is converted 9.4. Purity Analysis
to (NH4)2[PtCl6], precipitated as sulfide, isolated
as the metal by reduction with hydrogen, and The precious metal content of commercial grades
weighed. of PGMs can be determined more precisely by
measuring the total content of impurities by physi- 10. Uses [3], [5], [30], [31], [204], [167]
cal methods than by direct determination of the
main constituent. The most important of these 10.1. Jewelry, Coinage, Investment
methods are emission spectroscopy, e.g., with [166]
spark or glow discharge excitation. Recently, DC
arc spectrometry became important again, because In recent decades, platinum has been in such
the application of a solid-state detector [318] en- demand for jewelry and high-quality watchmak-
ables simultaneous background corrections. Spark ing that more than one-third of all the platinum
ablation ICP-OES offers an alternative method. consumed has been used for this purpose. Of this
When PGMs have been brought into solution (if amount, Japan uses about 90 %, with the United
necessary by dissolution in a mixture of HCl and States taking the next largest share. Most of the
HNO3 under pressure by conventional heating in a alloys employed contain 95 % platinum and are
sealed glass tube or by using a microwave furnace), stamped PLAT 950. The mechanically more
the metallic impurities can be determined simulta- stable alloys Pt 95 – Cu 5 (Pt96/Cu 4), the hard-
neously with a ICP-OE spectrometer with a solid- er alloys PtW 95/5, Pt 96 – Pd 4, and Pt 90 –
state detector [charge injection device (CID) or Ir 10 are used for mounting precious stones. Pt/
segmented-array charge-coupled device (SCD)]. Co is used for jewelry casting. A relatively new
Another solution technique of interest here is ICP- alloy has a Pt content 99.9 %; the hardness for
MS. Atomic absorption spectroscopy is of minor jewelry is obtained with a small amount of sili-
importance. Mass spectrometry with glow dis- con. Forming costs for platinum are considerably
charge ablation (GD-MS) is used in special cases, higher than those for gold because the metal is
e.g., for 99.995 % or purer metals. more difficult to work, and recycling costs are
high. These factors markedly affect total cost.
Very good resistance to corrosion and erosion
9.5. Trace Analysis is required of alloys used for the nib tips of high-
quality fountain pens [166]. These alloys are
The determination of traces of precious metals is based on ruthenium, iridium, and osmium.
of great importance in mineral prospecting. Here In the Russian Empire in 1828 – 1845, a total
metal contents of only a few mg/g are of interest. of 15 t of platinum was formed into 3-, 6-, and 12-
Methods such as graphite tube AAS, neutron rouble pieces by sintering, minted, and brought
activation analysis, total reflection X-ray fluores- into circulation.
cence analysis, and ICP mass spectrometry (ICP- The fineness was 99 % platinum or 99.2 % PGM
MS) are used after appropriate enrichment pro- [15]. Between 1977 and 1980, platinum coins were
cedures (e.g., by fire assay with nickel sulfide as again minted for the Moscow Olympic Games.
collector). These were 150-rouble pieces, fineness: 9999, 1/2
The analysis of traces of precious metals in ounce, in five designs. Since then, platinum coins
waste materials from the precious metal proces- have been officially minted in other states (e.g., a
sing industry, especially refineries, has always Platinum Noble in the UK, a Platinum Maple Leaf
been very important in monitoring the economics in Canada, and a Platinum Koala in Australia). The
of the process. standard issue of all these coins contained one troy
Trace analysis of platinum, palladium, and ounce (31.1035 g) of fine platinum. Small ingots,
rhodium has become important in recent years. usually containing 99.995 % platinum, are also
Whereas both the occurrence and the use of PGMs minted, intended mainly for small investors. The
have hitherto been located, automobile exhaust- use of palladium for this purpose has recently
gas catalysts now constitutes a widespread use. begun on a small scale.
Although no toxic effects on the environment
have thus been reported, methods of analysis must
be continually improved as permitted levels in the 10.2. Apparatus [205–208]
soil and the atmosphere become increasingly
strict. The collection of the PGMs in a nickel Laboratory Technology. Platinum cruci-
sulfide phase by fire assay followed by GFAAS or bles, dishes, boats, and electrodes (for electrogra-
ICP-MS is suitable for analysis in the ng/g range. vimetry) have long been basic items of equipment
in chemical laboratories. In earlier times, the purity In the manufacture of glass fibers and glass
of platinum was variable. Moreover, equipment wool, the spinnerets are made of Pt – Rh. Rock
made of pure platinum is not dimensionally stable, wool and slag wool are made by a centrifugal
so today the more stable alloys Pt 97 – Ir 3, Pt 95 spinning process with platinum centrifuges.
– Au 5, and occasionally Pt 99.7 – Ir 0.3, are
mainly used [209]. Textile Technology. Nozzles made of plat-
Another type of dimensionally stable plati- inum alloys such as Au 70 – Pt 30 and Pt 92 –
num is dispersion-hardened platinum, which Ir 8 are used for spinning viscose fibers [214].
contains 0.1 to 0.2 wt % of high-melting oxide
(e.g., ZrO2, Y2O3) in finely divided form [88]. Soldering Materials. Gold and palladium
The presence of this material reduces the mobili- have been used in some special solders.
ty of crystal imperfections. It is produced by
precipitation, internal oxidation, or mechanical
mixing followed by sintering of the powder. The 10.3. Heterogeneous Catalysts [92],
metal can be unalloyed platinum, or alloys of [215–220]
platinum with rhodium or gold. Rhodium and
iridium crucibles can resist extremely aggressive All platinum group metals have strong catalytic
conditions in nonoxidizing atmospheres. activity, especially for hydrogenation reactions.
The catalytic properties of the platinum metals
Chemical and Electrochemical Appara- group elements can be regarded in relation to
tus [210], [319]. The platinum metals and their those of the elements of group 8 – 10 of the first
compounds are of limited use in chemical pro- row of the periodic system. A clear correspon-
cess technology owing to their high cost. How- dence to the differences in their catalytic behav-
ever, platinum components are essential in fluo- ior has been found in their behavior in coordi-
rine chemistry. Bursting disks for protection nation formation, in complex formation, and in
against excessive pressure are occasionally made chemisorption behavior. The bond dissociation
of platinum or palladium. Single crystals for the energies of the related compounds, complexes,
optical industry and for laser technology are and adsorbed atoms or molecules are weaker for
