Gallium Indium Arsenide Nitride
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Gallium is a chemical element with the
symbol A symbol is a mark, sign, or word that indicates, signifies, or is understood as representing an idea, object, or relationship. Symbols allow people to go beyond what is known or seen by creating linkages between otherwise very different conc ...
Ga and atomic number 31. Discovered by
French French (french: français(e), link=no) may refer to: * Something of, from, or related to France ** French language, which originated in France, and its various dialects and accents ** French people, a nation and ethnic group identified with Franc ...
chemist Paul-Émile Lecoq de Boisbaudran in 1875, Gallium is in
group 13 The Group 13 network ( pl, Trzynastka, Yiddish: ''דאָס דרײַצענטל'') was a Jewish Nazi collaborationist organization in the Warsaw Ghetto during the German occupation of Poland in World War II. The rise and fall of the Group ...
of the periodic table and is similar to the other metals of the group ( aluminium, indium, and thallium). Elemental gallium is a soft, silvery metal in
standard temperature and pressure Standard temperature and pressure (STP) are standard sets of conditions for experimental measurements to be established to allow comparisons to be made between different sets of data. The most used standards are those of the International Union o ...
. In its liquid state, it becomes silvery white. If too much force is applied, the gallium may fracture conchoidally. Since its discovery in 1875, gallium has widely been used to make alloys with low melting points. It is also used in semiconductors, as a dopant in semiconductor substrates. The melting point of gallium is used as a temperature reference point. Gallium alloys are used in thermometers as a non-toxic and
environmentally friendly Environment friendly processes, or environmental-friendly processes (also referred to as eco-friendly, nature-friendly, and green), are sustainability and marketing terms referring to goods and services, laws, guidelines and policies that clai ...
alternative to mercury, and can withstand higher temperatures than mercury. An even lower melting point of , well below the freezing point of water, is claimed for the alloy
galinstan Galinstan (R) is a brand name for a alloy composed of gallium, indium, and tin which melts at and is thus liquid at room temperature. However, it is not a eutectic alloy but a near eutectic alloy. In scientific literature, galinstan is also used ...
(62–⁠95% gallium, 5–⁠22% indium, and 0–⁠16% tin by weight), but that may be the freezing point with the effect of supercooling. Gallium does not occur as a free element in nature, but as gallium(III) compounds in trace amounts in zinc ores (such as
sphalerite Sphalerite (sometimes spelled sphaelerite) is a sulfide mineral with the chemical formula . It is the most important ore of zinc. Sphalerite is found in a variety of deposit types, but it is primarily in Sedimentary exhalative deposits, sedimen ...
) and in bauxite. Elemental gallium is a liquid at temperatures greater than , and will melt in a person's hands at normal human body temperature of . Gallium is predominantly used in electronics.
Gallium arsenide Gallium arsenide (GaAs) is a III-V direct band gap semiconductor with a Zincblende (crystal structure), zinc blende crystal structure. Gallium arsenide is used in the manufacture of devices such as microwave frequency integrated circuits, monoli ...
, the primary chemical compound of gallium in electronics, is used in microwave circuits, high-speed switching circuits, and infrared circuits. Semiconducting gallium nitride and indium gallium nitride produce blue and violet light-emitting diodes and diode lasers. Gallium is also used in the production of artificial
gadolinium gallium garnet Gadolinium Gallium Garnet (GGG, ) is a synthetic crystalline material of the garnet group, with good mechanical, thermal, and optical properties. It is typically colorless. It has a cubic lattice, a density of 7.08 g/cm3 and its Mohs hardness is v ...
for jewelry. Gallium is considered a technology-critical element by the United States National Library of Medicine and
Frontiers Media Frontiers Media SA is a publisher of peer-reviewed, open access, scientific journals currently active in science, technology, and medicine. It was founded in 2007 by Kamila and Henry Markram, and has since expanded to other academic fields. Fro ...
. Gallium has no known natural role in biology. Gallium(III) behaves in a similar manner to ferric salts in biological systems and has been used in some medical applications, including pharmaceuticals and radiopharmaceuticals.


