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Platinum
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Platinum is a chemical element with the chemical symbol Pt and an atomic number of 78. Its name is derived from the Spanish term platina del Pinto, which is literally translated into "little silver of the Pinto River." It is in Group 10 of the periodic table of elements. A dense, malleable, ductile, precious, gray-white transition metal, platinum is resistant to corrosion and occurs in some nickel and copper ores along with some native deposits.
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Platinum is a chemical element with the chemical symbol Pt and an atomic number of 78. Its name is derived from the Spanish term platina del Pinto, which is literally translated into "little silver of the Pinto River." It is in Group 10 of the periodic table of elements. A dense, malleable, ductile, precious, gray-white transition metal, platinum is resistant to corrosion and occurs in some nickel and copper ores along with some native deposits. Platinum is used in jewelry, laboratory equipment, electrical contacts, dentistry, and catalytic converters. Platinum bullion has the ISO currency code of XPT. Platinum is a commodity with a value that fluxuates according to market forces. On December 23rd, 2008, Platinum was worth $845.00 per troy ounce (approximately $27.17 per gram).
Characteristics
As a pure metal, platinum is silvery-white in appearance, lustrous, ductile, and malleable. It does not oxidize at any temperature, although it is corroded by halogens, cyanides, sulfur, and caustic alkalis. Platinum is insoluble in hydrochloric and nitric acid, but dissolves in aqua regia to form chloroplatinic acid, H2PtCl6.
Platinum's wear- and tarnish-resistance characteristics are well suited for making fine jewelry. Platinum is more precious than silver. The price of platinum, like other industrial commodities, is more volatile than gold. In 2008 the price of platinum ranged from $774 to $2,252 per oz.
During periods of sustained economic stability and growth, the price of platinum tends to be as much as twice the price of gold, whereas during periods of economic uncertainty, the price of platinum tends to decrease due to reduced industrial demand, falling below the price of gold. Gold prices are more stable in slow economic times, as gold is considered a safe haven and gold demand is not driven by industrial uses. In the 18th century, platinum's rarity made King Louis XV of France declare it the only metal fit for a king.
Platinum possesses high resistance to chemical attack, excellent high-temperature characteristics, and stable electrical properties. All of these properties have been exploited for industrial applications.
Isotopes
Platinum has six naturally occurring isotopes: 190Pt, 192Pt, 194Pt, 195Pt, 196Pt, and 198Pt. The most abundant of these is 195Pt, comprising 33.83% of all platinum. 190Pt is the least abundant at only .01%. Of the naturally occurring isotopes, only 190Pt is unstable, though it decays with a half-life of 650 years. 198Pt undergoes alpha decay, but because its half-life is estimated as being greater than 320 years, it is considered stable. Platinum also has 31 synthetic isotopes ranging in atomic mass from 166 to 202, making the total number of known isotopes 37. The least stable of these is 166Pt with a half-life of 300 µs, while the most stable is 193Pt with a half-life of 50 years. Most of platinum's isotopes decay by some combination of beta decay and alpha decay. 188Pt, 191Pt, and 193Pt decay primarily by electron capture. 190Pt and 198Pt have double beta decay paths.
Chemistry and compounds
Platinum's most common oxidation states are +2, and +4. The +1 and +3 oxidation states are less common, and are often stabilized by metal bonding in bimetallic (or polymetallic) species. As is expected, tetracoordinate platinum(II) compounds tend to adopt a square planar geometry. While elemental platinum is generally unreactive, it dissolves in aqua regia to give soluble hexachloroplatinic acid ("H2PtCl6", formally (H3O)2PtCl6·nH2O ):
- Pt + 4 HNO3 + 6 HCl ? H2PtCl6 + 4 NO2 + 4 H2O
This compound has various applications in photography, zinc etchings, indelible ink, plating, mirrors, porcelain coloring, and as a catalyst.
Treatment of hexachloroplatinic acid with an ammonium salt, such as ammonium chloride, gives ammonium hexachloroplatinate, which is very insoluble in ammonium solutions. Heating the ammonium salt in the presence of hydrogen reduces it to elemental platinum. Platinum is often isolated from ores and recycled thus. Potassium hexachloroplatinate is similarly insoluble, such that the acid has been used in the determination of potassium ions by gravimetry.