grown in crucibles of platinum, rhodium, or the elements of the first two rows than for those
(most commonly) iridium [210]. For the electro- of the third row. Insofar, closer relation exists
chemical production of peroxo compounds, such between the catalytic characteristics of the ele-
as hydrogen peroxide and peroxosulfate, massive ments Fe, Co, Ni and Ru, Rh, Pd compared with
platinum anodes or hollow platinum wires are the elements of the third row. This special
used, although such use has decreased [319]. energetic situation allows easier intermolecular
exchange of p- and ps electrons, which takes
Glass Technology [210–213]. The corro- place in numerous heterocyclic and homoge-
sion and erosion resistance of platinum metals neous catalytic reaction. Examples are the reac-
toward molten glass is not matched by any other tion of carbon monoxide with hydrogen, hydro-
material [88]. High-purity optical glass is best formylation, reactions with methanol, and the
melted in crucibles of unalloyed platinum. Spe- catalysis of reactions with unsaturated hydro-
cial iron-free glass for sodium vapor lamps, X- carbons. The heterogeneous catalysts, including
ray windows, and cathode-ray tubes is melted in supported catalysts, are of major importance in
Pt – Rh vessels. chemical technology. As of 1998, 220 – 240 t
In the automated production of bottles by of platinum group metals are in use worldwide
large holding furnaces, the use of platinum com- in the form of supported catalysts. Next in order
ponents ensures problem-free operation over of importance are bulk metallic catalysts in the
long periods. These components include com- form of wire gauzes, highly dispersed carrier-
plete feeder systems, stirrers, plungers, skim- free metals, and oxides. Platinum and palladium
mers, pouring funnels, thermocouple protection are technically much more important than rho-
tubes, and level-measuring devices. Nowadays dium, ruthenium, iridium, and osmium. Often,
dispersion-hardened platinum in increasing two or more platinum group metals are com-
quantities is used in glassmaking technology. bined (Table 7).
Table 7. Modification 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 þ 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 better selectivity
to butadiene, methanol to formaldehyde
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
Supported Catalysts. The properties of aluminum silicates (zeolites) are also common.
supported catalysts are very dependent on the Supported palladium catalysts are used in hydro-
interaction between noble-metal catalysts and gen peroxide production.
support material. Classical support materials In the pharmaceutical industry, palladium/
were asbestos and pumice stone. Important sup- active carbon hydrogenation catalysts are widely
port materials today include aluminum oxides, used, mainly with a palladium content of 5 %.
activated carbon, silicates (e.g., zeolites), and Other catalysts used include rhodium/activated
silica, also in combinations and as washcoats. carbon, platinum/activated carbon, palladium –
Powdered support materials are used as suspen- platinum/activated carbon, and iridium/activated
sion catalysts; porous pressed shapes, pellets, and carbon, sometimes promoted by other elements,
monolithic structures in newer applications are e.g., vanadium, iron, or bismuth. Lindlar cata-
used as fixed-bed catalysts. Reactions catalyzed lysts (Pd, Pd/CaCO3) play an important role
by platinum group metals are listed in Table 8 in pharmaceutical industry. Platinum on electri-
[319]. cally conducting carbon black is used as catalyst
The largest demand for platinum catalysts in fuel cells. Furthermore precious metal formu-
comes from the petroleum industry [221], lations are used for exhaust gas catalysts, e.g., to
[222]. These are used in reforming high-boil- control automotive emissions (! Automobile
ing fractions from the distillation of crude oil Exhaust Control).
at atmospheric pressure. The most important
reactions are the dehydrogenation of alkylcy- Solid Metal Catalysts [223–226]. Plati-
clohexanes, the isomerization and dehydroge- num – rhodium gauzes are used as catalysts for
nation of alkylcyclopentanes, and the dehydro- the large-scale oxidation of ammonia to nitric
genation and cyclization of alkanes, all of oxide (Ostwald and Brauer process) in the man-
which form aromatics, as well as hydrogena- ufacture of nitric acid (! Nitric Acid, Nitrous
tive cleavage of alkanes and naphthenes, and Acid, and Nitrogen Oxides).
dealkylation of alkylaromatics. The resulting The oxidation reaction
product mixtures are gasolines with high oc-
tane numbers. The most important catalysts
are Pt – g-Al2O3 Pt, Re/g-Al2O3, and Pt, Sn/
g-Al2O3. Other catalysts such as Pt, Ir/
g-Al2O3, Pt, Pd/g-Al2O3 or Pt, Ge/g-Al2O3 takes place in reactors in which many fine-
may also be used. mesh gauzes are stacked above one another.
Another use for PGM catalysts in the petro- The rate of loss of noble metal varies between
leum industry is in hydrotreating processes. In 0.2 and 2.0 g per tonne of nitrogen reacted,
addition to base-metal catalysts, platinum and depending on process conditions. If a rhodi-
palladium catalysts supported on g-Al2O3 or um – platinum alloy is used, the rate of loss of
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/Al2O3
Ethylene ! acetaldehyde - PdCl2 in solution -
Amines ! nitriles Ag - -
Complete oxidation of organic compounds - - Pd/Al2O3
Disulfides to sulfoxides - RuO4 in CCl4 -
Alcohols to aldehydes, ketones - RuO4 in CCl4 -
Olefins, oxidative cleavage - RuO4 in CCl4 -
Synthesis or decomposition of organic compounds
CO þ H2 to methane - - Ru/Al2O3
to paraffin hydrocarbons - RuO2 Ru þ K2CO3
Addition of CO and H2 to
olefins to give alcohols - RhO3 -
olefins to give ketones - RhCl3 -
olefins to give esters - Rh oxide -
Addition of silane to olefins - - Pt/carbon Al2O3
Cleavage of formic acid Rh, Os Ru oxide Pt/asbestos
Leavage of formaldehyde Ru, Os OsO4 Pd/BaSO4
Inorganic catalysis
H2O2 ! H2O þ 1/2 O2 Ru, Pd - -
NO ! hydroxylamine - - Pt/C
PtAu5/C
PtIr1/C
Rh/C
NH3 ! NO PtRh10
b) Reduction and isomerization on noble metal catalysis
H2 addition to
acetylene and homologs Rh, Pd, Pt - Rh, Pd/Al2O3
Ag/Pd70/30/Al2O3
Pd and Pt/BaSO4
ethylene and homologs - - Ru/C
aromatic hydrocarbons - - Rh/Al2O3
aromatic compounds, hydrogenation of the aromatic ring - RuO2 Rh/Al2O3
heterocycles, hydrogenation of the aromatic ring - - Rh/Al2O3
Reforming of crude oil
dehydration (cracking) to aromatics Pd/Al2O3
isomerization/Cyclization - - Pt/Al2O3
PtIr/Al2O3
cleavage to alkanes - - Ru/SiO2
Reduction
of ketones to alcohols - - Ru/C
Pd/C
Pt/C
of carboxylic acids to alcohols - RuO2 Ru/C
Rh/C
nitrogen compounds to amines - PtO2 Pd/C
Pt/C
of disulfides to mercaptans - RuO2 -
of mercaptans to alcohols þ H2S - RuO2 -
noble metal is reduced; powdering of the CH4 þNH3 þ3=2 O2 !HCNþ3 H2 O

