Ruthenium

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44 technetiumRutheniumrhodium
Fe

Ru

Os
Periodic Table - Extended Periodic Table
General
Name, Symbol, Number Ruthenium, Ru, 44
Chemical series transition metals
Group, Period, Block 8, 5, d
Appearance silvery white metallic
Standard atomic weight 101.07(2)  g·mol−1
Electron configuration [Kr] 4d7 5s1
Electrons per shell 2, 8, 18, 15, 1
Physical properties
Density (near r.t.) 12.45  g·cm−3
Liquid density at m.p. 10.65  g·cm−3
Melting point 2607 K
(2334 °C, 4233 °F)
Boiling point 4423 K
(4150 °C, 7502 °F)
Heat of fusion 38.59  kJ·mol−1
Heat of vaporization 591.6  kJ·mol−1
Heat capacity (25 °C) 24.06  J·mol−1·K−1
Vapor pressure
P(Pa) 1 10 100 1 k 10 k 100 k
at T(K) 2588 2811 3087 3424 3845 4388
Atomic properties
Crystal structure hexagonal
Oxidation states 2, 3, 4, 6, 8
(mildly acidic oxide)
Electronegativity 2.2 (scale Pauling)
Ionization energies 1st: 710.2 kJ/mol
2nd: 1620 kJ/mol
3rd: 2747 kJ/mol
Atomic radius 130  pm
Atomic radius (calc.) 178  pm
Covalent radius 126  pm
Miscellaneous
Electrical resistivity (0 °C) 71 nΩ·m
Thermal conductivity (300 K) 117  W·m−1·K−1
Thermal expansion (25 °C) 6.4  µm·m−1·K−1
Speed of sound (thin rod) (20 °C) 5970 m/s
Young's modulus 447  GPa
Shear modulus 173  GPa
Bulk modulus 220  GPa
Poisson ratio 0.30
Mohs hardness 6.5
Brinell hardness 2160  MPa
CAS registry number 7440-18-8
Selected isotopes
Main article: Isotopes of ruthenium
iso NA half-life DM DE (MeV) DP
96Ru 5.52% Ru is stable with 52 neutrons
97Ru syn 2.9 d ε - 97Tc
γ 0.215, 0.324 -
98Ru 1.88% Ru is stable with 54 neutrons
99Ru 12.7% Ru is stable with 55 neutrons
100Ru 12.6% Ru is stable with 56 neutrons
101Ru 17.0% Ru is stable with 57 neutrons
102Ru 31.6% Ru is stable with 58 neutrons
103Ru syn 39.26 d β- 0.226 103Rh
γ 0.497 -
104Ru 18.7% Ru is stable with 60 neutrons
106Ru syn 373.59 d β- 0.039 106Rh
References

Ruthenium (IPA: /ruːˈθiːniəm/) is a chemical element that has the symbol Ru and atomic number 44. A rare transition metal of the platinum group of the periodic table, ruthenium is found associated with platinum ores and used as a catalyst in some platinum alloys.

Contents

  • 1 Notable characteristics
  • 2 Applications
  • 3 History
  • 4 Occurrence
    • 4.1 Normal mining
    • 4.2 From used nuclear fuels
  • 5 Compounds
  • 6 Isotopes
  • 7 Organometallic chemistry
  • 8 Precautions
  • 9 References
  • 10 External links

[edit] Notable characteristics

A polyvalent hard white metal, ruthenium is a member of the platinum group, has four crystal modifications and does not tarnish at normal temperatures, but does oxidize explosively. Ruthenium dissolves in fused alkalis, is not attacked by acids but is attacked by halogens at high temperatures. Small amounts of ruthenium can increase the hardness of platinum and palladium. The corrosion resistance of titanium is increased markedly by the addition of a small amount of ruthenium.

This metal can be plated either through electrodeposition or by thermal decomposition methods. One ruthenium-molybdenum alloy has been found to be superconductive at 10.6 K. The oxidation states of ruthenium range from +1 to +8, and -2 is known, though oxidation states of +2, +3, and +4 are most common.

[edit] Applications

Due to its highly effective ability to harden platinum and palladium, ruthenium is used in Pt and Pd alloys to make severe wear-resistant electrical contacts. It is sometimes alloyed with gold in jewelry.

0.1% ruthenium is added to titanium to improve its corrosion resistance a hundredfold.

Ruthenium will also be used in some advanced high-temperature single-crystal superalloys, with applications including the turbine blades in jet engines.

Fountain pen nibs are frequently tipped with alloys containing ruthenium. From 1944 onward, the famous Parker 51 fountain pen was outfitted with the "RU" nib, a 14K gold nib tipped with 96.2% ruthenium, and 3.8% iridium.

Ruthenium is also a versatile catalyst: hydrogen sulfide can be split by light by using an aqueous suspension of CdS particles loaded with ruthenium dioxide. This may be useful in the removal of H2S from oil refineries and from other industrial processes.

Ruthenium is a component of mixed-metal oxide (MMO) anodes used for cathodic protection of underground and submerged structures, and for electrolytic cells for chemical processes such as generating chlorine from saltwater.

Organometallic ruthenium carbene and allenylidene complexes have recently been found as highly efficient catalysts for olefin metathesis with important applications in organic and pharmaceutical chemistry.

Some ruthenium complexes absorb light throughout the visible spectrum and are being actively researched in various, potential, solar energy technologies.