When hexachloroplatinic acid is heated, it decomposes through platinum(IV) chloride and platinum(II) chloride to elemental platinum, although the reactions do not occur stepwise, cleanly:
- (H3O)2PtCl6·n H2O PtCl4 + 2 HCl + (n + 2) H2O
- PtCl4 PtCl2 + Cl2
- PtCl2 Pt + Cl2
All three reactions are reversible. Platinum(II) and platinum(IV) bromides are known as well. Platinum hexafluoride is a strong oxidizer.
Platinum(IV) oxide, PtO2, also known as Adams' Catalyst, is a black powder which is soluble in KOH solutions and concentrated acids. PtO2 and the less common PtO both decompose upon heating. Platinum(II,IV) oxide, Pt3O4, is formed in the following reaction:
- 2Pt2+ + Pt4+ + 4O2- ? Pt3O4
Platinum also forms a trioxide, which is actually in the +4 oxidation state.
Unlike palladium acetate, platinum(II) acetate is not commercially available. Where a base is desired, the halides have been used in conjunction with sodium acetate. The use of platinum(II) acetylacetonate has also been reported.
Zeise's salt, containing an ethylene ligand, was one of the first organometallic compounds discovered. Dichloro(cycloocta-1,5-diene)platinum(II) is a commercially available olefin complex, which contains easily-displaced cod ligands. The cod complex, in addition to the halides, are convenient starting points to platinum chemistry. As a soft acid, platinum has a great affinity for sulfur, such as on DMSO; numerous DMSO complexes have been reported and care should be taken in the choice of reaction solvent.
Cisplatin, or cis-diamminedichloroplatinum(II) is the first of a series of square planar platinum(II)-containing chemotherapy drugs, including carboplatin and oxaliplatin These compounds are capable of crosslinking DNA and kill cells by similar pathways to alkylating chemotherapeutic agents.
Occurrence
Platinum is an extremely rare metal, occurring as only 0.003 ppb in the Earth's crust, and is 30 times rarer than gold. It is sometimes mistaken for silver (Ag) but platinum is whiter in appearance.
Platinum is often found chemically uncombined as native platinum and alloyed with iridium as platiniridium. Most often the native platinum is found in secondary deposits, platinum is combined with the other platinum group metals in alluvial deposits. The alluvial deposits used by pre-Columbian people in the Chocó Department, Colombia are still a source for platinum group metals. Another large alluvial deposit was found in the Ural mountains, Russia, which is still mined.
In nickel and copper deposits platinum group metals occur as sulfides (i.e. (Pt,Pd)S)), tellurides (i.e. PtBiTe), antimonides (PdSb), and arsenides (i.e. PtAs2), and as end alloys with nickel or copper. Platinum arsenide, sperrylite (PtAs2), is a major source of platinum associated with nickel ores in the Sudbury Basin deposit in Ontario, Canada. The rare sulfide mineral cooperite, (Pt,Pd,Ni)S, contains platinum along with palladium and nickel. Cooperite occurs in the Merensky Reef within the Bushveld complex, Gauteng, South Africa.
The largest known primary reserves are in the Bushveld complex in South Africa, the large copper–nickel deposits near Norilsk in Russia, and the Sudbury Basin, Canada with its large ore deposits are the two other large deposits. In the Sudbury Basin the huge quantities of nickel ore processed makes up for the fact that platinum is present as only 0.5 ppm in the ore. Smaller reserves can be found in the United States, for example in the Absaroka Range in Montana. This is also shown in the production of 2005. In 2005, South Africa was the top producer of platinum with an almost 80% share followed by Russia and Canada.
Platinum exists in relatively higher abundances on the Moon and in meteorites. Correspondingly, platinum is found in slightly higher abundances at sites of bolide impact on the Earth that are associated with resulting post-impact volcanism, and can be mined economically; the Sudbury Basin is one such example.
Production
Platinum together with the rest of the platinum metals is obtained commercially as a by-product from nickel and copper mining and processing. During electrorefining of copper, noble metals such as silver, gold and the platinum group metals as well as selenium and tellurium settle to the bottom of the cell as anode mud, which forms the starting point for the extraction of the platinum group metals.
