Platinum metals Separation

Discovered in 1803 by Wollaston, Palladium is found with platinum and other metals of the platinum group in placer deposits of Russia, South America, North America, Ethiopia, and Australia. It is also found associated with the nickel-copper deposits of South Africa and Ontario. Palladium s separation from the platinum metals depends upon the type of ore in which it is found. 

Pemoval of Other Impurities. After softening, the impurities that may stiU remain in the lead are silver, gold, copper, tellurium, platinum metals, and bismuth. Whereas concentrations may be tolerable for some lead appHcations, the market values encourage separation and recovery. The Parkes process is used for removing noble metals and any residual copper, and the KroU-Betterton process for debismuthizing. 

The nine elements, Fe, Ru, Os Co, Rh, Ir Ni, Pd and Pt, together formed Group VIII of Mendeleev s periodic table. They will be treated here, like the other transition elements, in vertical triads, but because of the marked horizontal similarities it is not uncommon for Fe, Co and Ni to be distinguished from the other six elements (known collectively as the platinum metals) and the two sets of elements considered separately. 

Gold may also be separated from hydrochloric acid solutions of the platinum metals by extraction with diethyl ether or with ethyl acetate (compare Chapter 6) except in special cases these methods do not offer any special advantages over the reduction to the metal. 

The metals are obtained from the metallic phase of the sulphide matte or the anode slime from electrolytic refining of nickel. In the traditional process for the platinum metals, their separation was facilitated by their solubility in aqua regia and convertibility into PdCl - or PtCl - salts. Nowadays, substantial amounts are obtained using solvent extraction. 

In the solvent-extraction process, the platinum metal concentrate is solubilized in acid using chlorine oxidant. Ruthenium and osmium are separated by turning them into the volatile tetroxides. 

The strong selectivity of A A -dialkyl A-benzoylthiourea toward platinum metals has been favorably exploited to determine noble metals (Rh, Pd, Pt, and Au) in samples of ore and rocks by graphite fnmace atomic absorption spectroscopy (GFAAS) and UV detection after liquid chromatographic separation on silica HPTLC plates [23]. The results are presented in Table 14.3. 

Leidie A process for extracting the platinum metals from their ores by fusion with sodium peroxide, followed by a complex separation process. Developed by A. Quennessen, a leading French manufacturer of platinum in the 19th century, and E. Leidie. The process is still used for extracting precious metals, and in chemical analysis. 

Slow-cooled matte A process for extracting platinum metals from copper-nickel matte. The molten matte is cooled slowly, over several days. This causes the platinum metals to enter a nickel-iron phase which can be separated magnetically from the other components. Operated by Rustenberg Platinum Mines in South Africa, and INCO in Canada. 

Platinum family metals preparation. The platinum metals (with gold and silver) are commonly found together, and a number of schemes are in current use for their separation. Platinum metals not only are extracted from ores but, due to their high value, are also recovered from a wide range of industrial residues such as Pt, Rh gauze catalysts, defective components from glass industries, etc. 

The initial steps are similar to any other mineral extraction process. This involves crushing mineral, froth flotation, gravity concentration and other steps to obtain platinum metal concentrates that may contain about 30 to 40 wt% of platinum group metals. The concentrate is treated with aqua regia to separate soluble metals, gold, platinum, and palladium from other noble metals such as ruthenium, rhodium, iridium, osmium, and silver that remain in... 

The salt may be best described as a mixed-valence compound containing platinum in the 2.3+ oxidation state. The combination of the mixed-valence state, the very short Pt— Pt separation of 2.89 A (only approximately 0.1 A longer than in platinum metal), and the formation of linear Pt—Pt chains along the c axis gives rise to the high, anisotropic metallic conductivity in this material.1... 

When you see Dr. Wollaston give him a thousand compliments from me and then ask him if it would be possible to have a little malleable platinum, not separated from its natural alloy with palladium, rhodium, etc, to make a crucible. The crucibles I have bought recently from Cary are of a metal noticeably purer than those which I formerly had, and for that very reason infinitely more susceptible to attack by other substances (5). 

Similar to (SN)t in their one-dimenston.il conductivity properties arc the stacked columnar complexes typified by [Pl(CN)j i. These square planar ions adopt a closely spaced parallel arrangement, allowing for considerable interaction among the d i orbitals of the platinum atoms. These orbitals are normally filled with electrons, so in order to get a conduction band some oxidation (removal of electrons) must take place. This may be readily accomplished by adding a little elemental chlorine or bromine to the pure tetracyanoplatinate salt to get stoichiometries such as K-.[Pt(CN)jBr0, in which the platinum has an average oxidation state of +2.3. The oxidation may also be accomplished electrolytically. as in the preparation of Rbj(Pt(CN)4J(FHF)04 (Fig. 16.8). which has a short Pt—Pi separation. The Pt—Pt distance is only 280 pm. almost as short as that (bund in platinum metal itself (277 pm) and in oxidized platinum "pop complexes (270 to 278 pm see Chapter l5).4- Cold-bronze materials of this type were discovered as early as 1842. though they have been little understood until recent times. The complexes behave not only as one-dimensional conductors, but... 

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