Gallium

Gallium (pronounced /ˈɡæliəm/) is a chemical element that has the symbol Ga and
atomic number 31. Elemental gallium does not occur in nature, but as the Ga (III)
salt, in trace amounts in bauxite and zinc ores. A soft silvery metallic poor metal,
elemental gallium is a brittle solid at low temperatures. As it liquefies slightly above
room temperature, it will melt in the hand. Its melting point is used as a temperature
reference point, and from its discovery in 1875 to the semiconductor era, its primary
uses were in high-temperature thermometric applications and in preparation of metal
alloys with unusual properties of stability, or ease of melting; some being liquid at
room temperature (Ga-In eutectic, 75% Ga, 25% In, mp = 15.5°C).

In semiconductors, an important application is in the compounds gallium nitride and

gallium arsenide, used most notably in light-emitting diodes (LEDs). Semiconductor
use is now the primary industrial market for gallium, but new uses in alloys and fuel
cells continue to be discovered.

Gallium is not known to be essential in biology, but because of the biological

handling of gallium’s primary ionic salt Ga(III) as though it were iron(III), gallium ion
localizes to and interacts with many processes in the body in which iron(III) is
manipulated. As these processes include inflammation, which is present as a marker
for many disease states, several gallium salts are used, or are in development, as
both pharmaceuticals and radiopharmaceuticals in medicine.

Notable characteristics

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 silicon, germanium, bismuth, antimony 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 or steel , making them
very brittle. Also, gallium metal easily alloys with many metals, and was used in
small quantities in the core of the first atomic bomb to help stabilize the plutonium
crystal structure.

The melting point of 302.9146 K (29.7646°C, 85.5763°F) is near room temperature.

Gallium's melting point (mp) is one of the formal temperature reference points in the
International Temperature Scale of 1990 (ITS-90) established by BIPM.The triple
point of gallium of 302.9166 K (29.7666°C, 85.5799°F), is being used by NIST in
preference to gallium's melting point.
Gallium is a metal that will melt in one's hand. This metal has a strong tendency to
supercool below its melting point/freezing point. Seeding with a crystal helps to
initiate freezing. 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 dissolved slowly by mineral acids.

Gallium has no known biological role, although it has been observed to stimulate
metabolism.

History

Gallium (the Latin Gallia means "Gaul," essentially modern France) 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 had called the hypothetical element "eka-aluminium" on the basis
of its position in his periodic table). Later, in 1875, Boisbaudran obtained the free
metal by electrolysis of its hydroxide in potassium hydroxide 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 in the early 19th century, he
had also named gallium after himself, as his name, "Le coq," is the French for "the
rooster," and the Latin for "rooster" is "gallus"; however, in an 1877 article Le coq
denied this supposition. (The supposition was also noted in Building Blocks of the
Universe, a book on the elements by Isaac Asimov.)
Occurrence

Gallium does not exist in free form in nature, and the few high-gallium minerals such
as gallite (CuGaS2) are too rare to serve as a primary source of the element or its
compounds. Its abundance in the Earth's crust is approximately 16.9 ppm. Gallium
is found and extracted as a trace component in bauxite and to a small extent from
sphalerite. The amount extracted from coal, diaspore and germanite in which
gallium is also present is negligible. The United States Geological Survey (USGS)
estimates gallium reserves to exceed 1 million tonnes, 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 small quantities of gallium, typically less
than 1% by weight.

Production

The only two economic sources for gallium are as byproduct of aluminium and zinc
production, while the sphalerite for zinc production is the minor source. Most gallium
is extracted from the crude aluminium hydroxide solution of the Bayer process for
producing alumina and aluminium. 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. An exact
number for the world wide production is not available, but it is estimated that in 2007
the production of gallium was 184 tonnes with less than 100 tonnes from mining and
the rest from scrap recycling.

Applications

Gallium arsenide (GaAs) and gallium nitride (GaN) used in electronic components
represented about 98% of the gallium consumption in the United States.World wide
gallium arsenide makes up 95% of the annual global gallium consumption.