The fluorescence of some ruthenium complexes is quenched by oxygen, which has led to their use as optode sensors for oxygen.

Ruthenium red, [(NH3)5Ru-O-Ru(NH3)4-O-Ru(NH3)5]6+, is a biological stain used to visualize polyanionic areas of membranes.

Ruthenium-centered complexes are being researched for possible anticancer properties. Ruthenium, unlike traditional platinum complexes, show greater resistance to hydrolysis and more selective action on tumors. NAMI-A and KP1019 are two drugs undergoing clinical evaluation against metastatic tumors and colon cancers.

[edit] History

Ruthenium was discovered and isolated by Russian scientist Karl Klaus in 1844. Klaus showed that ruthenium oxide contained a new metal and obtained 6 grams of ruthenium from the part of crude platinum that is insoluble in aqua regia.

Jöns Berzelius and Gottfried Osann nearly discovered ruthenium in 1827. The men examined residues that were left after dissolving crude platinum from the Ural Mountains in aqua regia. Berzelius did not find any unusual metals, but Osann thought he found three new metals and named one of them ruthenium.

The name derives from Ruthenia, the Latin word for Rus', a historical area which includes present-day Ukraine, Belarus, and parts of Russia, the Baltics, Slovakia, and Poland. Karl Klaus named the element in honour of his birthland, as he was born in Tartu, Estonia, which was at the time a part of the Russian Empire.

It is also possible that Polish chemist Jędrzej Śniadecki isolated element 44 (which he called vestium) from platinum ores in 1807. However his work was never confirmed, and he later withdrew his claim of discovery.

[edit] Occurrence

[edit] Normal mining

This element is generally found in ores with the other platinum group metals in the Ural Mountains and in North and South America. Small but commercially important quantities are also found in pentlandite extracted from Sudbury, Ontario, Canada, and in pyroxenite deposits in South Africa.

This metal is commercially isolated through a complex chemical process in which hydrogen is used to reduce ammonium ruthenium chloride yielding a powder. The powder is then consolidated by powder metallurgy techniques or by argon-arc welding.

[edit] From used nuclear fuels

It is also possible to extract ruthenium from used nuclear fuel. Each kilo of fission products of 235U will contain 63.44 grams of ruthenium isotopes with halflives longer than a day. Since a typical used nuclear fuel contains about 3% fission products, one ton of used fuel will contain about 1.9 kg of ruthenium. The 103Ru and 106Ru will render the fission ruthenium very radioactive. If the fission occurs in an instant then the ruthenium thus formed will have an activity due to 103Ru of 109 TBq g-1 and 106Ru of 1.52 TBq g-1.

The radioactivity in MBq per gram of each of the platinum group metals which are formed by the fission of uranium. Of the metals shown, ruthenium is the most radioactive. Palladium has an almost constant activity due to the very long lived 107Pd while rhodium is the least radioactive

See also Ruthenium minerals.

[edit] Compounds

Ruthenium compounds are often similar in properties to those of osmium and exhibit at least eight oxidation states, but the +2, +3, and +4 states are the most common. Examples are ruthenium(IV) oxide (Ru(IV)O2, oxidation state +4), dipotassium ruthenate (K2Ru(VI)O4, +6), potassium perruthenate (KRu(VII)O4, +7) and ruthenium tetroxide (Ru(VIII)O4, +8). Compounds of ruthenium with chlorine are ruthenium(II) chloride (RuCl2) and ruthenium(III) chloride (RuCl3).

See also Ruthenium compounds.

[edit] Isotopes

Main article: isotopes of ruthenium

Naturally occurring ruthenium is composed of seven isotopes. The most stable radioisotopes are 106Ru with a half-life of 373.59 days, 103Ru with a half-life of 39.26 days and 97Ru with a half-life of 2.9 days.

Fifteen other radioisotopes have been characterized with atomic weights ranging from 89.93 u (90Ru) to 114.928 u (115Ru). Most of these have half-lives that are less than five minutes except 95Ru (half-life: 1.643 hours) and 105Ru (half-life: 4.44 hours).

The primary decay mode before the most abundant isotope, 102Ru, is electron capture and the primary mode after is beta emission. The primary decay product before 102Ru is technetium and the primary mode after is rhodium.

[edit] Organometallic chemistry

It is quite easy to form compounds with carbon ruthenium bonds, as these compounds tend to be darker and react more quickly than the osmium compounds. Recently, Professor Anthony Hill and his co-workers have been making compounds of ruthenium in which a boron atom binds to the metal atom[1].

The organometallic ruthenium compound that is easiest to make is RuHCl(CO)(PPh3)3. This compound has two forms (yellow and pink) that are identical once they are dissolved but different in the solid state.

An organometallic compound similar to ruthenocene, bis(2,4-dimethylpentadienyl)ruthenium, is readily synthesized in near quantitative yields and has applications in vapor-phase deposition of metallic ruthenium, as well as in catalysis, including Fischer-Tropsch synthesis of transportation fuels.

Important catalysts based on ruthenium are Grubbs' catalyst and Roper's complex.

[edit] Precautions

The compound ruthenium tetroxide, RuO4, similar to osmium tetroxide, is highly toxic[citation needed] and may explode. Ruthenium plays no biological role but does strongly stain human skin, may be carcinogenic[citation needed] and bio-accumulates in bone.