Basic information History, Occurrence, and Uses Physical Properties Reactions Recovery Safety Related Supplier
Rhodium Chemical Properties
- Melting point:1966 °C(lit.)
- Boiling point:3727 °C(lit.)
- Density 1.41 g/mL at 25 °C
- storage temp. Flammables area
- form wire
- color Red
- Specific Gravity12.41
- Resistivity4.33 μΩ-cm, 20°C
- Water Solubility Insoluble
- Merck 14,8186
- CAS DataBase Reference7440-16-6(CAS DataBase Reference)
- NIST Chemistry ReferenceRhodium(7440-16-6)
- EPA Substance Registry SystemRhodium (7440-16-6)
Rhodium Usage And Synthesis
- History, Occurrence, and UsesRhodium was discovered by W. H. Wollaston in 1803-04 in the aqua regia platium hexachloride, (NH4)2PtCl6, from the aqua regia extract, the resulting filtrate contained two new metals, palladium and rhodium. The element was named rhodium, derived from the Greek word rhodon for the beautiful rose color of its chloro salt and its aqueous solution.
Rhodium occurs in nature in trace quantities, always associated with other platinum metals. It is found in native form. Its average abundance in the earth’s crust is estimated to be 1mg/kg. Rhodium is used as a precious metal for making jewelry and decorative. Other important applications of this metal or its compounds are in making glass for mirrors or filtering light; in catalytic reactions to synthesize a number of products; as an alloying element for platinum; as a hardening agent for platinum and palladium at high temperatures; in electrical contact plates in radioand audio-frequency circuits. Rhodium alloyed with platinum is used in thermocouples. A 10% Rh-Pt alloy was introduced by LeChatelier in 1885 for use in thermocouples. Also, rhodium alloys are used in laboratory crucibles, electrodes, optical instruments, furnace linings, and making glass fibers.
- Physical PropertiesGrayish-white metal; face-centered cubic crystals; density 12.41 g/cm3; hardness, annealed 100-120 Vickers units; melts at 1,964°C; vaporizes at 3,695°C; electrical resistivity 4.33 microhm–cm at 0°C; tensile strength, annealed 50 tons/in2; Young’s modulus, annealed 2.3×104 tons/in2; magnetic susceptibility 0.99×10–6 cm3/g; thermal neutron absorption cross section 156 barns; insoluble in water; soluble in concentrated sulfuric or hydrochloric acid under boiling conditions; the metal in massive form is slightly soluble in aqua regia, but in small quantities or in thin plates it partially dissolves in aqua regia; forms solid solutions with platinum, palladium and iridium.
- ReactionsAt ordinary temperatures rhodium is stable in air. When heated above 600°C, it oxidizes to Rh2O3, forming a dark oxide coating on its surface. The gray crystalline sesquioxide has a corundom-like crystal structure. The sesquioxide, Rh2O3 , decomposes back to its elements when heated above 1,100°C. However, on further heating the metal starts to lose its weight similar to platinum, probably due to loss of its volatile oxide RhO2 dissolved in the metal. The molten metal readily absorbs gaseous oxygen.
The metal in powder form absorbs hydrogen when heated. When heated with carbon monoxide under pressure rhodium forms carbonyl, Rh4(CO)12. The metal combines with halogens at elevated temperatures. When heated with fluorine at 500 to 600°C, it forms a trifluoride, RhF3, a red rhombohedral crystalline powder insoluble in water, dilute acids, or alkalis. Also, a blue tetrafluoride, RhF4, is formed as a minor product. When heated with chlorine gas above 250°C, the brown-red trichloride, RhCl3, forms. It is hygroscopic, decomposing at 450°C.
Rhodium is attacked by fused caustic soda or caustic potash. Also, fused sodium or potassium cyanide and sodium bisulfate attack the metal.
- RecoveryWollaston’s earliest method involved recovery of rhodium from native platinum. Pt was digested with aqua regia. Rhodium in bulk form is slightly soluble in aqua regia. However, when present as a minor constituent in platinum alloys, the metal may be extracted with aqua regia. Platinum was precipitated from aqua regia extract as ammonium hexachloroplatinate, (NH4)2PtCl6. Addition of mercurous cyanide, Hg2(CN)2, to the filtrate separated palladium as yellow palladium cyanide, Pd(CN)2. Excess mercurous cyanide in the remaining solution was decomposed by evaporating the solution with hydrochloric acid. The residue was treated with ethanol. A dark red solid residue that remained after alcohol treatment was a double chloride, sodium chlororhodite, Na3RhCl6•18H2O. Heating this rhodium complex with hydrogen decomposed the double chloride forming sodium chloride, hydrogen chloride and rhodium metal:
2Na3RhCl6 + 3H2 → 6NaCl + 6HCl + 2Rh
Sodium chloride was removed by leaching with water. Rhodium powder was left as residue.
