Gallium

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31 zincgalliumgermanium
Al

Ga

In
General
Name, Symbol, Number gallium, Ga, 31
Chemical series poor metals
Group, Period, Block 13, 4, p
Appearance silvery white
Typical (melted blob) Crystallized
Atomic mass 69.723(1)  g·mol−1
Electron configuration [Ar] 3d10 4s2 4p1
Electrons per shell 2, 8, 18, 3
Physical properties
Phase solid
Density (near r.t.) 5.91  g·cm−3
Liquid density at m.p. 6.095  g·cm−3
Melting point 302.9146 K
(29.7646 °C, 85.5763 °F)
Boiling point 2477 K
(2204 °C, 3999 °F)
Heat of fusion 5.59  kJ·mol−1
Heat of vaporization 254  kJ·mol−1
Heat capacity (25 °C) 25.86  J·mol−1·K−1
Vapor pressure
P(Pa) 1 10 100 1 k 10 k 100 k
at T(K) 1310 1448 1620 1838 2125 2518
Atomic properties
Crystal structure orthorhombic
Oxidation states 3, 1
(amphoteric oxide)
Electronegativity 1.81 (Pauling scale)
Ionization energies
(more)
1st:  578.8  kJ·mol−1
2nd:  1979.3  kJ·mol−1
3rd:  2963  kJ·mol−1
Atomic radius 130pm
Atomic radius (calc.) 136  pm
Covalent radius 126  pm
Van der Waals radius 187 pm
Miscellaneous
Magnetic ordering no data
Thermal conductivity (300 K) 40.6  W·m−1·K−1
Speed of sound (thin rod) (20 °C) 2740 m/s
Mohs hardness 1.5
Brinell hardness 60  MPa
CAS registry number 7440-55-3
Selected isotopes
Main article: Isotopes of gallium
iso NA half-life DM DE (MeV) DP
69Ga 60.11% Ga is stable with 38 neutrons
71Ga 39.89% Ga is stable with 40 neutrons
References

Gallium (IPA: /ˈgaliəm/) is a chemical element that has the symbol Ga and atomic number 31. A soft silvery metallic poor metal, gallium is a brittle solid at low temperatures but liquefies slightly above room temperature and will melt in the hand. It occurs in trace amounts in bauxite and zinc ores. An important application is in the compounds gallium nitride and gallium arsenide, used as a semiconductor, most notably in light-emitting diodes (LEDs).

Contents

Elemental gallium is not found in nature, but it is easily obtained by smelting. Very pure gallium metal has a brilliant silvery color and its solid metal fractures conchoidally like glass. Gallium metal expands by 3.1 percent when it solidifies, and therefore storage in either glass or metal containers is avoided, due to the possibility of container rupture with freezing. Gallium shares the higher-density liquid state with only a few materials like germanium, bismuth and water.

Gallium also attacks most other metals by diffusing into their metal lattice. Gallium for example diffuses into the grain boundaries of Al/Zn alloys.[1] or steel.[2]Gallium metal easily alloys with many metals,[citation needed] and was used in small quantities in the core of the first atomic bomb to help stabilize the plutonium crystal structure.[citation needed]

The melting point temperature of 30 °C allows the metal to be melted in one's hand. This metal has a strong tendency to supercool below its melting point/freezing point, thus necessitating seeding in order to solidify. Gallium is one of the metals (with caesium, rubidium, francium and mercury) which are liquid at or near normal room temperature, and can therefore be used in metal-in-glass high-temperature thermometers. It is also notable for having one of the largest liquid ranges for a metal, and (unlike mercury) for having a low vapor pressure at high temperatures. Unlike mercury, liquid gallium metal wets glass and skin, making it mechanically more difficult to handle (even though it is substantially less toxic and requires far fewer precautions). For this reason as well as the metal contamination problem and freezing-expansion problems noted above, samples of gallium metal are usually supplied in polyethylene packets within other containers.

Gallium does not crystallize in any of the simple crystal structures. The stable phase under normal conditions is orthorhombic with 8 atoms in the conventional unit cell. Each atom has only one nearest neighbor (at a distance of 244 pm) and six other neighbors within additional 39 pm. Many stable and metastable phases are found as function of temperature and pressure.

The bonding between the nearest neighbors is found to be of covalent character, hence Ga2 dimers are seen as the fundamental building blocks of the crystal. The compound with arsenic, gallium arsenide is a semiconductor commonly used in light-emitting diodes.

High-purity gallium is attacked slowly by mineral acids.

Gallium (Latin Gallia meaning Gaul (essentially modern France); also gallus, meaning "rooster") was discovered spectroscopically by Lecoq de Boisbaudran in 1875 by its characteristic spectrum (two violet lines) in an examination of a zinc blende from the Pyrenees. Before its discovery, most of its properties had been predicted and described by Dmitri Mendeleev (who called the hypothetical element eka-aluminium) on the basis of its position in his periodic table. Later, in 1875, Boisbaudran obtained the free metal through the electrolysis of its hydroxide in KOH solution. He named the element "gallia" after his native land of France. It was later claimed that, in one of those multilingual puns so beloved of men of science of the early 19th century, he also named it after himself, as 'Lecoq' = the rooster, and Latin for rooster is "gallus"; however, he denied this in an 1877 article.