Physical properties

Elemental gallium is not found in nature, but it is easily obtained by smelting. Very pure gallium is a silvery blue metal that fractures conchoidally like glass. Gallium liquid expands by 3.10% when it solidifies; therefore, it should not be stored in glass or metal containers because the container may rupture when the gallium changes state. Gallium shares the higher-density liquid state with a short list of other materials that includes water, silicon,
germanium Germanium is a chemical element with the symbol Ge and atomic number 32. It is lustrous, hard-brittle, grayish-white and similar in appearance to silicon. It is a metalloid in the carbon group that is chemically similar to its group neighbors s ...
, bismuth, and plutonium.Greenwood and Earnshaw, p. 222 Gallium forms alloys with most metals. It readily diffuses into cracks or grain boundaries of some metals such as aluminium, aluminiumzinc alloys and
steel Steel is an alloy made up of iron with added carbon to improve its strength and fracture resistance compared to other forms of iron. Many other elements may be present or added. Stainless steels that are corrosion- and oxidation-resistant ty ...
, causing extreme loss of strength and ductility called liquid metal embrittlement. The melting point of gallium, at 302.9146 K (29.7646 °C, 85.5763 °F), is just above room temperature, and is approximately the same as the average summer daytime temperatures in Earth's mid-latitudes. This melting point (mp) is one of the formal temperature reference points in the
International Temperature Scale of 1990 The International Temperature Scale of 1990 (ITS-90) is an equipment calibration standard specified by the International Committee of Weights and Measures (CIPM) for making measurements on the Kelvin and Celsius temperature scales. It is an appro ...
(ITS-90) established by the International Bureau of Weights and Measures (BIPM). The triple point of gallium, 302.9166 K (29.7666 °C, 85.5799 °F), is used by the US National Institute of Standards and Technology (NIST) in preference to the melting point. The melting point of gallium allows it to melt in the human hand, and then solidify if removed. The liquid metal has a strong tendency to
supercool Supercooling, also known as undercooling, is the process of lowering the temperature of a liquid or a gas below its melting point without it becoming a solid. It achieves this in the absence of a seed crystal or nucleus around which a crystal ...
below its melting point/ freezing point: Ga nanoparticles can be kept in the liquid state below 90 K. Seeding with a crystal helps to initiate freezing. Gallium is one of the four non-radioactive metals (with
caesium Caesium (IUPAC spelling) (or cesium in American English) is a chemical element with the symbol Cs and atomic number 55. It is a soft, silvery-golden alkali metal with a melting point of , which makes it one of only five elemental metals that a ...
,
rubidium Rubidium is the chemical element with the symbol Rb and atomic number 37. It is a very soft, whitish-grey solid in the alkali metal group, similar to potassium and caesium. Rubidium is the first alkali metal in the group to have a density higher ...
, and
mercury Mercury commonly refers to: * Mercury (planet), the nearest planet to the Sun * Mercury (element), a metallic chemical element with the symbol Hg * Mercury (mythology), a Roman god Mercury or The Mercury may also refer to: Companies * Merc ...
) that are known to be liquid at, or near, normal room temperature. Of the four, gallium is the only one that is neither highly reactive (as are rubidium and caesium) nor highly toxic (as is mercury) 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 for having (unlike mercury) a low vapor pressure at high temperatures. Gallium's boiling point, 2673 K, is nearly nine times higher than its melting point on the absolute scale, the greatest ratio between melting point and boiling point of any element.Greenwood and Earnshaw, p. 224 Unlike mercury, liquid gallium metal wets glass and skin, along with most other materials (with the exceptions of quartz, graphite, gallium(III) oxide and
PTFE Polytetrafluoroethylene (PTFE) is a synthetic fluoropolymer of tetrafluoroethylene that has numerous applications. It is one of the best-known and widely applied PFAS. The commonly known brand name of PTFE-based composition is Teflon by Chemour ...
),Greenwood and Earnshaw, p. 221 making it mechanically more difficult to handle even though it is substantially less toxic and requires far fewer precautions than mercury. Gallium painted onto glass is a brilliant mirror. For this reason as well as the metal contamination and freezing-expansion problems, 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 In crystallography, the orthorhombic crystal system is one of the 7 crystal systems. Orthorhombic lattices result from stretching a cubic lattice along two of its orthogonal pairs by two different factors, resulting in a rectangular prism with a r ...
with 8 atoms in the conventional unit cell. Within a unit cell, each atom has only one nearest neighbor (at a distance of 244  pm). The remaining six unit cell neighbors are spaced 27, 30 and 39 pm farther away, and they are grouped in pairs with the same distance. Many stable and metastable phases are found as function of temperature and pressure. The bonding between the two nearest neighbors is covalent; hence Ga2 dimers are seen as the fundamental building blocks of the crystal. This explains the low melting point relative to the neighbor elements, aluminium and indium. This structure is strikingly similar to that of
iodine Iodine is a chemical element with the symbol I and atomic number 53. The heaviest of the stable halogens, it exists as a semi-lustrous, non-metallic solid at standard conditions that melts to form a deep violet liquid at , and boils to a vi ...
and may form because of interactions between the single 4p electrons of gallium atoms, further away from the nucleus than the 4s electrons and the rd10 core. This phenomenon recurs with
mercury Mercury commonly refers to: * Mercury (planet), the nearest planet to the Sun * Mercury (element), a metallic chemical element with the symbol Hg * Mercury (mythology), a Roman god Mercury or The Mercury may also refer to: Companies * Merc ...
with its "pseudo-noble-gas" ef145d106s2 electron configuration, which is liquid at room temperature.Greenwood and Earnshaw, p. 223 The 3d10 electrons do not shield the outer electrons very well from the nucleus and hence the first ionisation energy of gallium is greater than that of aluminium. Ga2 dimers do not persist in the liquid state and liquid gallium exhibits a complex low-coordinated structure in which each gallium atom is surrounded by 10 others, rather than 11–12 neighbors typical of most liquid metals. The physical properties of gallium are highly
anisotropic Anisotropy () is the property of a material which allows it to change or assume different properties in different directions, as opposed to isotropy. It can be defined as a difference, when measured along different axes, in a material's physic ...
, i.e. have different values along the three major crystallographic axes ''a'', ''b'', and ''c'' (see table), producing a significant difference between the linear (α) and volume thermal expansion coefficients. The properties of gallium are strongly temperature-dependent, particularly near the melting point. For example, the coefficient of thermal expansion increases by several hundred percent upon melting.