If pure platinum is found in placer deposits or other ores it is isolated from them by various methods of subtracting impurities. Because platinum is significantly denser than many of its impurities, the lighter impurities can be removed by simply floating them away in a water bath. Platinum is also non-magnetic, while nickel and iron are both magnetic. These two impurities are thus removed by running an electromagnet over the mixture. Because platinum has a higher melting point than most other substances, many impurities can be burned or melted away without melting the platinum. Finally, platinum is resistant to hydrochloric and sulfuric acids, while other substances are readily attacked by them. Metal impurities can be removed by stirring the mixture in either of the two acids and recovering the remaining platinum.
One suitable method for purification for the raw platinum, which contains platinum, gold, and the other platinum group metals, is to process it with aqua regia, in which palladium, gold and platinum are dissolved, while osmium, iridium, ruthenium and rhodium stay unreacted. The gold is precipitated by the addition of iron(III) chloride and after filtering of the gold, the platinum is precipitated by the addition of ammonium chloride as ammonium chloroplatinate. Ammonium chloroplatinate can be converted to the metal by heating.
Applications
Of the 239 tonnes of platinum sold in 2006, 130 tonnes were used for automobile emissions control devices, 49 tonnes were used for jewelry, 13.3 tonnes were used in electronics, and 11.2 tonnes were used by the chemical industry as a catalyst. The remaining 35.5 tonnes produced were used in various other minor applications, such as electrodes,
anticancer drugs, oxygen sensors, spark plugs and turbine engines.
Catalysis
The most common use of platinum is as catalyst in chemical reactions. It has been employed in this application since the early 1800s, when platinum powder was used to catalyze the ignition of hydrogen. The most important application of platinum is in automobiles as a catalytic converter, which allows the complete combustion of low concentrations of unburned hydrocarbon from the exhaust into carbon dioxide and water vapor. Platinum is also used in the petroleum industry as a catalysts in a number of separate processes, but especially in catalytic reforming of straight run naphthas into higher octane gasoline which becomes rich in aromatic compounds. PtO2, also known as Adams' catalyst, is used as a hydrogenation catalyst, specifically for vegetable oils. Platinum metal also strongly catalyzes the decomposition of hydrogen peroxide into water and oxygen gas.
Standard
From 1889 to 1960, the meter was defined as by the length of a platinum-iridium (90:10) alloy bar, known as the International Prototype Meter bar. The previous bar was made of platinum in 1799. The International Prototype Kilogram remains defined by a cylinder of the same platinum-iridium alloy made in 1879.
The standard hydrogen electrode also utilizes a platinized platinum electrode due to its corrosion resistance, and other attributes.
Precious metal
Platinum is a precious metal commodity; its bullion has the ISO currency code of XPT. Coins, bars, and ingots are traded or collected. Platinum finds use in jewelry, usually as a 90-95% alloy, due to its inertness and shine. In watchmaking, Vacheron Constantin, Patek Philippe, Rolex, Breitling and other companies use platinum for producing their limited edition watch series. Watchmakers highly appreciate the unique properties of platinum as it neither tarnishes nor wears out.
Other uses
In the laboratory, platinum wire is used for electrodes; platinum pans are used in thermogravimetric analysis. Platinum is used as an alloying agent for various metal products, including fine wires, noncorrosive laboratory containers, medical instruments, dental prostheses, electrical contacts, and thermocouples. Platinum-cobalt, an alloy comprised of roughly 3 parts platinum and 1 part cobalt, is used to make extremely strong permanent magnets. Platinum-based anodes are used in ships, pipelines, and steel piers.
Symbol of prestige
Platinum's rarity as a metal has caused advertisers to associate it with exclusivity and wealth. "Platinum" debit cards have greater privileges than do "gold" ones. "Platinum awards" are the second highest possible, ranking above "gold", "silver" and "bronze", but below Diamond. For example, in the United States a musical album that has sold more than 1,000,000 copies, will be credited as "platinum", whereas an album that sold more than 10,000,000 copies will be certified as “diamond”. Some products, such as blenders and vehicles, with a silvery-white color are identified as "platinum". Platinum is considered a precious metal, although its use is not as common as the use of gold or silver. The frame of the Crown of Queen Elizabeth the Queen Mother, manufactured for her Coronation as Consort of King George VI, is made of platinum. It was the first British crown to be made of this particular metal.
