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Platinum Group Metals and Compounds

Platinum Group Metals and Compounds

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Platinum Group Metals and Compounds
Platinum Group Metals and Compounds

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Ó
2012Wiley-VCHVerlagGmbH&Co.KGaA,Weinheim
Platinum Group Metals and Compounds
H
ERMANN
R
ENNER
,
Degussa AG, (retired), Hanau, Federal Republic of Germany
G
u
NTHER
S
CHLAMP
,
Demetron GmbH, (retired), Hanau, Federal Republic of Germany
I
NGO
K
LEINW
ACHTER
,
dmc2 Degussa Metals Catalysts Cerdec AG, Hanau, FederalRepublic of Germany
E
RNST
D
ROST
,
dmc2DegussaMetalsCatalystsCerdecAG,Hanau,FederalRepublicof Germany
H
ANS
M
ARTIN
L
u
SCHOW
,
Degussa-H
uls AG, (retired), Hanau, Federal Republic of Germany
P
ETER
T
EWS
,
Allgem. Gold und Silberscheideanstalt (AGOSI), Pforzheim, FederalRepublic of Germany
P
ETER
P
ANSTER
,
dmc2Degussa Metals Catalysts Cerdec AG, Hanau, FederalRepublicof Germany
M
ANFRED
D
IEHL
,
dmc2DegussaMetalsCatalystsCerdecAG,Hanau,FederalRepublicof Germany
J
UTTA
L
ANG
,
dmc2 Degussa Metals Catalysts Cerdec AG, Hanau, Federal Republic of Germany
T
HOMAS
K
REUZER
,
dmc2 Degussa Metals Catalysts Cerdec AG, Hanau, FederalRepublic of Germany
A
LFONS
K
N
o
DLER
,
Forschungsinstitut f 
ur Edelmetalle und Metallchemie, (retired),Schw
abisch Gm
und, Federal Republic of Germany
K
ARL
A
NTON
S
TARZ
,
dmc2 Degussa Metals Catalysts Cerdec AG, Hanau, FederalRepublic of Germany
K
LAUS
D
ERMANN
,
Ducera Dental GmbH und Co. KG, Hanau, Federal Republic of Germany
J
OSEF
R
OTHAUT
,
Ducera Dental GmbH und Co. KG, Hanau, Federal Republic of Germany
R
ALF
D
RIESELMANN
,
dmc2DegussaMetalsCatalystsCerdecAG,Frankfurt/M.,FederalRepublic of Germany
C
ATRIN
P
ETER
,
Klinikum der Friedrich Schiller Universit
at, Jena, Federal Republic of Germany
R
AINER
S
CHIELE
,
KlinikumderFriedrichSchillerUniversit
at,Jena,FederalRepublicof Germany
1. History
. . . . . . . . . . . . . . . . . . . . . . . . . 318
2. Properties
. . . . . . . . . . . . . . . . . . . . . . . 321
3. Occurrence
. . . . . . . . . . . . . . . . . . . . . . 323
3.1. Abundance
. . . . . . . . . . . . . . . . . . . . . . 323
3.2. Ores and Their Origin
. . . . . . . . . . . . . 325
3.3. Primary Deposits
. . . . . . . . . . . . . . . . . 326
3.4. Secondary Deposits
. . . . . . . . . . . . . . . . 328
3.5. Recovery of Secondary Platinum GroupMetals
. . . . . . . . . . . . . . . . . . . . . . . . . . 328
3.6. Reserves and Resources
. . . . . . . . . . . . . 330
4. Mineral Dressing and Beneficiation
. . . . 331
4.1. Treatment of Alluvial Platinum Deposits
331
4.2. Treatment of Primary Deposits
. . . . . . 331
4.3. Treatment of Nickel Ores
. . . . . . . . . . . 332
4.4. Treatment of Metal Scrap
. . . . . . . . . . 333
4.5. Treatment of Dross
. . . . . . . . . . . . . . . . 333
4.6. Treatment of Supported Catalysts
. . . . 334
4.7. Treatment of Solutions
. . . . . . . . . . . . . 334
DOI: 10.1002/14356007.a21_075
 
