History, Occurrence, and Uses
Ruthenium was recognized as a new element by G.W. Osann in 1828. He found it in insoluble residues from aqua regia extract of native platinum from alluvial deposits in the Ural mountains of Russia. He named it Ruthen after the Latin name Ruthenia for Russia. The discovery of this element, however, is credited to Klaus who in 1844 found that Osann’s ruthenium oxide was very impure and isolated pure Ru metal from crude platinum residues insoluble in aqua regia.
Ruthenium occurs in nature natively, found in minor quantities associated with other platinum metals. Its abundance in the earth’s crust is estimated to be 0.001 mg/kg, comparable to that of rhodium and iridium.
Ruthenium alloyed to platinum, palladium, titanium and molybdenum have many applications. It is an effective hardening element for platinum and palladium. Such alloys have high resistance to corrosion and oxidation and are used to make electrical contacts for resistance to severe wear. Ruthenium–palladium alloys are used in jewelry, decorations, and dental work. Addition of 0.1% ruthenium markedly improves corrosion resistance of titanium. Ruthenium alloys make tips for fountain pen nibs, instrument pivots, and electrical goods. Ruthenium catalysts are used in selective hydrogenation of carbonyl groups to convert aldehydes and ketones to alcohols.
Ruthenium is a hard, white-colored member of the PGE with a BP of 4150 °C (Lide, 2006). Like osmium, it can be used to create a hardened alloy with platinum or palladium. The addition of a small quantity of ruthenium to titanium makes an alloy with increased corrosion resistance (Lide, 2006). Ruthenium is also a versatile catalyst.
Hard silvery-white metal; hexagonal close-packed crystal structure; density 12.41 g/cm3 at 20°C; melts at 2,334°C; vaporizes at 4,150°C; electrical resistivity 7.1 microhm-cm at 0°C; hardness (annealed) 200-350 Vickers units; Young’s modulus 3.0×104 tons/in2; magnetic susceptibility 0.427 cm3/g; thermal neutron absorption cross section 2.6 barns; insoluble in water, cold or hot acids, and aqua regia; can be brought into aqueous phase by fusion of finely divided metal with alkaline hydroxides, peroxides, carbonates and cyanides.
Ruthenium is derived from platinum metal ores. Method of production depends on the type of ore. However, the extraction processes are similar to those of other noble metals (see Platinum, Rhodium and Iridium). Ruthenium, like Rhodium, may be obtained from accumulated anode sludges in electrolytic refining of nickel or copper from certain types of ores. Also, residues from refining nickel by Mond carbonyl process contain ruthenium and other precious metals at very low concentrations. The extraction processes are very lengthy, involving smelting with suitable fluxes and acid treatments.
Metals, such as gold, platinum, and palladium, are separated by digesting refining residues with aqua regia. These metals are soluble in aqua regia, leaving ruthenium, rhodium, iridium, osmium, and silver in the insoluble residue.
The treatment of this insoluble residue may vary. In one typical process, residue is subjected to fusion with sodium peroxide. Ruthenium and osmium are converted to water-soluble sodium ruthenate and osmate, which are leached with water. The aqueous solution is treated with chlorine gas and heated. The ruthenate and the osmate are converted to their tetroxides. Ruthenium tetroxide is distilled out and collected in hydrochloric acid. The tetroxide is converted into ruthenium chloride. Traces of osmium are removed from ruthenium chloride solution by boiling with nitric acid.
Nitric acid converts osmium to volatile osmium tetroxide but forms a nitrosyl complex with ruthenium that remains in the solution. After removal of trace osmium, the solution is treated with ammonium chloride. This precipitates ruthenium as crystals of ammonium chlororuthenate, NH4RuCl6. The precipitate is washed, dried, and ignited to form ruthenium black. This is reduced with hydrogen at 1,000°C to form very pure ruthenium powder.
