Родий: свойства, применение и история открытия

Rhodium is a chemical element; it has symbol Rh and atomic number 45. It is a very rare, silvery white, hard, corrosion resistant transition metal. It is a noble metal and a member of the platinum group. It has only one naturally occurring isotope, which is 103Rh. Naturally occurring rhodium is usually found as a free metal or as an alloy with similar metals and rarely as a chemical compound in minerals such as bowieite and rhodplumsite. It is one of the rarest and most valuable precious metals. Rhodium is found in platinum or nickel ores with the other members of the platinum group metals. It was discovered in 1803 by William Hyde Wollaston in one such ore, and named for the rose color of one of its chlorine compounds. The element's major use (consuming about 80% of world rhodium production) is as one of the catalysts in the three way catalytic converters in automobiles. Because rhodium metal is inert against corrosion and most aggressive chemicals, and because of its rarity, rhodium is usually alloyed with platinum or palladium and applied in high temperature and corrosion resistive coatings. White gold is often plated with a thin rhodium layer to improve its appearance, while sterling silver is often rhodium plated to resist tarnishing. Rhodium is sometimes used to cure silicones: a two part silicone in which one part containing a silicon hydride and the other containing a vinyl terminated silicone are mixed; one of these liquids contains a rhodium complex. Rhodium detectors are used in nuclear reactors to measure the neutron flux level. Other uses of rhodium include asymmetric hydrogenation used to form drug precursors and the processes for the production of acetic acid.

Rhodium (Greek rhodon (ῥόδον) meaning "rose") was discovered in 1803 by William Hyde Wollaston, soon after he discovered palladium. He used crude platinum ore presumably obtained from South America. His procedure dissolved the ore in aqua regia and neutralized the acid with sodium hydroxide (NaOH). He then precipitated the platinum as ammonium chloroplatinate by adding ammonium chloride (NH4Cl). Most other metals like copper, lead, palladium, and rhodium were precipitated with zinc. Diluted nitric acid dissolved all but palladium and rhodium. Of these, palladium dissolved in aqua regia but rhodium did not, and the rhodium was precipitated by the addition of sodium chloride as After being washed with ethanol, the rose red precipitate was reacted with zinc, which displaced the rhodium in the ionic compound and thereby released the rhodium as free metal. For decades, the rare element had only minor applications; for example, by the turn of the century, rhodium containing thermocouples were used to measure temperatures up to 1800 °C. They have exceptionally good stability in the temperature range of 1300 to 1800 °C. The first major application was electroplating for decorative uses and as corrosion resistant coating. The introduction of the three way catalytic converter by Volvo in 1976 increased the demand for rhodium. The previous catalytic converters used platinum or palladium, while the three way catalytic converter used rhodium to reduce the amount of NOx in the exhaust.

Z Element No. of electrons/shell 27 cobalt 2, 8, 15, 2 45 rhodium 2, 8, 18, 16, 1 77 iridium 2, 8, 18, 32, 15, 2 109 meitnerium 2, 8, 18, 32, 32, 15, 2 (predicted)
Rhodium is a hard, silvery, durable metal that has a high reflectance. Rhodium metal does not normally form an oxide, even when heated. Oxygen is absorbed from the atmosphere only at the melting point of rhodium, but is released on solidification. Rhodium has both a higher melting point and lower density than platinum. It is not attacked by most acids: it is completely insoluble in nitric acid and dissolves slightly in aqua regia.

Naturally occurring rhodium is composed of only one isotope, 103Rh. The most stable radioisotopes are 101Rh with a half life of 3.3 years, 102Rh with a half life of 207 days, 102mRh with a half life of 2.9 years, and 99Rh with a half life of 16.1 days. Twenty other radioisotopes have been characterized with atomic weights ranging from 92.926 u (93Rh) to 116.925 u (117Rh). Most of these have half lives shorter than an hour, except 100Rh (20.8 hours) and 105Rh (35.36 hours). Rhodium has numerous meta states, the most stable being 102mRh (0.141 MeV) with a half life of about 2.9 years and 101mRh (0.157 MeV) with a half life of 4.34 days (see isotopes of rhodium). In isotopes weighing less than 103 (the stable isotope), the primary decay mode is electron capture and the primary decay product is ruthenium. In isotopes greater than 103, the primary decay mode is beta emission and the primary product is palladium.

Rhodium is one of the rarest elements in the Earth's crust, comprising an estimated 0.0002 parts per million (2 × 10−10). Its rarity affects its price and its use in commercial applications. The concentration of rhodium in nickel meteorites is typically 1 part per billion. Rhodium has been measured in some potatoes with concentrations between 0.8 and 30 ppt.

The industrial extraction of rhodium is complex because the ores are mixed with other metals such as palladium, silver, platinum, and gold and there are very few rhodium bearing minerals. It is found in platinum ores and extracted as a white inert metal that is difficult to fuse. Principal sources are located in South Africa; in river sands of the Ural Mountains in Russia; and in North America, including the copper nickel sulfide mining area of the Sudbury, Ontario, region. Although the rhodium abundance at Sudbury is very small, the large amount of processed nickel ore makes rhodium recovery cost effective. The main exporter of rhodium is South Africa (approximately 80% in 2010) followed by Russia.

The primary use of this element is in automobiles as a catalytic converter, changing harmful unburned hydrocarbons, carbon monoxide, and nitrogen oxide exhaust emissions into less noxious gases. Of 30,000 kg of rhodium consumed worldwide in 2012, 81% (24,300 kg) went into this application, and 8,060 kg was recovered from old converters. About 964 kg of rhodium was used in the glass industry, mostly for production of fiberglass and flat panel glass, and 2,520 kg was used in the chemical industry.

Rhodium finds use in jewelry and for decorations. It is electroplated on white gold and platinum to give it a reflective white surface at time of sale, after which the thin layer wears away with use. This is known as rhodium flashing in the jewelry business. It may also be used in coating sterling silver to protect against tarnish (silver sulfide, Ag2S, produced from atmospheric hydrogen sulfide, H2S). Solid (pure) rhodium jewelry is very rare, more because of the difficulty of fabrication (high melting point and poor malleability) than because of the high price. The high cost ensures that rhodium is applied only as an electroplate. Rhodium has also been used for honors or to signify elite status, when more commonly used metals such as silver, gold or platinum were deemed insufficient. In 1979 the Guinness Book of World Records gave Paul McCartney a rhodium plated disc for being history's all time best selling songwriter and recording artist.

Being a noble metal, pure rhodium is inert and harmless in elemental form. However, chemical complexes of rhodium can be reactive. For rhodium chloride, the median lethal dose (LD50) for rats is 198 mg per kilogram of body weight. Like the other noble metals, rhodium has not been found to serve any biological function. People can be exposed to rhodium in the workplace by inhalation. The Occupational Safety and Health Administration (OSHA) has specified the legal limit (Permissible exposure limit) for rhodium exposure in the workplace at 0.1 mg/m3 over an 8 hour workday, and the National Institute for Occupational Safety and Health (NIOSH) has set the recommended exposure limit (REL), at the same level. At levels of 100 mg/m3, rhodium is immediately dangerous to life or health. For soluble compounds, the PEL and REL are both 0.001 mg/m3.