- Chemical PropertiesRhodium, together with platinum, palladium, iridium, ruthenium, and osmium, is one of the platinum-group metals in Group VIII of the Periodic Table. Rhodium metal is a white, hard, ductile, malleable solid with a bluish-gray luster. soluble in ether, alcohol, and water. The alloys of rhodium can also be used in high temperature conditions (i.e., thermocouples and crucibles). It also can be used in electroplating glass products due to its reflective properties.
- Physical propertiesRhodium is a hard shiny-white metal that resists corrosion from oxygen, moisture, andacids at room temperatures. As a member of group 8 (VIII), 45Rh shares many chemical andphysical properties with cobalt (27Co) just above it and iridium (77Ir) below it in the verticalgroup. Therefore, it is considered one of the elements that are transitory between metals andnonmetals. It is rare and only found in combination with platinum ores.
Rhodium’s melting point is 1,966°C, its boiling point is 3,727°C, and its density is 12.41g/cm3.
- IsotopesThere are 52 isotopes of rhodium, ranging from Rh-89 to Rh-122. All are producedartificially with relatively short half-lives except one stable isotope, Rh-103, whichconstitutes 100% of the element’s existence in the Earth’s crust.
- Origin of NameNamed after the Greek word rhodon, which means “rose,” because of the reddish color of its salt compounds.
- OccurrenceRhodium is rare, but not as rare as ruthenium. It makes up only 1 part in 20 million of theelements found in the Earth’s crust. Even so, it is considered the 79th most abundant elementand is found mixed with platinum ore, and to a lesser extent, it is found with copper andnickel ores. It is found in Siberia, South Africa, and Ontario, Canada.
Rhodium is recovered from platinum and other ores by refining and purification processesthat start by dissolving the other platinum group metals and related impurities with strongacids that do not affect the rhodium itself. Any remaining platinum group elements areremoved by oxidation and bathing the mixture in chlorine and ammonia.
Rhodium is usually produced as a powder and can be formed by either casting or powdermetallurgy.
- CharacteristicsRhodium is one of the six platinum transition elements that include Ru, Rh, Pd, Os, Ir, andPt. Of these metals, rhodium has the highest electrical and thermal conductivity. Although arelatively scarce metal, rhodium makes an excellent electroplated surface that is hard, wearswell, and is permanently bright—ideal for plating the reflectors in automobile headlights.
- HistoryWollaston discovered rhodium in 1803-4 in crude platinum ore he presumably obtained from South America. Rhodium occurs native with other platinum metals in river sands of the Urals and in North and South America. It is also found with other platinum metals in the copper-nickel sulfide ores of the Sudbury, Ontario region. Although the quantity occurring here is very small, the large tonnages of nickel processed make the recovery commercially feasible. The annual world production of rhodium in 1999 was only about 9000 kg. The metal is silvery white and at red heat slowly changes in air to the sesquioxide. At higher temperatures it converts back to the element. Rhodium has a higher melting point and lower density than platinum. Its major use is as an alloying agent to harden platinum and palladium. Such alloys are used for furnace windings, thermocouple elements, bushings for glass fiber production, electrodes for aircraft spark plugs, and laboratory crucibles. It is useful as an electrical contact material as it has a low electrical resistance, a low and stable contact resistance, and is highly resistant to corrosion. Plated rhodium, produced by electroplating or evaporation, is exceptionally hard and is used for optical instruments. It has a high reflectance and is hard and durable. Rhodium is also used for jewelry, for decoration, and as a catalyst. Fifty-two and isomers are now known. Rhodium metal (powder) costs about $180/g (99.9%).isotopes
- UsesRhodium is a transition metal catalyst used in a multitude of inorganic synthesis.
- UsesAs an alloy with platinum; as a corrosion-resistant electroplate for protecting silverware from tarnishing; for making high-reflectivity mirrors for cinema projectors, searchlights. Spongy or black rhodium is used as a catalyst in various organic hydrogenation and oxidation reactions.
- UsesRhodium is commercially used as an alloy metal with other metals to form durable hightemperatureelectrical equipment, thermocouples, electrical contacts and switches, and laboratorycrucibles.
Because of its high reflectivity, it is used to electroplate jewelry, silverware, optical instruments,mirrors, and reflectors in lighting devices.
When rhodium is combined with platinum and palladium, the elements together form theinternal metals of automobile catalytic converters, which convert hot unburned hydrocarbonexhaust gases to less harmful CO2 and H2O. Similar alloys are used to manufacture hightemperatureproducts such as electric coils for metal refining furnaces and high-temperaturespark plugs.
- Production MethodsPure rhodium is prepared by the reduction of its ammonium salt (dichloropentaaminorhodium).