Isotopes

Gallium has 31 known isotopes, ranging in mass number from 56 to 86. Only two isotopes are stable and occur naturally, gallium-69 and gallium-71. Gallium-69 is more abundant: it makes up about 60.1% of natural gallium, while gallium-71 makes up the remaining 39.9%. All the other isotopes are radioactive, with gallium-67 being the longest-lived (half-life 3.261 days). Isotopes lighter than gallium-69 usually decay through
beta plus decay Positron emission, beta plus decay, or β+ decay is a subtype of radioactive decay called beta decay, in which a proton inside a radionuclide nucleus is converted into a neutron while releasing a positron and an electron neutrino (). Positron emis ...
(positron emission) or electron capture to isotopes of zinc, although the lightest few (mass numbers 56–59) decay through prompt proton emission. Isotopes heavier than gallium-71 decay through beta minus decay (electron emission), possibly with delayed neutron emission, to isotopes of
germanium Germanium is a chemical element with the symbol Ge and atomic number 32. It is lustrous, hard-brittle, grayish-white and similar in appearance to silicon. It is a metalloid in the carbon group that is chemically similar to its group neighbors s ...
, while gallium-70 can decay through both beta minus decay and electron capture. Gallium-67 is unique among the light isotopes in having only electron capture as a decay mode, as its decay energy is not sufficient to allow positron emission. Gallium-67 and gallium-68 (half-life 67.7 min) are both used in nuclear medicine.


Chemical properties

Gallium is found primarily in the +3 oxidation state. The +1 oxidation state is also found in some compounds, although it is less common than it is for gallium's heavier congeners indium and thallium. For example, the very stable GaCl2 contains both gallium(I) and gallium(III) and can be formulated as GaIGaIIICl4; in contrast, the monochloride is unstable above 0 °C,
disproportionating In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. More generally, the term can b ...
into elemental gallium and gallium(III) chloride. Compounds containing Ga–Ga bonds are true gallium(II) compounds, such as GaS (which can be formulated as Ga24+(S2−)2) and the
dioxan 1,4-Dioxane () is a Heterocyclic compound, heterocyclic organic compound, classified as an ether. It is a colorless liquid with a faint sweet odor similar to that of diethyl ether. The compound is often called simply dioxane because the other ...
complex Ga2Cl4(C4H8O2)2.Greenwood and Earnshaw, p. 240


Aqueous chemistry

Strong acids dissolve gallium, forming gallium(III) salts such as (gallium nitrate). Aqueous solutions of gallium(III) salts contain the hydrated gallium ion, . Gallium(III) hydroxide, , may be precipitated from gallium(III) solutions by adding ammonia. Dehydrating at 100 °C produces gallium oxide hydroxide, GaO(OH). Alkaline hydroxide solutions dissolve gallium, forming ''gallate'' salts (not to be confused with identically named gallic acid salts) containing the anion. Gallium hydroxide, which is amphoteric, also dissolves in alkali to form gallate salts. Although earlier work suggested as another possible gallate anion, it was not found in later work.


