Iridium alloys chlorides

The insertion of platinum microelectrodes into the surface of lead and some lead alloys has been found to promote the formation of lead dioxide in chloride solutions" " . Experiments with silver and titanium microelectrodes have shown that these do not result in this improvement". Similar results to those when using platinum have been found with graphite and iridium, and although only a very small total surface area of microelectrodes is required to achieve benefit, the larger the ratio of platinum to lead surface, the faster the passivation". Platinised titanium microelectrodes have also been utilised. 

Iridium has been deposited from chloride-sulphamate and from bromide electrolytes , but coating characteristics have not been fully evaluated. The bromide electrolytes were further developed by Tyrrell for the deposition of a range of binary and some ternary alloys of the platinum metals, but, other than the platinum-iridium system, no commercial exploitation of these processes has yet been made. 

The nozzle of original design was fabricated from a niobium alloy coated with niobium silicide and could not operate above 1320°C. This was replaced by a thin shell of rhenium protected on the inside by a thin layer of iridium. The iridium was deposited first on a disposable mandrel, from iridium acetylacetonate (pentadionate) (see Ch. 6). The rhenium was then deposited over the iridium by hydrogen reduction of the chloride. The mandrel was then chemically removed. Iridium has a high melting point (2410°C) and provides good corrosion protection for the rhenium. The nozzle was tested at 2000°C and survived 400 cycles in a high oxidizer to fuel ratio with no measurable corrosion.O l... 

Phillips and Timms [599] described a less general method. They converted germanium and silicon in alloys into hydrides and further into chlorides by contact with gold trichloride. They performed GC on a column packed with 13% of silicone 702 on Celite with the use of a gas-density balance for detection. Juvet and Fischer [600] developed a special reactor coupled directly to the chromatographic column, in which they fluorinated metals in alloys, carbides, oxides, sulphides and salts. In these samples, they determined quantitatively uranium, sulphur, selenium, technetium, tungsten, molybdenum, rhenium, silicon, boron, osmium, vanadium, iridium and platinum as fluorides. They performed the analysis on a PTFE column packed with 15% of Kel-F oil No. 10 on Chromosorb T. Prior to analysis the column was conditioned with fluorine and chlorine trifluoride in order to remove moisture and reactive organic compounds. The thermal conductivity detector was equipped with nickel-coated filaments resistant to corrosion with metal fluorides. Fig. 5.34 illustrates the analysis of tungsten, rhenium and osmium fluorides by this method. 

Reducing agents Aluminum hydride. Bis-3-methyl-2-butylborane. n-Butyllithium-Pyridine. Calcium borohydride. Chloroiridic acid. Chromous acetate. Chromous chloride. Chromous sulfate. Copper chromite. Diborane. Diborane-Boron trifluoride. Diborane-Sodium borohydride. Diethyl phosphonate. Diimide. Diisobutylaluminum hydride. Dimethyl sulfide. Hexamethylphosphorous triamide. Iridium tetrachloride. Lead. Lithium alkyla-mines. Lithium aluminum hydride. Lithium aluminum hydride-Aluminum chloride. Lithium-Ammonia. Lithium diisobutylmethylaluminum hydride. Lithium-Diphenyl. Lithium ethylenediamine. Lithium-Hexamethylphosphoric triamide. Lithium hydride. Lithium triethoxyaluminum hydride. Lithium tri-/-butoxyaluminum hydride. Nickel-aluminum alloy. Pyridine-n-Butyllithium. Sodium amalgam. Sodium-Ammonia. Sodium borohydride. Sodium borohydride-BFs, see DDQ. Sodium dihydrobis-(2-methoxyethoxy) aluminate. Sodium hydrosulflte. Sodium telluride. Stannous chloride. Tin-HBr. Tri-n-butyltin hydride. Trimethyl phosphite, see Dinitrogen tetroxide. 

The most commonly used working electrode material is platinum, sometimes alloyed with a few per cent of iridium. Two difficulties can arise. First, in chloride media, the Pt anode may dissolve and codeposit with the intended metal on the cathode platinum dissolution can be suppressed using a depolarizer such as hydrazine sulfate. Second, electrode cleaning is difficult when the deposited metal alloys with platinum. This arises with Bi, Cd, Ga, Hg, Pb, Sn, and Zn but can be prevented by precoating Pt with Cu or Ag. 

In chloride electrolyte systems, titanium anodes with iridium or ruthenium compound catalytic coatings are used to allow evolution of chlorine at the anodes. For these anodes, each short circuit from nodules and dendrites not only destroys the local active coating and its catalytic effect but also completely destroys any ability for that area to oxidize chloride to chlorine. Shorts thereby reduce the life of these anodes which is important since these anodes are relatively expensive compared to lead alloy anodes normally utilized in sulphate based systems. The use of such catalytic anodes is expanding with some sulphate electrolyte copper electrowinning plants now moving to a form of these titanium catalytic anodes a nickel plant has these anodes for mixed chloride/sulphate duty and there appears scope for further expansion into nickel sulphate electrowinning. 

The platinum group metals occur jointly as alloys and as mineral compounds in placer deposits of varying compositions. Ru and Os are separated from the PGM mix by distillation of their volatile oxides, whereas platinum, iridium, palladium, and rhodium are separated by repeated solution and precipitation as complex PGM chlorides, or by solvent extraction and thermal decomposition to sponge or powder. PGM scrap is recycled by melting with collector metals (lead, iron, or copper) followed by element-specific extraction. 

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