gauze takes place more slowly, and its lifetime
is increased. platinum – rhodium or platinum – iridium
In the production of hydrogen cyanide gauzes are used as catalysts (! Cyano Com-
(Andrussow process), pounds, Inorganic, Section 1.2.1.).
The Degussa process cause of the required CO tolerance when working

with reformed gas platinum/ruthenium catalysts
CH4 þNH3 !HCNþ3 H2 are preferred. For AFC platinum/gold associated
works with a-Al2O3 tubes coated on the inside with nickel is applied. For PAFC quaternary
with a platinum film, forming a platinum – alu- catalysts with platinum are used; platinum/rho-
minum alloy. dium/iron was reported as cathode catalysts; on
the anode side normally platinum is used. The
Finely Divided Metallic Catalysts. The so- DMFC, similar to the PEM, works with platinum/
called platinum metal blacks are well-estab- ruthenium on the anode side, sometimes addi-
lished catalysts for hydrogenation, dehydroge- tionally containing tungsten, and with platinum
nation, and oxidation, mainly on a laboratory on the cathode side.
scale. Their high degree of dispersion is shown
by their large specific surface area (> 20 m2/g).
10.5. Homogeneous Catalysts [30],
These catalysts are very active even at low tem-
perature, so reactions with labile molecules are [88], [228–230], [322]
possible. In the production of hydrogen peroxide
by the anthraquinone process (! Hydrogen Per- Homogeneous catalysis by platinum group me-
oxide, Section 4.1.2.2.), palladium black is used tals, especially rhodium, has made a major im-
to a considerable extent in suspension in a non- pact in industrial chemistry. Important charac-
aqueous medium or as a fixed bed to catalyze the teristics of these catalysts include high activity
reduction of alkylanthraquinone to the corre- and, therefore, low concentration; high selectiv-
sponding hydroquinone. The platinum oxide PtO2 ity leading to absence of side products; and mild
H2O (Adam’s catalyst) is used widely as an reaction conditions, enabling the use of low
unsupported catalyst in the pharmaceutical indus- temperature and pressure and facilitating the
try for the hydrogenation of alkenes and carbonyl control of reaction conditions. These factors are
groups. Nishimura’s catalyst contains rhodium of great importance and allow expensive PGMs
oxide in addition to platinum oxide. to be used economically. The discovery of chlor-
otris(triphenylphosphine)rhodium(I), [RhCl{P
Catalyst Poisoning and Regeneration (C6H5)3}3], a highly effective hydrogenation cat-
[227]. All catalysts are liable to be deactivated alyst, by WILKINSON [231] opened a new chapter in
(poisoned) by chemical, mechanical, and thermal homogeneous catalysis and in the complex chem-
means. Typical contact poisons for platinum istry of rhodium. Today, a number of modified
group metals include sulfur, phosphorus, carbon complexes of this and similar types are known.
monoxide, hydrogen cyanide, lead, and mercury. Homogeneous catalysis by rhodium com-
Reactivation is often possible, especially with plexes in oxo synthesis (hydroformylation) has
supported catalysts, by heating, steam treatment, attained great importance and made possible the
reaction with oxidizing or reducing gases, or synthesis of industrially important aldehydes
washing. from alkenes (see ! Oxo Synthesis). This pro-
cess was formerly carried out with homogeneous
cobalt catalysts.
10.4. Fuel Cells By using [RhH(CO){P(C6H5)3}3] as the cata-
lyst, reaction temperatures between 60 and
Precious metals are used as anode and cathode 120 C and pressures of less than 50 bar could
catalysts in low-temperature fuel cells such as the be realized, in contrast to the cobalt catalysts, for
AFC (Alkaline Fuel Cell), PAFC (Phosphoric which temperatures up to 200 C and pressures
Acid Fuel Cell), PEMFC (Protone Exchange as high as 300 bar are necessary. Often other
Membrane Fuel Cell) and DMFC (Direct Meth- compounds are used as precursors from which
anol Fuel Cell). In the interesting PEMFC, which the actual catalyst is formed during the reaction.
has a significant potential for replacing automo- These include [Rh(CO)2(acac)] and [Rh(CO){P
bile internal combustion engines, for the cathode (C6H5}3(acac)] (acac ¼ acetylacetonate).
side platinum catalysts supported on carbon Another approach to oxo synthesis is to work
black are used. For the anode side, mainly be- in a biphasic system. In this case a watersoluble
ligand like P(C6H4SO3Na)3 and a rhodium salt the air – fuel ratio by means of a l-sensor (see
(e.g., nitrate, acetate, or sulfate) is used as cata- Section 10.7). Exhaust control catalysts have
lyst precursor [325]. their optimum activity only if the engine and the
The Monsanto acetic acid process uses RhIII catalytic unit are matched. The initially used
iodide as the catalyst precursor. In the cativa pellet catalysts have since been replaced by
process [323] BP uses Ir acetate as complex monolith-type catalysts. The exhaust gas passes
precursor. through numerous parallel channels of extruded
The most important application of platinum in bodies (monoliths) that are coated with a catalyt-
homogeneous catalysis is the vulcanization of ically active layer, the so-called wash-coat. The
silicon rubber. In addition, the synthesis of se- wash-coat consists of the PGM on g-Al2O3, rare
lected organofunctional silanes can be realized earth oxides, and other metal oxides. The oxide
by homogeneous precious metal catalysis [326]. mixture is designed to provide high thermal
A new era in homogeneous catalysis started stability and the ability to compensate fluctua-
with the discovery of asymmetric hydrogenation tions of the air fuel ratio through oxygen storage.
to produce enantiomerically pure compounds by In some applications monoliths made from foils
using metal complexes with chiral ligands [225], are also used.
[328]. Many other known reactions [322], [324] Each catalytic converter contains approxi-
are now also performed under asymmetric mately 2 g of PGM. The demand for these
conditions like the isomerization of allylamines materials worldwide amounts to more than
[327], [328], allylsubstitution [329] and Heck one-third of the annual production of platinum
reactions [327–329]. The products are mainly and more than four-fifths of the annual pro-
intermediates like amino acids, amines, and ster- duction of rhodium. In the early 1990s the use
oids for production of pharmaceutical and agro- of Pd has increased significantly. The PGM
chemicals. Examples of such ligands are DiAMP catalysts are the only practicable materials for
[331], BINAP [332], [333], Deguphos [334], this purpose. The required lifetime of an ex-
Josiphos [335], DuPhos [336], [337]; products haust-gas catalyst, as laid down by the widely
include L-Dopa (drug for the treatment of accepted U.S. standard, corresponds to 80 000
Parkinson’s disease), L-Menthol (aroma), and or 160 000 km.
Metolachlor (herbizide). The catalysts are Tighter standards in the future and the devel-
formed in situ by reaction a precursor like [Rh opment of engines with higher fuel efficiency
(cod)2]BFa or [Rh(cod)acac] (cod ¼ 1,5-cy- (lean-burn engines, new diesel engines) have
clooctadiene) with the chiral ligand. spurred the further development of these tech-
nologies, e.g., catalysts with the ability to tem-
porarely store hydrocarbons or nitrogen oxides,
10.6. Automotive Emission Control electrically heated catalysts, and catalysts that
Catalysts [32], [233–236], [338–345] also reduce soot emissions from diesel engines.
All these catalyst types use PGMs.
The use of supported noble-metal catalysts for the Catalysts similar to those used for the treat-
treatment of exhaust gases from automobiles has ment of automobile exhaust gases are also used to
been introduced beginning in the 1970s, around treat emissions from thermal power plants and
the world (see also ! Automobile Exhaust Con- industrial waste gases contaminated with harm-
trol). Regulations controlling the quality of ex- ful organic materials.
haust gases can be complied with only by the use
of such catalysts. In particular, carbon monoxide
(CO), hydrocarbons (CHx), and nitrogen oxides 10.7. Sensors [30], [88], [166], [167]
(NOx) must be reduced to a small percentage of
their initial concentrations. Metals that have a Thermocouples. Platinum metals and their
catalytic action on exhaust gases include Pt, Pd, alloys are widely used in thermocouples (Table 9),
and Rh and all combinations thereof. because these have longer lifetimes than those
Formulations that can reduce all three harmful made of base metals and can be used at higher
components are known as three-way catalysts. temperature. The most important thermocouple
The three-way technique also includes control of element pair used in industry is Pt 90/Rh 10 – Pt
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
(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-coefficient of electrical resistance
(TCR) of high-purity platinum is
3.927 103/K. Basic values of the changes of
resistance over temperature ranges (e.g., 200