Oxides and chalcogenides

Gallium reacts with the chalcogens only at relatively high temperatures. At room temperature, gallium metal is not reactive with air and water because it forms a passive, protective
oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of −2. Most of the E ...
layer. At higher temperatures, however, it reacts with atmospheric oxygen to form gallium(III) oxide, . Reducing with elemental gallium in vacuum at 500 °C to 700 °C yields the dark brown gallium(I) oxide, . is a very strong reducing agent, capable of reducing to . It disproportionates at 800 °C back to gallium and .
Gallium(III) sulfide Gallium(III) sulfide, Ga2S3, is a compound of sulfur and gallium, that is a semiconductor that has applications in electronics and photonics. Structure There are four polymorphs, α (hexagonal), α' (monoclinic), β(hexagonal) and γ(cubic). Th ...
, , has 3 possible crystal modifications. It can be made by the reaction of gallium with
hydrogen sulfide Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. The unde ...
() at 950 °C. Alternatively, can be used at 747 °C: :2 + 3 → + 6 Reacting a mixture of alkali metal carbonates and with leads to the formation of ''thiogallates'' containing the anion. Strong acids decompose these salts, releasing in the process. The mercury salt, , can be used as a
phosphor A phosphor is a substance that exhibits the phenomenon of luminescence; it emits light when exposed to some type of radiant energy. The term is used both for fluorescent or phosphorescent substances which glow on exposure to ultraviolet or vi ...
. Gallium also forms sulfides in lower oxidation states, such as
gallium(II) sulfide Gallium(II) sulfide, GaS, is a chemical compound of gallium and sulfur. The normal form of gallium(II) sulfide as made from the elements has a hexagonal layer structure containing Ga24+ units which have a Ga-Ga distance of 248pm. This layer struct ...
and the green
gallium(I) sulfide Gallium is a chemical element with the symbol Ga and atomic number 31. Discovered by French chemist Paul-Émile Lecoq de Boisbaudran in 1875, Gallium is in group 13 of the periodic table and is similar to the other metals of the group (aluminium, ...
, the latter of which is produced from the former by heating to 1000 °C under a stream of nitrogen. The other binary chalcogenides, and , have the zincblende structure. They are all semiconductors but are easily hydrolysed and have limited utility.


Nitrides and pnictides

Gallium reacts with ammonia at 1050 °C to form gallium nitride, GaN. Gallium also forms binary compounds with phosphorus, arsenic, and antimony: gallium phosphide (GaP),
gallium arsenide Gallium arsenide (GaAs) is a III-V direct band gap semiconductor with a Zincblende (crystal structure), zinc blende crystal structure. Gallium arsenide is used in the manufacture of devices such as microwave frequency integrated circuits, monoli ...
(GaAs), and
gallium antimonide Gallium antimonide (GaSb) is a semiconducting compound of gallium and antimony of the III-V family. It has a lattice constant of about 0.61 nm. It has a band gap of 0.67 eV. History The intermetallic compound GaSb was first prepared in 1926 by Vi ...
(GaSb). These compounds have the same structure as ZnS, and have important semiconducting properties. GaP, GaAs, and GaSb can be synthesized by the direct reaction of gallium with elemental phosphorus, arsenic, or antimony. They exhibit higher electrical conductivity than GaN. GaP can also be synthesized by reacting with phosphorus at low temperatures. Gallium forms ternary nitrides; for example: : + → Similar compounds with phosphorus and arsenic are possible: and . These compounds are easily hydrolyzed by dilute
acid In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a sequ ...
s and water.