5. Dissolution Methods
. . . . . . . . . . . . . . . 335
5.1. Dissolution in Aqua Regia
. . . . . . . . . . . 335
5.2. Dissolution in Hydrochloric Acid Chlorine
. . . . . . . . . . . . . . . . . . . . . . . . . 335
5.3. Dissolution in Hydrochloric Acid Bromine
. . . . . . . . . . . . . . . . . . . . . . . . . 336
5.4. Other Dissolution Processes
. . . . . . . . . . 336
5.5. Dissolution by Salt Fusion
. . . . . . . . . . 336
6. Separation of Platinum Group Metals
. 337
6.1. Chemistry of Platinum Group MetalSeparation
. . . . . . . . . . . . . . . . . . . . . . 337
6.2. Older Separation Processes
. . . . . . . . . 340
6.3. Current Separation Processes
. . . . . . . . 341
6.4. Processes Used in Coarse Separation
. . 343
6.5. Purication
. . . . . . . . . . . . . . . . . . . . . . 346
6.6. Conversion of Salts into Metals
. . . . . . 348
6.7. Partial Purification
. . . . . . . . . . . . . . . . 350
6.8. Treatment of Internally Recycled Material
350
6.9. Construction Materials
. . . . . . . . . . . . . 350
7. Platinum Group Metal Compounds
. . . 351
7.1. Inorganic Compounds
. . . . . . . . . . . . . . 3517.1.1. Platinum Compounds. . . . . . . . . . . . . . . . 3517.1.2. Palladium Compounds . . . . . . . . . . . . . . 3527.1.3. Rhodium Compounds . . . . . . . . . . . . . . . 3537.1.4. Iridium Compounds. . . . . . . . . . . . . . . . . 3537.1.5. Ruthenium Compounds . . . . . . . . . . . . . . 3547.1.6. Osmium Compounds . . . . . . . . . . . . . . . . 354
7.2. Organic Compounds
. . . . . . . . . . . . . . . 354
8. Alloys
. . . . . . . . . . . . . . . . . . . . . . . . . . 355
8.1. Alloy Systems
. . . . . . . . . . . . . . . . . . . . . 355
8.2. Special Alloys
. . . . . . . . . . . . . . . . . . . . . 356
8.3. Methods of Treatment
. . . . . . . . . . . . . 361
9. Quality Specifications and Analysis
. . . 361
9.1. Quality Specifications
. . . . . . . . . . . . . . 361
9.2. Qualitative Analysis
. . . . . . . . . . . . . . . . 362
9.3. Quantitative Analysis
. . . . . . . . . . . . . . 362
9.4. Purity Analysis
. . . . . . . . . . . . . . . . . . . 363
9.5. Trace Analysis
. . . . . . . . . . . . . . . . . . . . 364
10. Uses
. . . . . . . . . . . . . . . . . . . . . . . . . . . 364
10.1. Jewelry, Coinage, Investment
. . . . . . . . 364
10.2. Apparatus
. . . . . . . . . . . . . . . . . . . . . . . 364
10.3. Heterogeneous Catalysts
. . . . . . . . . . . . 365
10.4. Fuel Cells
. . . . . . . . . . . . . . . . . . . . . . . . 368
10.5. Homogeneous Catalysts
. . . . . . . . . . . . 368
10.6. Automotive Emission Control Catalysts
369
10.7. Sensors
. . . . . . . . . . . . . . . . . . . . . . . . . 369
10.8. Electrical Technology
. . . . . . . . . . . . . . 371
10.9. Electronics
. . . . . . . . . . . . . . . . . . . . . . . 372
10.10. Coatings
. . . . . . . . . . . . . . . . . . . . . . . . 37410.10.1. Coatings Produced by Electrolysis . . . . . . 37510.10.2. Coatings Produced by Chemical Reaction 37610.10.3. Coatings Produced by Physical Methods . 376
10.11. Dental Materials
. . . . . . . . . . . . . . . . . . 376
11. Economic Aspects
. . . . . . . . . . . . . . . . . 377
11.1. Supply
. . . .. . . . . . . . . . . . . . . . . . . . . . 377
11.2. Demand
. . . . . . . . . . . . . . . . . . . . . . . . . 378
11.3. Prices
. . . . . . . . . . . . . . . . . . . . . . . . . . . 378
11.4. Commercial Aspects
. . . . . . . . . . . . . . . 378
12. Toxicology
. . . . . . . . . . . . . . . . . . . . . . . 379
References
. . . . . . . . . . . . . . . . . . . . . . . 380
1. History
[1–10], [166], [167]
Figure 1 gives an historical survey of importantplatinum group metal discoveries and platinumgroup metal technology.
Early Times.
The earliest evidence of plat-inum is provided by a gold etui covered withhieroglyphic inscriptions, dating from the 7thcentury
B
.
C
. Around 1900, B
ERTHELOT
(1827 –1907)investigatedtheetui,whichwaskeptintheLouvre, and found that some of the inlays hith-erto thought to be silver were in fact platinum.In ca. 1900, jewelry made of native platinumwasdiscoveredinEcuador,whichwaspartoftheInca empire in pre-Columbian times. This prob-ably dates from the first five centuries
A
.
D
.In ancient times, the technique of washingriver sands and fusing together the grains of platinum was undoubtedly known, as was themakingofalloysbyheatingalluvialplatinumandgold with a blowpipe, these methods being simi-lar to those used in gold extraction and working.Pre-Columbian Indians were familiar with apowder metallurgy technique.
16th–18th Century
[11], [12]. In theirsearch for gold in the New World, particularlyin the area of present-day Colombia, the Spanishoften found alluvial (‘‘placer’’) platinum. Theearliest written report of the metal was made in1557 by J. C. S
CALIGER
(1484 – 1558). Howev-er, platinum was worked to produce jewelry andutensilsonlyaftermanhadlearnedthatthemetal,initially believedtobeinfusible, couldbe meltedand cast by first adding other metals to lower itsmelting point. Platinum was essentially regardedas a troublesome material, accompanying goldand silver, which lowered their workability. TheSpanish named the metal
platina
, the diminutiveform of 
plata
(silver), as a derogatory termbecause it was found only in small quantities or
318 Platinum Group Metals and Compounds Vol. 28
 
Figure 1.
Historical survey of important platinum group metal discoveries and platinum group metal technology
Vol. 28 Platinum Group Metals and Compounds 319

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