C and þ 850 C) of platinum resistance ther-
mometers are specified 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 Figure 34. a) Platinum layer resistor element (dim 2 2.3
mm) with welded connecting wires, layer resistance adjusted
0.5 atom % iron or alloys of gold with 1.15 at- by laser cuts. b) enlarged view of platinum layer paths on the
om % manganese show due to magnetic effects ceramic substrate. Path width ca. 15 mm (Diehl et al. [167])
an increasing TCR with decreasing temperature
(Kondo effect [347]) to sufficient high, measur-
able values. are joined to the thin film by special bonding
Platinum wire-wound resistors, whose resis- processes, also consist of noble metals or their
tance is determined by the length and cross compounds. Modern resistance thermometers
section of the wire, have been almost completely based on thin-film technology have the advan-
displaced by so-called thin-film resistors, man- tage over wire-wound resistance thermometers
ufactured by thin-film technology. A film of because they can be manufactured by highly
platinum ca. 1 mm thick is deposited on an automated methods and require only small
insulating ceramic substrate by vacuum deposi- amounts of PGM (<1 mg per device).
tion or cathodic sputtering. The required resis- Iridium-layers have values of thermal expan-
tance value is adjusted by laser cutting. A mean- sion which are comparable to those of the ce-
drous resistance path is formed in the film of ramic. They are therefore applied on devices for
noble metal by cutting with a laser beam or by temperature measurements at temperatures down
ionic etching through a masking coating pro- to about 200 C.
duced by photolithography (Fig. 34). The thick- Resistance thermometers are used today in a
ness of the film and the total path length deter- wide range of technologies, from household
mine the resistance at 0 C. Path widths are in the appliances to chemical equipment, and from road
region of 20 mm. The connecting leads, which transportation to air and space travel.
Special Sensor Devices [348]. Oxygen se-

lective sensors (‘‘lambda-probes’’), use the high
electrical conductivity imparted to solid electro-
lytes (e.g., ZrO2) 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 Figure 35. Optical switching device with a palladium thin
layer [350]
(Nernst electromotive force) between the elec-
trodes. Lambda probes are used in automotive
cars to maintain an accurate air/fuel ratio and to from mirror reflection (YH1.8) to transparency
monitor the performance of the emissions control (YH2.9). Switching occurs in less than 0.1 s.
system (automobile exhaust-gas catalysts in Applications are expected for automotive and
Otto-engines). construction parts [351], [352]. An other hydro-
Noble-metal catalysts are also used in sensors gen-concentration-dependent device consists of
for detecting combustible gases in air or explo- an inner NbH layer, covered on both sides by iron
sive gas mixtures. Heat evolution is normally plates. The system behaves ferromagnetically at
detected by sensors known as Pellistors, which low H concentration; higher H concentration
consist of platinum wire in a small sphere of effect the transition to the antiferromagnetic
Al2O3 (diameter: 1.5 mm). The sphere is satu- state. The system is suited as magnetic-field
rated with a noble-metal catalyst. If a chemical sensor, for instance, in read and write heads of
reaction takes place on the catalyst, a temperature computer hard disks.
increase occurs that can be measured by the
change in resistance of the platinum wire. These Osmium -bipyridil-redox polymers com-
heat evolution sensors are used in explosion bined with a redox enzyme can be used as minia-
protection equipment. ture in vivo sensor for implantation into diabetes
patients for continuous monitoring of their blood
Platinum and Palladium porphyrin com- glucose levels (‘‘Wired enzyme bio-sensor’’,
plexes and ruthenium(II) diimines are used in [353]). The divalent and the trivalent complexed
optical oxygen sensors. These sensors respond osmium ions can exchange electrons at high rates.
specifically to molecular oxygen by a change in The osmium polymer electrically connects the
the intensity of luminescence which is emitted redox centres of the enzymes by introducing
from a probe molecule. The luminescence is re- electron relays close to the enzyme active site.
versibly quenched by molecular oxygen. Optical A sol-gel based amperometric biosensor in-
sensors have been developed for oxygen detection corporates an osmium redox polymer as mediator
in hydrogen, carbon dioxide, and as biosensor for for detection of lactate [354].
determine the level of glucose [349].
Thin palladium layers act as hydrogen filters 10.8. Electrical Technology [205], [237]
in optical switching devices. These systems are
based on the hydrogen-dependent transition from In low-current technology, electrical contacts of
the metallic state of yttrium hydride YH1.8 to the gold, silver, palladium, rhodium, platinum, and
transparent state YH2.9 (Fig. 35). Thin yttrium their alloys are used. Contacts made of bulk noble
layers are deposited by molecular-beam epitaxy metals are becoming less common than those
on transparent glass plates covered with a pro- coated by electrolytic and mechanical processes.
tective niobium layer and an upper palladium For a long time, large numbers of so-called
layer. The palladium layer impedes oxidation of reed contacts have been used in telephone relays.
the yttrium hydride and provides a catalytic These are Ag – Pd-, rhodium-, or ruthenium-
surface hydrogen dissociation and diffusion into coated contacts operating under a protective gas.
or out of the yttrium hydride layer. Depending on Such contacts must be resistant to sparking,
the hydrogen concentration, the cell switches corrosion, and erosion, and must not become
welded together. During a lifetime of 30 years, devices (ABS, airbag), and so-called passive
they must carry out millions of switching opera- components (e.g., resistors, capacitors). The me-
tions without damage. Furthermore, their contact tals are mainly applied as surface layers, but also
resistance must be low, and their nominal resis- in form of bulk material (sintered from powder) in
tance must be constant. discrete capacitor and resistor devices.
Platinum sealing wires are also now used only Important applications of platinum metals in
for specialty light bulbs and transmitter tubes. electronics are layer arrays of conductor and
Heating elements made of platinum metals or resistor paths deposited on substrate plates to
their compounds are used in resistance-heated form electronic circuits. The main types of elec-
furnaces above 1200 C. Windings of Pt 70 – tronic circuits are printed circuits (PC) and thick-
Rh 30 can be used up to 1500 C, and ribbon film and thin-film circuits. They are usually
windings of rhodium up to 1800 C. Furnace additionally loaded with discrete active and pas-
elements made of platinum metals can be used sive electronic components (hybrid technology).
without a protective gas. Platinum, rhodium, On printed circuits boards, metallizing is pri-
iridium, and ruthenium are used as susceptor marily carried out by electroplating. In thick-film
materials in induction furnaces. circuity, the noble metal layers are produced by
Platinum – iridium alloys are useful for spark the use of paste preparations, which consist of
plug contacts for high-power aeroplane and au- noble metal powders, glass frits, and organic
tomobile engines. binders. They are applied by screen printing onto
ceramic substrates, followed either by drying or
by firing at elevated temperatures. The glass frits
10.9. Electronics act as adhesives to the ceramic substrates.
In thin-film circuits the noble metal layers are
The platinum group metals and their alloys are precipitated on glass or special ceramic sub-
key materials in electronic devices and compo- strates by sputtering, by evaporation, or by ther-
nents (Table 10). Those include ‘‘active’’ discrete mal decomposition of noble metal resinates.
semiconductor devices (e.g., diodes, transistors, The powders used in the pastes are generally
semiconductor memories), single-crystal inte- produced by reduction of noble metal salts
grated circuits (ICs), automotive electronic de- [355]. The reaction conditions determine shape,
vices for engine-management systems, automo- size, and specific surface area of the powder.
tive oxygen sensors (lambda sensors), and safety 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 thick-film circuits Mo – Ru