Halides

Gallium(III) oxide reacts with fluorinating agents such as HF or to form
gallium(III) fluoride Gallium(III) fluoride ( Ga F3) is a chemical compound. It is a white solid that melts under pressure above 1000 °C but sublimes around 950 °C. It has the FeF3 structure where the gallium atoms are 6-coordinate. GaF3 can be prepared by reacting ...
, . It is an ionic compound strongly insoluble in water. However, it dissolves in
hydrofluoric acid Hydrofluoric acid is a Solution (chemistry), solution of hydrogen fluoride (HF) in water. Solutions of HF are colourless, acidic and highly Corrosive substance, corrosive. It is used to make most fluorine-containing compounds; examples include th ...
, in which it forms an adduct with water, . Attempting to dehydrate this adduct forms . The adduct reacts with ammonia to form , which can then be heated to form anhydrous .
Gallium trichloride Gallium trichloride is the chemical compound with the formula GaCl3. Solid gallium trichloride exists as a dimer with the formula Ga2Cl6. It is colourless and soluble in virtually all solvents, even alkanes, which is truly unusual for a metal h ...
is formed by the reaction of gallium metal with chlorine gas. Unlike the trifluoride, gallium(III) chloride exists as dimeric molecules, , with a melting point of 78 °C. Eqivalent compounds are formed with bromine and iodine, and . Like the other group 13 trihalides, gallium(III) halides are
Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any sp ...
s, reacting as halide acceptors with alkali metal halides to form salts containing anions, where X is a halogen. They also react with alkyl halides to form
carbocation A carbocation is an ion with a positively charged carbon atom. Among the simplest examples are the methenium , methanium and vinyl cations. Occasionally, carbocations that bear more than one positively charged carbon atom are also encountere ...
s and . When heated to a high temperature, gallium(III) halides react with elemental gallium to form the respective gallium(I) halides. For example, reacts with Ga to form : :2 Ga + 3 GaCl (g) At lower temperatures, the equilibrium shifts toward the left and GaCl disproportionates back to elemental gallium and . GaCl can also be produced by reacting Ga with HCl at 950 °C; the product can be condensed as a red solid. Gallium(I) compounds can be stabilized by forming adducts with Lewis acids. For example: :GaCl + → The so-called "gallium(II) halides", , are actually adducts of gallium(I) halides with the respective gallium(III) halides, having the structure . For example: :GaCl + →


Hydrides

Like aluminium, gallium also forms a hydride, , known as '' gallane'', which may be produced by reacting lithium gallanate () with gallium(III) chloride at −30 °C: :3 + → 3 LiCl + 4 In the presence of
dimethyl ether Dimethyl ether (DME; also known as methoxymethane) is the organic compound with the formula CH3OCH3, (sometimes ambiguously simplified to C2H6O as it is an isomer of ethanol). The simplest ether, it is a colorless gas that is a useful precursor ...
as solvent, polymerizes to . If no solvent is used, the dimer (''
digallane Digallane (systematically named digallane(6)) is an inorganic compound with the chemical formula (also written or ). It is the dimer of the monomeric compound gallane. The eventual preparation of the pure compound, reported in 1989, was hailed ...
'') is formed as a gas. Its structure is similar to diborane, having two hydrogen atoms bridging the two gallium centers, unlike α- in which aluminium has a coordination number of 6. Gallane is unstable above −10 °C, decomposing to elemental gallium and hydrogen.


Organogallium compounds

Organogallium compounds are of similar reactivity to organoindium compounds, less reactive than
organoaluminium Organoaluminium chemistry is the study of compounds containing bonds between carbon and aluminium. It is one of the major themes within organometallic chemistry. Illustrative organoaluminium compounds are the dimer trimethylaluminium, the monomer ...
compounds, but more reactive than organothallium compounds.Greenwoood and Earnshaw, pp. 262–5 Alkylgalliums are monomeric.
Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any sp ...
ity decreases in the order Al > Ga > In and as a result organogallium compounds do not form bridged dimers as organoaluminium compounds do. Organogallium compounds are also less reactive than organoaluminium compounds. They do form stable peroxides. These alkylgalliums are liquids at room temperature, having low melting points, and are quite mobile and flammable. Triphenylgallium is monomeric in solution, but its crystals form chain structures due to weak intermolecluar Ga···C interactions. Gallium trichloride is a common starting reagent for the formation of organogallium compounds, such as in carbogallation reactions. Gallium trichloride reacts with lithium cyclopentadienide in diethyl ether to form the trigonal planar gallium cyclopentadienyl complex GaCp3. Gallium(I) forms complexes with arene
ligands In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electro ...
such as hexamethylbenzene. Because this ligand is quite bulky, the structure of the a(η6-C6Me6)sup>+ is that of a half-sandwich. Less bulky ligands such as mesitylene allow two ligands to be attached to the central gallium atom in a bent sandwich structure. Benzene is even less bulky and allows the formation of dimers: an example is a(η6-C6H6)2 aCl43C6H6.