When heated in air at 500 to 700°C, ruthenium converts to its dioxide, RuO2, a black crystalline solid of rutile structure. A trioxide of ruthenium, RuO3, also is known; formed when the metal is heated above 1,000°C. Above 1,100°C the metal loses weight because trioxide partially volatilizes. Ruthenium also forms a tetroxide, RuO4, which, unlike osmium, is not produced by direct union of the elements.
Halogens react with the metal at elevated temperatures. Fluorine reacts with ruthenium at 300°C forming colorless vapors of pentafluoride, RuF5, which at ordinary temperatures converts to a green solid. Chlorine combines with the metal at 450°C to form black trichloride, RuCl3, which is insoluble in water. Ru metal at ambient temperature is attacked by chlorine water, bromine water, or alcoholic solution of iodine.
Ruthenium is stable in practically all acids including aqua regia. Fusion with an alkali in the presence of an oxidizing agent forms ruthenate, RuO42– and perruthenate, RuO4¯.
When finely-divided Ru metal is heated with carbon monoxide under 200 atm pressure, ruthenium converts to pentacarbonyl, Ru(CO)5, a colorless liquid that decomposes on heating to diruthenium nonacarbonyl, Ru2(CO)9, a yellow crystalline solid. Ruthenium reacts with cyclopentadiene in ether to form a sandwich complex, a yellow crystalline compound, bis(cyclopentadiene) ruthenium(0), also known as ruthenocene.
Elemental ruthenium has a close-packed hexagonal crystal structure. The seven stable isotopes are 96Ru, 98Ru through 102Ru, and 104Ru.
Ruthenium, a transition element, belongs to group VIII
(iron) of the periodic classification and to the light platinum
metals triad. It is a hard and brittle metal that resembles
platinum. It crystallizes in hexagonal form and occurs in the
form of seven stable isotopes: 96 (5.46%), 98 (1.87%), 99
(12.63%), 100 (12.53%), 101 (17.02%), 102 (31.6%), and
104 (18.87%). There are also several radioactive isotopes—93, 94, 95, 97, 103, 105, 106, 107, and 108—of which the
106 isotope characterized by strong β radiation and has a
half-life of 368 days; since it is produced in large quantities
in the nuclear reactors, it deserves special attention. Ruthenium
is the rarest of the platinum group elements (abundance
in the Earth’s crust ~0.0004 ppm). In chemical
compounds, it occurs at oxidation states from +2 to +8;
the most frequent is +3 in ruthenium compounds. Rutheniumis
resistant to acids and aqua regia, it is not oxidized in
the air at room temperature, and in the form of powder it
reacts with oxygen at elevated temperatures. It is dissolved
in molten strong alkalis and reacts with alkaline metal
peroxides and perchlorides. Ruthenium powder reacts
with chlorine above 200°C and with bromine at 300–
700°C.
Ruthenium compounds are usually dark brown (ranging
from yellow to black). Ruthenium forms alloys with platinum,
palladium, cobalt, nickel, and tungsten.
Ruthenium is a rare, hard, silvery-white metallic element located in group 8, just aboveosmium and below iron, with which it shares some chemical and physical properties.Both ruthenium and osmium are heavier and harder than pure iron, making them morebrittle and difficult to refine. Both ruthenium and osmium are less tractable and malleable than iron. Although there are some similar characteristics between ruthenium and iron,ruthenium’s properties are more like those of osmium. Even so, ruthenium is less stablethan osmium. They are both rare and difficult to separate from minerals and ores that containother elements. These factors make it more difficult to determine ruthenium’s accurateatomic weight.
The oxidation state of +8 for ruthenium and its “mate” osmium is the highest oxidationstate of all elements in the transition series. Ruthenium’s melting point is 2,310°C, its boilingpoint is 3,900°C, and its density is 12.45 g/cm3.