special tubes (resistor pastes for high-temperature
hybrid circuits) solders for electron
tubes
Rh slide contacts, hard contact layers for metallizing pastes
coating of Cu pressure contacts on Ag for sensor surfaces
disks for thyristors, surfaces, corrosion
surface hardening protection
of Ag coatings on
pressure contacts
Pd bonding wires plug-in plug-in contacts multilayer capacitors conductor and electrode Ag – Cu – Pd solders
for transistors, contacts paste for thick-film for electron tubes
diodes circuits, multilayer package joining
capacitors
Pt test resistors test resistors, diffusion
barriers, IC technology
mechanical mixing to give composite blends or pending on grain size and substrate material.
by coprecipitation, followed by thermal treat- Palladium is also used as component in silver-
ment of the dried powders. Their specific sur- based conductor pastes and for resistor ele-
face area is usually between 1.5 and 10 m2/g. ments in thick-film circuity. As an additive in
The particle shapes can be spheroidal, micro- silver metallizing pastes, Pd improves the
crystalline, or flake. resistance to silver ion migration.
Platinum finds application as barrier layers Electroless (by chemical reduction) deposit-
and as contact pads on semiconductor chips. ed, thin palladium coatings form the first met-
Platinum interlayers on RuO2 electrodes of allization step for metallizing bare polyimide
ferroelectric capacitors (lead zirconate titanate surfaces, followed by chemical and galvanic
PZT) improve their stability and reduce leak- deposition of thicker copper layers. This proce-
age losses [356]. Platinum additions in silver- dure is especially applied for the plating of holes
based metallizing preparations and thick-film in the polyimide substrates to connect electrical
conductor pastes for screen printing of hybrid functions in multilayer PCs.
circuits serve as stabilizing component against Ruthenium is the most important base ele-
silver migration. In Ag-, AgPd-, or Au-con- ment of screen-printed resistor layers in thick-
taining thick-film pastes, Pt powder increases film circuits. These layers are printed with
the resistance to scavenging during soldering paste preparations consisting of RuO2 with
operations with Sn and Sn – Pb solder alloys. additions of PbO and Bi2O3. They form by
Palladium, pure or in combination with silver, firing complex ruthenium compounds of high
is the most important component in pastes thermal stability and with very low tempera-
used for the production of the inner electrodes ture coefficients of electrical resistivity. Exact
of multilayer capacitors. Special fine-grain resistance values are adjusted by applying
powders are needed to obtain sufficiently thin small cuts by means of laser beam into the
and homogeneous layer structures (Fig. 36). It resistor layer (‘‘laser trimming’’).
is produced by chemical reduction of aqueous Platinum resinates are used for the production
Pd(NO3)2 or PdCl2 solution. It is used in pure of conductive coatings on ceramic substrates
form or alloyed or mixed with silver powder onto which further layers can be deposited elec-
(mainly of composition Ag – Pd30 wt %). trolytically. Thin-film cobalt – platinum alloys
Corresponding electrode pastes are applied to and multilayers play an important role as mag-
BaTiO3 substrates and fired at temperatures netic media on hard disks for magnetic and
depending between 1100 and 1300 C, de- 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 from water, from hydrogen sulfide, 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 film between
two glass plates which have been coated with
transparent conducting oxide layers (Fig. 37).
The sensitizer part is separated from the counter-
electrode by an triiodide/iodide electrolyte. A
platinum coat on the transparent conducting
Figure 36. Fine-grain palladium powder for the production oxide layer catalyzes the cathodic reduction of
of electrodes in multilayer ceramic capacitors [167] triiodide to iodide. The light-induced charge
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 [359–363].
A tandem device that achieves the direct cleav-
age of water into hydrogen and oxygen by visible
light works by connection of two photosystems: a
first film of nanocrystalline WO3 and a second,
dye-sensitized nanocrystalline TiO2 film. The
blue part of the spectrum is absorbed by the first
layer, creating by band gap excitation valence
band holes which serve to oxidize water to oxy-
gen. The second film 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-
Figure 37. Layout of a nanocrystalline TiO2 solar cell. The vices (e.g., optical switches, fast recording de-
transparent dye derivatized titanium dioxide film is sand- vices, miniaturized sensors) electronically to the
wiched between two conducting glass electrodes. It harvest surrounding assembly. Their function is to pro-
light from both front and back sides. TCO is a transparent
conducting oxide coating layer with a highly active, stable
vide electronic connection between spatially
platinum electrocatalyst [357] remote redox-active subunits. They must main-
(courtesy Platinum Metals Review) tain strict stereochemical integrity of the final
assembly. Unidirectional electron flow is pro-
moted by external stimulation (e.g., absorption
transfer from the excited sensitizer to the semi- of a photon, application of a potential at an
conductor takes the route via interlocking organ- attached electrode, or by chemical means).
ic groups. The charge separation is accomplished RuO2/TiN storage electrodes serve for the
by the fact that the forward electron transfer from production of dynamic random access memory
the metal via the ligand into the TiO2 semicon- capacitors [366]. Surface layers of osmium and
ductor membrane is orders of magnitude faster ruthenium on dispenser cathodes lower the elec-
(< 1 ps) than the back diffusion because of the tronic work function [367].
less favorable electronic coupling between the
semiconductor and the oxidized ruthenium(III)
ion. The overall efficiency for solar light conver- 10.10. Coatings [30], [31], [93], [166]
sion to electricity in this arrangement reaches
10 – 11 %. Higher efficiency is expected to be Coatings of platinum metals may be applied to a
achieved by replacing the liquid electrolyte by a substrate by various methods.
10.10.1. Coatings Produced by Electrolysis ring contacts and optical reflectors, and were
[338], [368], [369] at one time used for reed contacts in telephone
technology.
Platinum. Lustrous thin films for decorative Rhodium sulfate or phosphate baths contain-
purposes are deposited from an electrolyte ob- ing 2 g/L of rhodium are used for decorative
tained by treating potassium tetranitritoplatinate purposes and give strongly reflective thin films
(II), K2[Pt(NO2)4], with sulfuric acid. The active (0.1 – 0.5 mm) that prevent silver or white gold
complex is H2[Pt(NO2)2SO4]. This is more stable from tarnishing. They are also used for plating
than other platinum plating baths. eyeglass frames.
Relatively thick coatings can be deposited
from alkaline solutions of sodium hexahydroxy Palladium [168]. Palladium can sometimes
platinate(IV), Na2[Pt(OH)6]. replace gold in coatings for electronics. The
A typical bath is sodium hexahydroxoplati- plating baths contain palladium(II) diamminedi-
nate 20 g/L, sodium hydroxide 10 g/L, pH 13, nitrite, [Pd(NH3)2(NO2)2] (palladium P-salt),
75 C, current density 0.8 A/dm2. A disadvan- with additions of sodium and ammonium ni-
tage is the low stability due to decomposition of trates, or sulfamates [377], [378].
the hydroxy salt. The use of the corresponding Successful results have recently been ob-
potassium salts eliminates this difficulty [370], tained with plating baths based on organopalla-
[371]. dium complexes. Concentrated hydrochloric ac-
Platinum(II) diamminedinitrite, [Pt id plating baths with dissolving palladium anodes
(NH3)2(NO2)2] (‘‘P salt’’), was formerly very are rarely used now.
widely used and today along with Na2[Pt(OH)6], Palladium – nickel alloys with 70 – 75 % Pd
is used for coating titanium by aqueous electrol- can be electrodeposited from ammoniacal solu-
ysis. These coatings are of lower quality than tions. Such deposits, overflashed with gold are
those produced by high-temperature electrolysis. used as a replacement for gold in the electronics
Also, extensive pretreatment of the substrate industry [379], [380].
metal is necessary, mainly to prevent cathodic
absorption of hydrogen. Ruthenium [381–383] is deposited electro-
The Q bath is based on a solution of [Pt lytically from solutions of ruthenium complexes
(NH3)4]2þ (Pt concentration 5 – 20 g/L) in a with a bridging nitrido ligand, for example,
dilute phosphate buffer, pH 10.3 – 10.5. At op- nitridooctachlorodiaquodiruthenate(IV),
erating temperatures above 90 C, high-quality, (NH4)3[H2O(Cl4Ru)–N–(RuCl4)H2O], the basis
thick Pt deposites are obtained which are exten- of the so-called RuNC baths. The corresponding
sively used in the engineering industry when complex with hydroxo ligands instead of chloro
components are subjected to high-temperature ligands can also be used.
corrosion [372], [373]. Ruthenium baths based on ruthenium nitro-
sylsulfamate are also used.
Rhodium [169], [374–376]. Rhodium coat-
ings are superior to all other PGM coatings, High-Temperature Electrolysis (HTE)
having better hardness, mechanical and chemi- [30], [88], [239–241], [384], [385]. Platinum
cal stability, and reflectivity. For these reasons, group metals can be deposited electrolytically
rhodium is more widely used than the other from cyanide-containing melts in which a soluble
platinum group metals (see also ! Electro- anode provides the noble metal that is deposited
chemical and Chemical Deposition, Section on the cathode. The metal most widely used in
8.16.). this process is platinum, although iridium is
Electrolytes consisting of rhodium sulfate sometimes used.
(10 – 20 g/L Rh) in sulfuric acid can give The molten salt, an eutectic mixture of
comparatively thick coatings (10 – 12 mm). KCN and NaCN, is maintained at 500 – 600 C
Crack formation can be countered by addition in an electrically heated crucible. The platinum
of sulfite, selenic acid, magnesium sulfate, or is deposited from the melt onto the substrate,
magnesium sulfamate. These baths are used to which forms the cathode in the electric
produce rhodium coatings for heavy-duty slip circuit.
Process parameters are as follows: produce conductive platinum coatings on ceram-