History

In 1871, the existence of gallium was first predicted by Russian chemist
Dmitri Mendeleev Dmitri Ivanovich Mendeleev (sometimes transliterated as Mendeleyev or Mendeleef) ( ; russian: links=no, Дмитрий Иванович Менделеев, tr. , ; 8 February Old_Style_and_New_Style_dates">O.S._27_January.html" ;"title="O ...
, who named it " eka-aluminium" from its position in his
periodic table The periodic table, also known as the periodic table of the (chemical) elements, is a rows and columns arrangement of the chemical elements. It is widely used in chemistry, physics, and other sciences, and is generally seen as an icon of ch ...
. He also predicted several properties of eka-aluminium that correspond closely to the real properties of gallium, such as its density, melting point, oxide character, and bonding in chloride. : Mendeleev further predicted that eka-aluminium would be discovered by means of the spectroscope, and that metallic eka-aluminium would dissolve slowly in both acids and alkalis and would not react with air. He also predicted that M2O3 would dissolve in acids to give MX3 salts, that eka-aluminium salts would form basic salts, that eka-aluminium sulfate should form
alum An alum () is a type of chemical compound, usually a hydrated double salt, double sulfate salt (chemistry), salt of aluminium with the general chemical formula, formula , where is a valence (chemistry), monovalent cation such as potassium or a ...
s, and that anhydrous MCl3 should have a greater volatility than ZnCl2: all of these predictions turned out to be true. Gallium was discovered using
spectroscopy Spectroscopy is the field of study that measures and interprets the electromagnetic spectra that result from the interaction between electromagnetic radiation and matter as a function of the wavelength or frequency of the radiation. Matter wa ...
by French chemist
Paul Emile Lecoq de Boisbaudran Paul may refer to: *Paul (given name), a given name (includes a list of people with that name) *Paul (surname), a list of people People Christianity *Paul the Apostle (AD c.5–c.64/65), also known as Saul of Tarsus or Saint Paul, early Chris ...
in 1875 from its characteristic spectrum (two
violet Violet may refer to: Common meanings * Violet (color), a spectral color with wavelengths shorter than blue * One of a list of plants known as violet, particularly: ** ''Viola'' (plant), a genus of flowering plants Places United States * Viol ...
lines) in a sample of
sphalerite Sphalerite (sometimes spelled sphaelerite) is a sulfide mineral with the chemical formula . It is the most important ore of zinc. Sphalerite is found in a variety of deposit types, but it is primarily in Sedimentary exhalative deposits, sedimen ...
. Later that year, Lecoq obtained the free metal by
electrolysis In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from n ...
of the hydroxide in potassium hydroxide solution. He named the element "gallia", from Latin ''Gallia'' meaning Gaul, after his native land of France. It was later claimed that, in a multilingual pun of a kind favoured by men of science in the 19th century, he had also named gallium after himself: "Le coq" is French for "the rooster" and the Latin word for "rooster" is "''gallus''". In an 1877 article, Lecoq denied this conjecture. Originally, de Boisbaudran determined the density of gallium as 4.7 g/cm3, the only property that failed to match Mendeleev's predictions; Mendeleev then wrote to him and suggested that he should remeasure the density, and de Boisbaudran then obtained the correct value of 5.9 g/cm3, that Mendeleev had predicted exactly. From its discovery in 1875 until the era of semiconductors, the primary uses of gallium were high-temperature thermometrics and metal alloys with unusual properties of stability or ease of melting (some such being liquid at room temperature). The development of
gallium arsenide Gallium arsenide (GaAs) is a III-V direct band gap semiconductor with a Zincblende (crystal structure), zinc blende crystal structure. Gallium arsenide is used in the manufacture of devices such as microwave frequency integrated circuits, monoli ...
as a direct bandgap semiconductor in the 1960s ushered in the most important stage in the applications of gallium. In 1978, the electronics industry used gallium to fabricate light emitting diodes, photovoltaics and semiconductors, while the metals business used it to reduce the melting point of alloys.