- DefinitionMetallic element having atomic number 45, group VIII of the periodic table, aw 102.9055, no isotopes, valence = 3.
- DefinitionA rare silvery hard transition metal. It is difficult to work and highly resistant to corrosion. Rhodium occurs native but most is obtained from copper and nickel ores. It is used in protective finishes, alloys, and as a catalyst. Symbol: Rh; m.p. 1966°C; b.p. 3730°C; r.d. 12.41 (20°C); p.n. 45; r.a.m. 102.90550.
- Definitionrhodium: Symbol Rh. A silvery whitemetallic transition element;a.n. 45; r.a.m. 102.9; r.d. 12.4; m.p.1966°C; b.p. 3727°C. It occurs withplatinum and is used in certain platinumalloys (e.g. for thermocouples)and in plating jewellery and opticalreflectors. Chemically, it is not attackedby acids (dissolves only slowlyin aqua regia) and reacts with nonmetals(e.g. oxygen and chlorine) atred heat. Its main oxidation state is+3 although it also forms complexesin the +4 state. The element was discoveredin 1803 by William Wollaston(1766–1828).
- HazardFlammable in powder form. Upper respira- tory tract irritant. Questionable carcinogen.
- HazardThe powder and dust of rhodium metal are flammable in air. Some of the compounds maycause skin irritations. It is best to use approved laboratory procedures when handling any ofthe six elements in the platinum family of metals.
- Industrial usesMetallic rhodium is the whitest of the platinum metals and does not tarnish under atmospheric conditions. It is insoluble in most acids, including aqua regia, but is attacked by chlorine at elevated temperatures and by hot fuming sulfuric acid. Liquid rhodium dissolves oxygen, and ingots are made by argon-arc melting. At temperatures above 1200 C, rhodium reacts with oxygen to form rhodium oxide, Rh2O3. Rhodium is used to make the nibs of writing pens, to make resistance windings in high-temperature furnaces, for high-temperature thermocouples, as a catalyst, and for laboratory dishes. It is the hardest of the platinum-group metals; the annealed metal has a Brinell hardness of 135. Rhodium is also valued for electroplating jewelry, electric contacts, hospital and surgical instruments, and especially reflectors.
The most important alloys of rhodium are rhodium platinum. They form solid solutions in any proportion, but alloys of more than 40% rhodium are rare. Rhodium is not a potent hardener of platinum but increases its high-temperature strength. It is easily workable and does not tarnish or oxidize at high temperatures. These alloys are used for thermocouples and in the glass industry.
- Safety ProfileHandle carefully. It may be a sensitizer but not to the same extent as platinum. Most rholum compounds have only moderate toxicity by ingestion. Flammable when exposed to heat or flame. Violent reaction with chlorine, bromine pentafluoride, bromine trifluoride, and OF2. A catalytic metal
- Potential ExposureRhodium has few applications by itself, as in rhodium plating of white gold jewelry or plat- ing of electrical parts, such as commutator slip rings, but, mainly, rhodium is used as a component of platinum alloys. Rhodium-containing catalysts have been proposed for use in automotive catalytic converters for exhaust gas cleanup.
- ShippingFlammable powder, Hazard Class: 4.1; Labels: 4.1-Flammable solid.
- IncompatibilitiesFlammable as a dust, fume, or powder may form explosive mixture with air. Incompatible with strong oxidizers (chlorates, nitrates, peroxides, permanga- nates, perchlorates, chlorine, bromine, fluorine, etc.); con- tact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides, bromine pentafluoride, and bromine trifluoride; chlorine trifluoride; oxygen difluoride.
- Waste DisposalRecovery in view of the high economic value. Recovery techniques for recycling of rhodium in plating wastes and spent catalysts have been described in the literature.
Rhodium Preparation Products And Raw materials
- Platinum dioxide Dichloro(1,5-cyclooctadien)ruthenium(II) polymer RHODIUM (III) BROMIDE DIHYDRATE RHODIUM(II) ACETATE DIMER,RHODIUM ACETATE DIMER 1,1,3,3-TETRAMETHYLBUTYL ISOCYANIDE Tosylmethyl isocyanide RHODIUM(III) CHLORIDE,RHODIUM CHLORIDE RHODIUM(III) OXIDE PHENYLSELENOL Tris(triphenylphosphine)rhodiu N-BUTYLISOCYANIDE RHODIUM(I) CHLORIDE 1,5-CYCLOOCTADIENE COMPLEX DIMER Ethyl isocyanoacetate SALCOMINE RHODIUM AMMONIUM CHLORIDE SODIUM HEXACHLORORHODATE(III) METHYL ISOCYANOACETATE DICARBONYL(CHLORO)RHODIUM(I), DIMER
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