History
Platinum occurs naturally in the alluvial sands of various rivers, though there is little evidence of its use by ancient peoples. However, the metal was used by pre-Columbian Americans near modern-day Esmeraldas, Ecuador to produce artifacts of a white gold-platinum alloy. The first European reference to platinum appears in 1557 in the writings of the Italian humanist Julius Caesar Scaliger as a description of an unknown noble metal found between Darién and Mexico, "which no fire nor any Spanish artifice has yet been able to liquefy."
In 1741, Charles Wood, a British metallurgist, found various samples of Columbian platinum in Jamaica, which he sent to William Brownrigg for further investigation. Antonio de Ulloa, also credited with the discovery of platinum, returned to Spain from the French Geodesic Mission in 1746 after having been there for eight years. His historical account of the expedition included a description of platinum as being neither separable nor calcinable. Ulloa also anticipated the discovery of platinum mines. After publishing the report in 1748, Ulloa did not continue to investigate the new metal. In 1758, he was sent to superintend mercury mining operations in Huancavelica.
In 1750, after studying the platinum sent to him by Wood, Brownrigg presented a detailed account of the metal to the Royal Society, mentioning that he had seen no mention of it in any previous accounts of known minerals. Brownrigg also made note of platinum's extremely high melting point and refractoriness toward borax. Other chemists across Europe soon began studying platinum, including Torbern Bergman, Jöns Jakob Berzelius, William Lewis, and Pierre Macquer. In 1752, Henrik Scheffer published a detailed scientific description of the metal, which he referred to as "white gold", including an account of how he succeeded in fusing platinum ore with the aid of arsenic. Scheffer described platinum as being less pliable than gold, but with similar resistance to corrosion.
Carl von Sickingen researched platinum extensively in 1772. He succeeded in making malleable platinum by alloying it with gold, dissolving the alloy in aqua regia, precipitating the platinum with ammonium chloride, igniting the ammonium chloroplatinate, and hammering the resulting finely-divided platinum to make it cohere. Franz Karl Achard made the first platinum crucible in 1784. He worked with the platinum by fusing it with arsenic, then later volatilizing the arsenic.
In 1786, Charles III of Spain provided a library and laboratory to Pierre-François Chabaneau to aid in his research of platinum. Chabaneau succeeded in removing various impurities from the ore, including gold, mercury, lead, copper, and iron. This led him to believe that he was working with a single metal, but in truth the ore still contained the yet-undiscovered platinum group metals. This led to inconsistent results in his experiments. At times the platinum seemed malleable, but when it was alloyed with iridium, it would be much more brittle. Sometimes the metal was entirely incombustible, but when alloyed with osmium, it would volatilize. After several months, Chabaneau succeeded in producing 23 kilograms of pure, malleable platinum by hammering and compressing the sponge form while white-hot. Chabeneau realized that the infusibility of platinum would lend value to objects made of it, and so started a business with Joaquín Cabezas producing platinum ingots and utensils. This started what is known as the "platinum age" in Spain.
From 1875 to 1960 the SI unit of length (the standard metre) was defined as the distance between two lines on a standard bar of an alloy of ninety percent platinum and ten percent iridium, measured at 0 degrees Celsius.
In 2007 Gerhard Ertl won the Nobel Prize in Chemistry for determining the detailed molecular mechanisms of the catalytic oxidation of carbon monoxide over platinum (catalytic converter).
Precautions
According to the Centers for Disease Control and Prevention, short-term exposure to platinum salts "may cause irritation of the eyes, nose, and throat" and long-term exposure "may cause both respiratory and skin allergies." The current OSHA standard is 0.002 milligram per cubic meter of air averaged over an 8-hour work shift.
Certain platinum complexes are used in chemotherapy and show good anti-tumor activity for some tumours. Cisplatin is particularly effective against testicular cancer; cure rate was improved from 10% to 85%. However, the side effects are severe. Cisplatin causes cumulative, irreversible kidney damage and deafness.. As with other ototoxic agents, deafness may be secondary to interactions with melanin in the stria vascularis.
As platinum is a catalyst in the manufacture of the silicone rubber and gel components of several types of medical implants (breast implants, joint replacement prosthetics, artificial lumbar discs, vascular access ports), the possibility that platinum free radicals could enter the body and cause adverse effects has merited study. The FDA and other countries have reviewed the issue and found no evidence to suggest toxicity in vivo.
See also
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