Rhodium

History, Occurrence, and Uses

Rhodium 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 Properties

Grayish-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.

Reactions

At 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.

Recovery

Wollaston’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.

Description

Rhodium is one of the platinum group elements, and is found at very low concentrations in the Earths crust. Rhodium was discovered by William Hyde Wollaston (England) in 1804. The origin of the name comes from the Greek word rhodon, meaning rose. The plated solid is very corrosion resistant and exceptionally hard. While inert in air and acids, it can produce a violent reaction to chlorine, bromine pentafluoride, bromine trifluoride, and fluorine monoxide.

Chemical Properties

Rhodium, 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 properties

Rhodium 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.

Isotopes

There 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 Name

Named after the Greek word rhodon, which means “rose,” because of the reddish color of its salt compounds.

Occurrence

Rhodium 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.

Characteristics

Rhodium 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.

History

Wollaston 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

Uses

As 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.

Uses

Rhodium is a transition metal catalyst used in a multitude of inorganic synthesis.

Uses

Rhodium 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.

Definition

rhodium: 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).

Production Methods

Pure rhodium is prepared by the reduction of its ammonium salt (dichloropentaaminorhodium).

Definition

A 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.

Definition

Metallic element having atomic number 45, group VIII of the periodic table, aw 102.9055, no isotopes, valence = 3.

General Description

This product has been enhanced for energy efficiency.

Hazard

Flammable in powder form. Upper respira- tory tract irritant. Questionable carcinogen.

Hazard

The 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.

Health Hazard

There are no data demonstrating acute or chronic rhodium-related diseases; irritation and sensitization have occasionally been reported in humans from exposure to the salts of rhodium. Solutions of insoluble salts splashed in the eye may cause mild irritation.

Flammability and Explosibility

Not classified

Industrial uses

Metallic 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 Profile

Handle 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 Exposure

Rhodium 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.

First aid

If this chemical gets into the eyes, remove anycontact lenses at once and irrigate immediately for at least15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts theskin, remove contaminated clothing and wash immediatelywith soap and water. Seek medical attention immediately. Ifthis chemical has been inhaled, remove from exposure,begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR ifheart action has stopped. Transfer promptly to a medicalfacility. When this chemical has been swallowed, get medical attention. Give large quantities of water and inducevomiting. Do not make an unconscious person vomit. Ifmetal fume fever develops, it may last less than 36 h.Note to physician: In case of fume inhalation, treat for pulmonary edema. Give prednisone or other corticosteroidorally to reduce tissue response to fume. Positive-pressureventilation may be necessary. Treat metal fume fever withbed rest, analgesics, and antipyretics.

Carcinogenicity

Chick embryos exposed to rhodium on the eighth day of incubation were stunted; mild reduction of limb size and feather growth inhibition were also observed. A number of rhodium compounds have tested positive in bacterial assays for genetic altering capability.

Environmental Fate

The most common route by which rhodium enters the environment is as a component of automobile exhaust resulting from use of catalytic converters. Rhodium is insoluble in water and all acids, with the exception that very finely separated material may be dissolved in concentrated sulfuric acid and aqua regia.
Being largely inert, rhodium can undergo long-range transport, and particulate phase matter generally leaves the atmosphere by wet or dry deposition. In an aqueous environment, rhodium can form complexes with halide and nitrogen donor ligands, which may be water soluble, but reactions can be dictated by pH, redox potential, and what material is available for creating ligands. Reactions in soil can depend on these same factors, as well as chloride concentrations, and rhodium is seen to be mobile only in highly acidic soils.
Rhodium has been seen to bioaccumulate in both fresh and salt water species, and has the potential to biomagnify.

storage

Color Code—Red (powder): FlammabilityHazard: Store in a flammable materials storage area. Priorto working with this material you should be trained on itsproper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from strong oxidizers and sources of ignition. Where possible, automaticallytransfer material from drums or other storage containers toprocess containers. Sources of ignition, such as smokingand open flames, are prohibited where this chemical is handled, used, or stored. Metal containers involving the transferof this chemical should be grounded and bonded. Whereverthis chemical is used, handled, manufactured, or stored, useexplosion-proof electrical equipment and fittings.

Shipping

Flammable powder, Hazard Class: 4.1; Labels: 4.1-Flammable solid.

Toxicity evaluation

Enzymes that have essential sulfhydryl groups in or near the activation sites are completely inhibited. It is thought that rhodium compounds bond to DNA, RNA, or the corresponding purines and inhibit their synthesis.

Incompatibilities

Flammable 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 Disposal

Recovery 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.