There are 37 isotopes for ruthenium, ranging in atomic mass numbers from87 to 120. Seven of these are stable isotopes. The atomic masses and percentage ofcontribution to the natural occurrence of the element on Earth are as follows: Ru-96 =5.54%, Ru-98 = 1.87%, Ru-99 = 12.76%, Ru-100 = 12.60%, Ru-101 = 17.06%, Ru-102 = 31.55%, and Ru-104 = 18.62%.
“Ruthenium” is derived from the Latin word Ruthenia meaning “Russia,”
where it is found in the Ural Mountains.
Ruthenium is a rare element that makes up about 0.01 ppm in the Earth’s crust. Even so, itis considered the 74th most abundant element found on Earth. It is usually found in amountsup to 2% in platinum ores and is recovered when the ore is refined. It is difficult to separatefrom the leftover residue of refined platinum ore.
Ruthenium is found in South America and the Ural Mountains of Russia. There are someminor platinum and ruthenium ores found in the western United States and Canada. All ofthe radioactive isotopes of ruthenium are produced in nuclear reactors.
Ruthenium also belongs to the platinum group, which includes six elements with similarchemical characteristics. They are located in the middle of the second and third series of thetransition elements. The platinum group consists of ruthenium, rhodium,palladium, osmium, iridium, and platinum.
Ruthenium is a hard brittle metal that resists corrosion from all acids but is vulnerable tostrong alkalis (bases). Small amounts, when alloyed with other metals, will prevent corrosionof that metal.
Berzelius and Osann in 1827 examined the residues left after dissolving crude platinum from the Ural
mountains in aqua regia. While Berzelius found no unusual
metals, Osann thought he found three new metals, one of
which he named ruthenium. In 1844 Klaus, generally recognized
as the discoverer, showed that Osann’s ruthenium oxide
was very impure and that it contained a new metal. Klaus
obtained 6 g of ruthenium from the portion of crude platinum
that is insoluble in aqua regia. A member of the platinum
group, ruthenium occurs native with other members of
the group of ores found in the Ural mountains and in North
and South America. It is also found along with other platinum
metals in small but commercial quantities in pentlandite of
the Sudbury, Ontario, nickel-mining region, and in pyroxinite
deposits of South Africa. Natural ruthenium contains seven
isotopes. Twenty-eight other isotopes and isomers are known,
all of which are radioactive. The metal is isolated commercially
by a complex chemical process, the final stage of which
is the hydrogen reduction of ammonium ruthenium chloride,
which yields a powder. The powder is consolidated by powder
metallurgy techniques or by argon-arc welding. Ruthenium is
a hard, white metal and has four crystal modifications. It does
not tarnish at room temperatures, but oxidizes in air at about
800°C. The metal is not attacked by hot or cold acids or aqua
regia, but when potassium chlorate is added to the solution,
it oxidizes explosively. It is attacked by halogens, hydroxides,
etc. Ruthenium can be plated by electrodeposition or by thermal
decomposition methods. The metal is one of the most effective
hardeners for platinum and palladium, and is alloyed
with these metals to make electrical contacts for severe wear
resistance. A ruthenium–molybdenum alloy is said to be superconductive
at 10.6 K. The corrosion resistance of titanium
is improved a hundredfold by addition of 0.1% ruthenium. It
is a versatile catalyst. Hydrogen sulfide can be split catalytically
by light using an aqueous suspension of CdS particles
loaded with ruthenium dioxide. It is thought this may have
application to removal of H2S in oil refining and other industrial
processes. Compounds in at least eight oxidation states
have been found, but of these, the +2. +3. and +4 states are the
most common. Ruthenium tetroxide, like osmium tetroxide,
is highly toxic. In addition, it may explode. Ruthenium compounds
show a marked resemblance to those of osmium. The
metal is priced at about $25/g (99.95% pure).