ic substrates, onto which further layers can be
deposited electrolytically. Platinum coatings are
Electrolyte K2[Pt(CN)4] in KCN – NaCN
Operating temperature 500 – 600 C
also used for decorative purposes.
Deposition voltage 0.1 – 2 V Hexachlororuthenic(III) acid, H3[RuCl6],
Cathodic current density 1 – 5 A/dm2 dissolved in alcohol, is painted onto the sub-
Cathodic current yield > 60 % strate, dried, and heated strongly in air to
Mean rate of deposition 10 – 20 mm/h
produce an extremely adherent coating of
RuO2 [246], [247]. Titanium sheet, coated in
Oxidation of the melt and of the metal is pre- this way, has outstanding electrochemical prop-
vented by a protective atmosphere of high-purity erties and is being used in chloralkali electroly-
argon. Suitable substrate materials for HTE plat- sis as dimensionally stable anodes. The RuO2
inum deposition include refractory metals such coatings are also used in the production of
as titanium, niobium, tantalum, molybdenum, circuit boards by screen printing.
tungsten, zirconium; steels; and other metals
such as copper. They must generally be pre-
treated by sandblasting and degreasing. 10.10.3. Coatings Produced by Physical
Advantages of HTE platinum coatings, com- Methods [88], [167]
pared with those produced by aqueous electroly-
sis, include low porosity; a wide range of film Platinum can be deposited as a thin film on sub-
thicknesses (1 – 400 mm), excellent adhesion; strates by evaporating the metal in a high vacuum.
good resistance to mechanical impact, thermal Modern thin-film technology is based mainly on
shock, and sliding wear; high thermal conductiv- the generation of fine particles from a cathode
ity; and high ductility. (cathodic sputtering). Due to the high kinetic
The largest use is in producing anodes for energy of these metal particles, extremely good
cathodic corrosion protection [242] (often in the adhesion is obtained. In the case of platinum group
form of expanded metal) or insoluble anodes for metals, sputtering targets are used for microelec-
electrolytic technology. Platinum-coated molybde- tronics and for resistance thermometers. Ion plat-
num wire is used in the construction of thermionic ing is also used to produce high-quality coatings.
tubes and for fusion with glass. High-temperature Roll-bonded PGM coatings are no longer
electrolysis is also used for electroforming. important.
10.10.2. Coatings Produced by Chemical 10.11. Dental Materials [88]