Gallium does not exist in free form in nature, nor do any high-gallium minerals exist to serve as a primary source of extraction of the element or its compounds. Gallium is found and extracted as a trace component in bauxite, coal, diaspore, germanite, and sphalerite. The United States Geological Survey (USGC) estimates gallium reserves based on 50 ppm by weight concentration in known reserves of bauxite and zinc ores. Some flue dusts from burning coal have been shown to contain as much as 1.5 percent gallium.

Most gallium is extracted from the crude aluminium hydroxide solution of the Bayer process for producing alumina and aluminum. A mercury cell electrolysis and hydrolysis of the amalgam with sodium hydroxide leads to sodium gallate. Electrolysis then gives gallium metal. For semiconductor use, further purification is carried out using zone melting, or else single crystal extraction from a melt (Czochralski process). Purities of 99.9999% are routinely achieved and commercially widely available.

As of 2006, the current price for 1 kg gallium of 99.9999% purity seems to be at about 400 US$.

Semiconductor and electronic industry. The semiconductor applications are the main reason for the low-cost commercial availability of the extremely high-purity (99.9999+%) metal:

As a wetting, and alloy improvement agent:

For liquid alloys:

  • It has been suggested that a liquid gallium-tin alloy could be used to cool computer chips in place of water. As it conducts heat approximately 65 times better than water it can make a comparable coolant. [1] Gallium has a specific heat capacity of 0.37 J/(g·K). Gallium's high specific gravity of 5.91 gives it a volumetric heat capacity of 0.37 x 5.91 = 2.187 J/cm³, meaning that a volume of gallium will heat by 4.184/2.187 = 1.9 times more than an equal volume of water in a cooling device. However given water's benign handling characteristics and plentiful abundance in most developed countries, gallium alloys are only really likely to see use in specialised applications such as cooling supercomputers.
  • Gallium is used in some high temperature thermometers.

Biomedical applications:

  • A low temperature liquid eutectic alloy of gallium, indium, and tin, is widely available in medical thermometers (fever thermometers), replacing problematic mercury. This alloy, with the trade name Galinstan (with the "-stan" referring to the tin), has a freezing point of −20 °C.
  • Gallium salts such as gallium citrate and gallium nitrate are used as radiopharmaceutical agents in nuclear medicine imaging. (The form or salt is not important, since it is the free dissolved gallium ion Ga+3 which is active). For these applications, a radioactive isotope such as 67Ga is used. The body handles Ga+3 in many ways as though it were iron, and thus it is bound (and concentrates) in areas of inflammation, such as infection, and also areas of rapid cell division. This allows such sites to be imaged by nuclear scan techniques. See gallium scan. This use has largely been replaced by FDG Positron emission tomography, "PET" scan.
  • Gallium nitrate, both oral and topical, is finding use in treating arthritis.[2]
  • Much research is being devoted to gallium alloys as substitutes for mercury dental amalgams, but these compounds have yet to see wide acceptance.
  • Research is being conducted to determine whether gallium can be used to fight becterial infections in people with cystic fibrosis. Gallium is similar in size to iron, an essential nutrient for respiration. When gallium is mistakenly picked up by bacteria such as Pseudomonas, the bacteria's ability to respire is interferred with and the bacteria die. The mechanism behind this is that iron is redox active, which allows for the transfer of electrons during respiration, but gallium is redox inactive. [3]New Link on this research: http://www.medpagetoday.com/InfectiousDisease/GeneralInfectiousDisease/tb/5266


Miscellaneous:

  • Magnesium gallate containing impurities (such as Mn+2), is beginning to be used in ultraviolet-activated phosphor powder.
  • Neutrino detection. Possibly the largest amount of pure gallium ever collected in a single spot was the GALLEX neutrino detector operated in the early 1990's in an Italian mountain tunnel. The detector contained 12.2 tons of watered gallium-71. Solar neutrinos caused a few atoms of Ga-71 to become radioactive Ge-71, which were detected. The solar neutrino flux deduced was found to have a deficit of 40% from theory. This was not explained until better solar neutrino detectors and theories were constructed (see SNO)[3]

While not considered toxic, the data about gallium is inconclusive. Some sources suggest that it may cause dermatitis from prolonged exposure; other tests have not caused a positive reaction. Like most metals, finely divided gallium loses its luster. Powdered gallium appears gray. When gallium is handled with bare hands, the extremely fine dispersion of liquid gallium droplets which results from wetting skin with the metal may appear as a gray skin stain.

  1. ^ W. L. Tsai, Y. Hwu, C. H. Chen, L. W. Chang, J. H. Je, H. M. Lin, G. Margaritondo (2003). "Grain boundary imaging, gallium diffusion and the fracture behavior of Al–Zn Alloy – An in situ study". Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 199: 457-463. DOI:10.1016/S0168-583X(02)01533-1. 
  2. ^ Liquid Metal Embrittlement of ASTM A723 Gun Steel by Indium and Gallium, VIGILANTE, GREGORY N. ; TROlANO, EDWARD ; MOSSEY, CHARLES
  3. ^ A Trojan-horse strategy selected to fight bacteria

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