Occurrence

Gallium does not exist as a free element in the Earth's crust, and the few high-content minerals, such as gallite (CuGaS2), are too rare to serve as a primary source. The abundance in the Earth's crust is approximately 16.9  ppm. This is comparable to the crustal abundances of lead, cobalt, and
niobium Niobium is a chemical element with chemical symbol Nb (formerly columbium, Cb) and atomic number 41. It is a light grey, crystalline, and ductile transition metal. Pure niobium has a Mohs hardness rating similar to pure titanium, and it has sim ...
. Yet unlike these elements, gallium does not form its own ore deposits with concentrations of > 0.1 wt.% in ore. Rather it occurs at trace concentrations similar to the crustal value in zinc ores, and at somewhat higher values (~ 50 ppm) in aluminium ores, from both of which it is extracted as a by-product. This lack of independent deposits is due to gallium's geochemical behaviour, showing no strong enrichment in the processes relevant to the formation of most ore deposits. The United States Geological Survey (USGS) estimates that more than 1 million tons of gallium is contained in known reserves of bauxite and zinc ores. Some coal flue dusts contain small quantities of gallium, typically less than 1% by weight. However, these amounts are not extractable without mining of the host materials (see below). Thus, the availability of gallium is fundamentally determined by the rate at which bauxite, zinc ores (and coal) are extracted.


Production and availability

Gallium is produced exclusively as a
by-product A by-product or byproduct is a secondary product derived from a production process, manufacturing process or chemical reaction; it is not the primary product or service being produced. A by-product can be useful and marketable or it can be consid ...
during the processing of the ores of other metals. Its main source material is bauxite, the chief ore of aluminium, but minor amounts are also extracted from sulfidic zinc ores (
sphalerite Sphalerite (sometimes spelled sphaelerite) is a sulfide mineral with the chemical formula . It is the most important ore of zinc. Sphalerite is found in a variety of deposit types, but it is primarily in Sedimentary exhalative deposits, sedimen ...
being the main host mineral). In the past, certain coals were an important source. During the processing of bauxite to alumina in the
Bayer process The Bayer process is the principal industrial means of refining bauxite to produce alumina (aluminium oxide) and was developed by Carl Josef Bayer. Bauxite, the most important ore of aluminium, contains only 30–60% aluminium oxide (Al2O3), the ...
, gallium accumulates in the
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula NaOH. It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly caustic base and alkali ...
liquor. From this it can be extracted by a variety of methods. The most recent is the use of ion-exchange resin. Achievable extraction efficiencies critically depend on the original concentration in the feed bauxite. At a typical feed concentration of 50 ppm, about 15% of the contained gallium is extractable. The remainder reports to the red mud and aluminium hydroxide streams. Gallium is removed from the ion-exchange resin in solution. Electrolysis then gives gallium metal. For semiconductor use, it is further purified with zone melting or single-crystal extraction from a melt ( Czochralski process). Purities of 99.9999% are routinely achieved and commercially available. Its by-product status means that gallium production is constrained by the amount of bauxite, sulfidic zinc ores (and coal) extracted per year. Therefore, its availability needs to be discussed in terms of supply potential. The supply potential of a by-product is defined as that amount which is economically extractable from its host materials ''per year'' under current market conditions (i.e. technology and price). Reserves and resources are not relevant for by-products, since they ''cannot'' be extracted independently from the main-products. Recent estimates put the supply potential of gallium at a minimum of 2,100 t/yr from bauxite, 85 t/yr from sulfidic zinc ores, and potentially 590 t/yr from coal. These figures are significantly greater than current production (375 t in 2016). Thus, major future increases in the by-product production of gallium will be possible without significant increases in production costs or price. The average price for low-grade gallium was $120 per kilogram in 2016 and $135–140 per kilogram in 2017. In 2017, the world's production of low-grade gallium was ca. 315 tons — an increase of 15% from 2016. China, Japan, South Korea, Russia, and Ukraine were the leading producers, while Germany ceased primary production of gallium in 2016. The yield of high-purity gallium was ca. 180 tons, mostly originating from China, Japan, Slovakia, UK and U.S. The 2017 world annual production capacity was estimated at 730 tons for low-grade and 320 tons for refined gallium.Galium
USGS (2018)
China produced ca. 250 tons of low-grade gallium in 2016 and ca. 300 tons in 2017. It also accounted for more than half of global LED production.


Applications

Semiconductor applications dominate the commercial demand for gallium, accounting for 98% of the total. The next major application is for
gadolinium gallium garnet Gadolinium Gallium Garnet (GGG, ) is a synthetic crystalline material of the garnet group, with good mechanical, thermal, and optical properties. It is typically colorless. It has a cubic lattice, a density of 7.08 g/cm3 and its Mohs hardness is v ...
s.Greber, J. F. (2012) "Gallium and Gallium Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, .