Ruthenium is used in wear-resistant electrical contacts and the production of thick-film resistors. Its use in some platinum alloys, and as a catalyst. It is a most effective hardeners for platinum and palladium. It is also used in some advanced high-temperature single-crystal super alloys, with applications including the turbine blades in jet engines and fountain pen nibs.
Since ruthenium is rare and difficult to isolate in pure form, there are few uses for it. Itsmain uses are as an alloy to produce noncorrosive steel and as an additive to jewelry metalssuch as platinum, palladium, and gold, making them more durable.
It is also used as an alloy to make electrical contacts harder and wear longer, for medicalinstruments, and more recently, as an experimental metal for direct conversion of solar cellmaterial to electrical energy.
Ruthenium is used as a catalyst to affect the speed of chemical reactions, but is not alteredby the chemical process. It is also used as a drug to treat eye diseases.
As substitute for platinum in jewelry; for pen nibs; as hardener in electrical contact alloys, electrical filaments; in ceramic colors; catalyst in synthesis of long chain hydrocarbons.
A transition
metal that occurs naturally with platinum.
It forms alloys with platinum that
are used in electrical contacts. Ruthenium
is also used in jewelry alloyed with palladium.Symbol: Ru; m.p. 2310°C; b.p.
3900°C; r.d. 12.37 (20°C); p.n. 44; r.a.m.
101.07.
Elemental ruthenium occurs in native alloys of iridium and
osmium (irridosmine, siskerite) and in sulfide and other ores
(pentlandite, laurite, etc.) in very small quantities that are
commercially recovered.
The element is separated from the other platinum metals
by a sequence involving treatment with aqua regia (separation
of insoluble osmium, rhodium, ruthenium, and iridium),
fusion with sodium bisulfate (with which rhodium reacts),
and fusion with sodium peroxide (dissolution of osmium and
ruthenium). The resulting solution of ruthenate and osmate is
treated with ethanol to precipitate ruthenium dioxide. The
ruthenium dioxide is purified by treatment with hydrochloric
acid and chlorine and reduced with hydrogen gas to pure
metal.
Ruthenium is recovered from exhausted catalytic converters
or, in a similar manner, from the waste produced during
platinum and nickel ore processing.
ruthenium: Symbol Ru. A hardwhite metallic transition element;a.n. 44; r.a.m. 101.07; r.d. 12.3; m.p.2310°C; b.p. 3900°C. It is found associatedwith platinum and is used as acatalyst and in certain platinum alloys.Chemically, it dissolves in fusedalkalis but is not attacked by acids. Itreacts with oxygen and halogens at high temperatures. It also formscomplexes with a range of oxidationstates. The element was isolated byK. K. Klaus in 1844.
This product has been enhanced for energy efficiency.
The main hazard is the explosiveness of ruthenium fine power or dust. The metal willrapidly oxidize (explode) when exposed to oxidizer-type chemicals such as potassium chlorideat room temperature. Most of its few compounds are toxic and their fumes should beavoided.
Flammability and Explosibility
Not classified
Pharmaceutical Applications
Ruthenium is the chemical element with the symbol Ru and atomic number 44. It occurs as a minor side
product in the mining of platinum. Ruthenium is relatively inert to most chemicals. Its main applications are
in the area of specialised electrical parts.
The success of cisplatin, together with the occurrence of dose-limiting resistances and severe side effects
such as nausea and nephrotoxicity, encouraged the research into other metal-based anticancer agents. Ruthenium
is one of those metals under intense research, and first results look very promising, with two candidates
– NAMI-A and KP1019 – having entered clinical trials.
Most ruthenium compounds are poisons. Ruthenium is retained in the bones for a long time. Flammable in the form of dust when exposed to heat or flame. Violent reaction with ruthenium oxide. Explosive reaction with aqua rega + potassium chlorate. When heated to decomposition it emits very toxic fumes of RuO, and Ru, which are hghly injurious to the eyes and lung and can
produce nasal ulcerations. See also RUTHENIUM COMPOUNDS.