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Platinum group
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The platinum group metals (abbreviated as the PGMs; alternatively, the platinum group or platinum metals) sometimes collectively refers to six metallic elements clustered together in the periodic table.
These elements are all transition metals, lying in the d-block (groups 8, 9, and 10, periods 5 and 6 — in Mendeleev's original table, this area was called "Group VIII").
The six platinum group metals are ruthenium, rhodium, palladium, osmium, iridium, and platinum.
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Encyclopedia
The platinum group metals (abbreviated as the PGMs; alternatively, the platinum group or platinum metals) sometimes collectively refers to six metallic elements clustered together in the periodic table.
These elements are all transition metals, lying in the d-block (groups 8, 9, and 10, periods 5 and 6 — in Mendeleev's original table, this area was called "Group VIII").
The six platinum group metals are ruthenium, rhodium, palladium, osmium, iridium, and platinum. They have similar physical and chemical properties, and tend to occur together in the same mineral deposits.
Strictly taken, the three elements iron, cobalt and nickel in the same group have similar physical (e.g. high melting points, high density for period 4 of the periodic table) and chemical properties such as being able to be used as a catalyst, forming complex ions such as Fe(CN)64-, and the ability of nickel to absorb hydrogen (like Pd and Pt).
History
Naturally occurring platinum and platinum-rich alloys have been known for a long time. Though the metal was used by pre-Columbian peoples, the first European reference to platinum appears in 1557 in the writings of the Italian humanist Julius Caesar Scaliger (1484-1558) as a description of a mysterious metal found in Central American mines between Darién (Panama) and Mexico ("up until now impossible to melt by any of the Spanish arts").
The Spaniards named the metal platina ("little silver") when they first encountered it in Colombia. They regarded platinum as an unwanted impurity in the silver they were mining.
Properties
The platinum metals have outstanding catalytic properties. They are highly resistant to wear and tarnish, making platinum, in particular, well suited for fine jewelry. Other distinctive properties include resistance to chemical attack, excellent high-temperature characteristics, and stable electrical properties. All these properties have been exploited for industrial applications.
Applications
Platinum, platinum alloys, and iridium are used as crucible materials for the growth of single crystals, especially oxides. The chemical industry uses a significant amount of either platinum or a platinum-rhodium alloy catalyst in the form of gauze to catalyze the partial oxidation of ammonia to yield nitric oxide, which is the raw material for fertilizers, explosives, and nitric acid.
In recent years, a number of platinum-group metals have become important as catalysts in synthetic organic chemistry. Ruthenium dioxide is used as coatings on dimensionally stable titanium anodes used in the production of chlorine and sodium hydroxide.
Platinum supported catalysts are used in the refining of crude oil, reforming, and other processes used in the production of high-octane gasoline and aromatic compounds for the petrochemical industry. Since 1979, the automotive industry has emerged as the principal consumer of platinum-group metals. Palladium, platinum, and rhodium have been used as oxidation catalyst in catalytic converters to treat automobile exhaust emissions. A wide range of platinum-group metal alloy compositions are used in low-voltage and low-energy contacts, thick- and thin-film circuits, thermocouples and furnace components, and electrodes.
Sources
Platinum
- Sperrylite (platinum arsenide, PtAs2) ore is a major source of this metal. A naturally occurring platinum-iridium alloy, platiniridium, is found in the mineral cooperite (platinum sulfide, PtS). Platinum in a native state, often accompanied by small amounts of other platinum metals, is found in alluvial and placer deposits in Colombia, Ontario, the Ural Mountains, and in certain western American states. Platinum is also produced commercially as a by-product of nickel ore processing. The huge quantities of nickel ore processed makes up for the fact that platinum makes up only two parts per million of the ore. South Africa, with vast platinum ore deposits in the Merensky Reef of the Bushveld complex, is the world's largest producer of platinum, followed by Russia.
Osmium
- Iridiosmium is a naturally occurring alloy of iridium and osmium found in platinum-bearing river sands in the Ural Mountains and in North and South America. Trace amounts of osmium also exist in nickel-bearing ores found in the Sudbury, Ontario region along with other platinum group metals. Even though the quantity of platinum metals found in these ores is small, the large volume of nickel ores processed makes commercial recovery possible.
Iridium
- Metallic iridium is found with platinum and other platinum group metals in alluvial deposits. Naturally occurring iridium alloys include osmiridium and iridiosmium, both of which are mixtures of iridium and osmium. It is recovered commercially as a by-product from nickel mining and processing.
Ruthenium
- Ruthenium is generally found in ores with the other platinum group metals in the Ural Mountains and in North and South America. Small but commercially important quantities are also found in pentlandite extracted from Sudbury, Ontario and in pyroxenite deposits in South Africa. Ruthenium is commercially isolated through a complex chemical process in which hydrogen is used to reduce ammonium ruthenium chloride yielding a powder. The powder is then consolidated by powder metallurgy techniques or by argon-arc welding.
Rhodium
- The industrial extraction of rhodium is complex as the metal occurs in ores mixed with other metals such as palladium, silver, platinum, and gold. It is found in platinum ores and obtained free as a white inert metal which is very difficult to fuse. Principal sources of this element are located in river sands of the Ural Mountains, in North and South America and also in the copper-nickel sulfide mining area of the Sudbury Basin region. Although the quantity at Sudbury is very small, the large amount of nickel ore processed makes rhodium recovery cost effective. However, the annual world production of this element is only 7 or 8 tons and there are very few rhodium minerals.
Palladium
- Palladium is found as a free metal and alloyed with platinum and gold with platinum group metals in placer deposits of the Ural Mountains, Australia, Ethiopia, South and North America. However it is commercially produced from nickel-copper deposits found in South Africa and Ontario. The huge volume of nickel-copper ore processed makes this extraction profitable in spite of its low concentration in these ores.
Production
The production of pure platinum group metals normally starts from residues of the production of other metals with a mixture of several of those metals. One typical starting product is the anode residue of gold or nickel production. The differences in chemical reactivity and solubility of several compounds of the metals under extraction are used to separate them.
A first step is to dissolve all the metals in aqua regia forming their respective nitrates. If silver is still present, this is then separated by forming insoluble silver chloride. Rhodium sulfate is separated after the salts have been melted together with sodium hydrogensulfate and leached with water. The residue is then melted together with sodium peroxide, which dissolves all the metals and leaves the iridium. The two remaining metals, ruthenium and osmium, form ruthenium and osmium tetroxides after chlorine has been added to solution. The osmium tetroxide is then dissolved in alcoholic sodium hydroxide and separated from the ruthenium tetroxides. All of these metals' final chemical compounds can ultimately be reduced to the elemental metal using hydrogen.
Production in nuclear reactors
Significant quantities of platinum group metals - Ruthenium, Rhodium and Palladium are formed as fission products in nuclear reactor. With escalating prices and increasing global demand, reactor produced noble metals are emerging as an alternative source. Various reports are available on the possibility of recovering fission noble metals from spent nuclear fuel.
Recently there is an upsurge in the recovery of valuable fission products which reflects in the form of articles in leading scientific journals. Palladium has been of special interest due to its less complex behavior when compared to rhodium and ruthenium. The special interest in palladium may be also due to its wide spread application in chemical catalysis and electronic industry. Several research groups are exploring the possibility of recovering palladium by various methods like - direct electrolysis of high-level liquid waste , , using room temperature ionic liquids (RTILs) as electrolyte for nuclear fuel dissolution and recovery , solvent extraction, ion exchange, etc. Room temperature ionic liquids have been employed to recover rhodium also recently.
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