Reaction [31]
Platinum and palladium have major importance
Surface coatings of platinum metals can be de- in dentistry (! Dental Materials, Section 2.3.).
posited onto metallic or nonmetallic substrates Up to ca. 1900, dental protheses such as gold
by chemical reduction or thermal decomposition fillings, crowns, and bridges were made mainly
of PGM compounds. of alloys with the same composition as those used
Platinum acetylacetonate is used for platini- in coinage and jewelry, and later of 22-carat gold
zation of titanium. The titanium articles are (83.3 %). Platinum was used only to make fixing
painted with a solution of this compound, dried, pins.
and heated. Repeated application is necessary. Important quality requirements such as oral
The process is not widely used due to allergic stability, biological compatibility, color, strength,
reaction and the low quality of the coatings. and good functional properties are achieved only
Platinum coatings are produced on ceramic by modern dental alloys. These complex alloys,
tubes by a new technique using a lacquer [243], unlike the earlier gold-containing ones, have a very
[386]. Such tubes are used as catalysts for the fine-grained, homogeneous crystalline structure,
synthesis of hydrogen cyanide. giving much better corrosion resistance. Also, their
Platinum metal resinates are used as ceramic hardness is controllable over a wide range and can
colorants [244], [245]. These can be employed to be adapted to particular requirements.
Standard Alloys. Modern alloys for making developed to reduce cost. Silver-free and sil-
dentures or prostheses have compositions mainly ver-containing alloys are available. Both contain
in the range 65 – 85 % gold, 1 – 10 % platinum, very small amounts, if any, of gold and platinum.
1 – 4 % palladium, 10 – 15 % silver, 0 – 10 % The range of compositions for the silver-contain-
copper, and 0 – 1 % zinc. ing palladium-based alloys is 53 – 61 % palladi-
In low-gold alloys, which are cheaper, the gold um, 28 – 38 % silver, 0 – 12 % tin, indium, zinc,
is replaced partially by silver or palladium. These and gallium. For the silver-free palladium-based
alloys contain 40 – 60 % gold, 0 – 2 % platinum, alloys, the composition range is 73 – 88 % pal-
3 – 10 % palladium, 23 – 35 % silver, 0 –12 % ladium, 0 – 2 % gold, and 12 – 26 % of the base
copper, and 0 – 5 % tin, indium, and zinc. metals copper, cobalt, tin, indium, and gallium.
Silver-base alloys have very low gold content.
Adequate oral stability can be achieved by in-
cluding at least 25 % platinum group metals or 11. Economic Aspects [5], [10], [24],
gold. Inexpensive alloys in this category contain [30], [46], [48], [57–63],[76], [235],
at least 20 – 25 % palladium, 0 – 3 % gold, ca.
55 –70 % silver, and copper and zinc, and are
[248–255]
therefore no longer yellow, but white. 11.1. Supply
Alloys with Ceramic Veneering have been The most important PGM-producing mines are
developed in the early 1960s. With the help of these located in
alloys ceramics can be fused on a cast metal
framework. The main properties of the alloys nec- . South Africa (Amplats, Lonmin Platinum, Im-
essary for this task are a thermal expansion coeffi- pala, Northham, Kroondal Platinum, Trojan
cient similar to that of the ceramic and a solidus Platinum)
temperature sufficiently above the fusing tempera- . Russia (Noril’sk Nickel, Koryak and Kondyor
ture of the ceramic. With early ceramics firing was mines)
carried out at 980 C. Alloys for these ceramics . Canada (Inco, Falconbridge, North American
needed a solidus temperature above 1050 C. To Palladium)
achieve this goal the content of platinum and/or . USA (Stillwater)
palladium in the alloy had to be increased, which . Zimbabwe (Hartley PLatinum, Zimbabwe
caused whitening of the alloy beside an increase of Platinum, Anglo-American Zimbabwe).
the melting range. In recent years, low fusing
ceramics became available, which allow to use The world total output 1998 of platinum,
alloys with compositions closer to the standard palladium and rhodium is listed in Table 11 and
alloys and alloys with a more yellow color. shown in Fig. 38.
Alloys for high fusing ceramics with a high In addition to PGMs obtained from ores, a
gold content have compositions in the range considerable amount of secondary material ex-
75 – 90 % gold, 5 – 10 % platinum, 1 – 10 % ists. The extent of this is very variable and
palladium, 0 – 3 % silver, with small additions fluctuates with time.
of iron, indium, tin, zinc, and other elements. Averaged over all the PGMs, it amounts at
Attempts have been made to reduce the cost of present to ca. 20 % of primary production, with
these alloys by replacing gold by palladium and the greatest emphasis on platinum and especially
silver. Typical Au – Pd – Ag alloys have com- palladium. The present effort directed toward
positions in the following range: 42 – 62 % gold,
25 – 43 % palladium, 5 – 20 % silver, and 4 – Table 11. World supply of Pt, Pd, and Rh in 1998 by region (in 106 oz)
10 % base metals such as copper, tin, indium,
gallium, and zinc. Typical silver-free Au – Pd Pt Pd Rh
alloys have the following composition: 45 – South Africa 3680 1820 400
60 % gold, 32 –40 % palladium, and 0 – 14 % Russia 1300 5800 110
of the base metals tin, indium, zinc, or gallium. North America 285 660 16
Others 135 120 4
Palladium-base dental alloys were introduced
Total 5400 8400 530
in Germany in the early 1980s. These were
Table 12. PGM demand in 1998 by application (in 106 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
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

Figure 38. World palladium, rhodium, and platinum supply
in 1998 by region (in 106 oz) a) palladium (total 8400); Since 1975, a so-called London free market price
b) rhodium (total 530); c) platinum (total 5400) for platinum is calculated and published twice
daily. Since 1976, a London palladium quotation
recovery from spent automobile catalysts will has also been available. Both of these were only
considerably increase the proportional secondary price indications, not to be compared with the
production of platinum and rhodium. fixed quotations for gold and silver. The London
A high proportion of the PGMs is recycled by Platinum and Palladium Market (LPPM) has
the users or, in the case of contract suppliers of since been established and publishes fixed quota-
semifinished products (e.g., catalysts), by the tions twice daily.
producers. These materials do not appear on the Platinum and palladium are also traded on the
market either on the supply or on the demand New York Mercantile exchange (NYMEX) and
side, so supply figures essentially reflect only on the TOCOM in Tokyo.
mined products. Trading in platinum on the New York
exchange is in the form of contracts for units
of 50 troy ounces. The purity of platinum
11.2. Demand supplied in fulfillment of such a contract must
be at least 99.9 %, and the platinum must
Table 12 and Figure 39 show the demand for originate from a producer or assayer registered
platinum, palladium, rhodium, iridium and ru- with the exchange. For palladium, the contract
thenium by application. amount is 100 troy ounces, and the purity must
be 99.9 %.
Spot transactions (immediate delivery and
11.3. Prices payment) are guided by the London quotation
and the New York exchange quotation.
The prices of the PGMs are strongly influenced Palladium in recent years has found increas-
by factors of demand for new technical applica- ing utilization in the production of automotive
tions, by availability of supply, and by specula- catalysts. Due to very unstable supply from the
Figure 39. World PGM demand in 1998 by application (in 106 oz). Total quantities include recycled material (PA
405 106 oz, Pd 175 106 oz, Rh 57 106 oz) a) platinum (total 5755); b) palladium (total 8365); c) rhodium (total
573); d) iridium (total 105); e) ruthenium (total 375)
main palladium producer of the world, Russia, are sickness, vomiting, hypersensitivity reac-
palladium prices increased more than threefold in tions, ototoxicity and nephrotoxicity [387].
the period from December 1996 to May 1998. The tetroxides of osmium and ruthenium
strongly irritate and corrode the conjunctiva
and cornea of the eye and the mucous mem-
12. Toxicology branes of the respiratory tract. Temporary toxic
effects can occur in bone marrow, liver, and
Platinum is used in therapy; cisplatin is currently kidneys. The salts of hexachloroplatinic acid
used for cancer treatment. Known side-effects H2[PtCl6] [16941-12-1] have a strong allergenic
potential (see below); platinum metal is not
allergenic.
Table 13. PGM price lows and highs (1996 – 1998, in $/oz)
The MAK value for platinum compounds has
1996 1997 1998 been set as low as 2 mg/m3 (as Pt), not because of
their toxicity but due to allergenic potential. For
low high low high low high osmium tetroxide [20816-12-0] the MAK value
Pt 367 433 342 497 334 429 is even lower because of its strong irritating
Pd 114 143 117 245 201 417 effect: 0.2 mg/m3. In the United States, TLVs
Rh 320 345 200 370 370 780 for water-soluble rhodium salts are 1 – 10 mg/
Ir 60 10 110 290 270 575
Ru 29 55 38 41 39 65
m3. For other platinum group metals toxicologi-
cal limits have not yet been established.
The median concentrations of platinum in potential. Recently, skin allergies to the plati-
blood, plasma/serum, and urine are about 1 ng/L num-base alloys used in dental materials have
[388]. The limit for platinum and osmium in been reported but are still under discussion. The
industrial effluents is 3 mg/L [389]. In the United German government has recommended to test
States, most platinum group metals are classified the corrosion resistance and biocompatibility of
as ‘‘poisonous’’ or ‘‘very poisonous’’ in waste- palladium – copper alloys prior to their use in
water treatment plants [390]. dental restoration [393].
Automotive Emission Control Catalysts.

Toxicological effects of platinum-group metals
have been studied increasingly because of their References
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Platinum Group Metals and Compounds

1. History . . . . . . . . . . . . . . . . . . . . . . . . . 318 3.6. Reserves and Resources . . . . . . . . . . . . . 330

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

5. Dissolution Methods . . . . . . . . . . . . . . . 335 8.3. Methods of Treatment . . . . . . . . . . . . . 361

Sverdlovsk). However, at the result of an ideo-

The other properties typical of transition metals are

Ru: 2, 0, þ2, þ3, þ4, þ5, þ6, þ7, þ8

Table 3. Chemical resistance of the platinum group metals

Reagent Conditions Temperature, C Pd Pt Rh Ir Ru Os

Nitric acid 65 % 100 – – – –

Hydrobromic acid 60 % 100 . – – .

Hydroiodic acid 57 % 100 – – – .

Acetic acid 99 % 100 – – – – –

Hydrochloric acid/chlorine 20 %/saturated 80

Aqua regia 100 – –

Aqua regia 150 .

Hydrochloric acid/H2O2 100

Hydrobromic acid/bromine 60 % 100

Sodium cyanide solution 20 . –

Reagent Conditions Temperature, C Pd Pt Rh Ir Ru Os

KCN melt þair 700 . . .

NaCN/KCN melt (2 : 1) þair 550 . . . .

Bromine liquid dry 20 . – – –

Bromine liquid moist 20 . – – – .

Mass loss 10 mg cm2 h1; suitable for dissolution processes.

Figure 3. Geology and platinum mines of the Bushveld Complex

Merensky UG 2 South Africa, Sudbury, Noril’sk, Stillwater,

Natural Reserves. Data concerning re- Industrial Residues. Industrial residues

Figure 4. World platinum group metal reserves (total 70 000 t)

slow-cooling matte separation process, a finely

4.3. Treatment of Nickel Ores [63], [64]

In the processing of sulfide nickel ores, which

5. Dissolution Methods [36], [48],

the dissolution rates for platinum and platinum- or

Ruthenium is converted into water-soluble In general, coarse separation is followed by a

generally quite large and can be utilized or must

Redox Reactions and Stability of Com-

Figure 8. Dependence of the solubility of platinum group

tion, but also to solvent extraction and distilla-

Hydrolysis [96], [104], [117]. Hydrolytic

Table 5. Stability of platinum group metal chloro complexes

The extracted metal is stripped from the or-

6.2. Older Separation Processes [31]

Some separation methods, shown in Figures 9,

Figure 10. Older separation process B (Siebert)

may still be used today or included with more

Separation Process A (Fig. 9) [36], [43].

platinate. Recovery of the rarer platinum group

Separation Process C (Fig. 11) [36], [134],

6.3. Current Separation Processes

Modern separation processes (see Figs. 12, 13,

Separation Process D (Fig. 12) [31], [88].

Figure 12. Modern separation process D

solution due to H[AgCl2] formation. Lowering

Separation of Gold. The usual process for

Selective Dissolution Reactions and Melt

Separation of Platinum, Iridium, and Pal-

½RhðH2 OÞ6 3þ