Semiconductors

Extremely high-purity (>99.9999%) gallium is commercially available to serve the semiconductor industry.
Gallium arsenide Gallium arsenide (GaAs) is a III-V direct band gap semiconductor with a Zincblende (crystal structure), zinc blende crystal structure. Gallium arsenide is used in the manufacture of devices such as microwave frequency integrated circuits, monoli ...
(GaAs) and gallium nitride (GaN) used in electronic components represented about 98% of the gallium consumption in the United States in 2007. About 66% of semiconductor gallium is used in the U.S. in integrated circuits (mostly gallium arsenide), such as the manufacture of ultra-high-speed logic chips and MESFETs for low-noise microwave preamplifiers in cell phones. About 20% of this gallium is used in optoelectronics. Worldwide, gallium arsenide makes up 95% of the annual global gallium consumption. It amounted to $7.5 billion in 2016, with 53% originating from cell phones, 27% from wireless communications, and the rest from automotive, consumer, fiber-optic, and military applications. The recent increase in GaAs consumption is mostly related to the emergence of 3G and 4G smartphones, which use 10 times more GaAs than older models. Gallium arsenide and gallium nitride can also be found in a variety of optoelectronic devices which had a market share of $15.3 billion in 2015 and $18.5 billion in 2016. Aluminium gallium arsenide (AlGaAs) is used in high-power infrared laser diodes. The semiconductors gallium nitride and indium gallium nitride are used in blue and violet optoelectronic devices, mostly laser diodes and light-emitting diodes. For example, gallium nitride 405 nm diode lasers are used as a violet light source for higher-density
Blu-ray Disc The Blu-ray Disc (BD), often known simply as Blu-ray, is a Digital media, digital optical disc data storage format. It was invented and developed in 2005 and released on June 20, 2006 worldwide. It is designed to supersede the DVD format, and c ...
compact data disc drives. Other major application of gallium nitride are cable television transmission, commercial wireless infrastructure, power electronics, and satellites. The GaN radio frequency device market alone was estimated at $370 million in 2016 and $420 million in 2016. Multijunction photovoltaic cells, developed for satellite power applications, are made by molecular-beam epitaxy or
metalorganic vapour-phase epitaxy Metalorganic vapour-phase epitaxy (MOVPE), also known as organometallic vapour-phase epitaxy (OMVPE) or metalorganic chemical vapour deposition (MOCVD), is a chemical vapour deposition method used to produce single- or polycrystalline thin films. ...
of thin films of gallium arsenide, indium gallium phosphide, or indium gallium arsenide. The Mars Exploration Rovers and several satellites use triple-junction gallium arsenide on germanium cells. Gallium is also a component in
photovoltaic Photovoltaics (PV) is the conversion of light into electricity using semiconducting materials that exhibit the photovoltaic effect, a phenomenon studied in physics, photochemistry, and electrochemistry. The photovoltaic effect is commercially us ...
compounds (such as copper indium gallium selenium sulfide ) used in solar panels as a cost-efficient alternative to crystalline silicon.


Galinstan and other alloys

Gallium readily alloys with most metals, and is used as an ingredient in
low-melting alloy A fusible alloy is a metal alloy capable of being easily fused, i.e. easily meltable, at relatively low temperatures. Fusible alloys are commonly, but not necessarily, eutectic alloys. Sometimes the term "fusible alloy" is used to describe alloys ...
s. The nearly eutectic alloy of gallium, indium, and tin is a room temperature liquid used in medical thermometers. This alloy, with the trade-name ''
Galinstan Galinstan (R) is a brand name for a alloy composed of gallium, indium, and tin which melts at and is thus liquid at room temperature. However, it is not a eutectic alloy but a near eutectic alloy. In scientific literature, galinstan is also used ...
'' (with the "-stan" referring to the tin, ''stannum'' in Latin), has a low melting point of −19 °C (−2.2 °F). It has been suggested that this family of alloys could also be used to cool computer chips in place of water, and is often used as a replacement for thermal paste in high-performance computing. Gallium alloys have been evaluated as substitutes for mercury
dental amalgam Dental amalgam is a liquid mercury and metal alloy mixture used in dentistry to fill cavities caused by tooth decay. Low-copper amalgam commonly consists of mercury (50%), silver (~22–32%), tin (~14%), zinc (~8%) and other trace metals. Den ...
s, but these materials have yet to see wide acceptance. Liquid alloys containing mostly gallium and indium have been found to precipitate gaseous CO2 into solid carbon and are being researched as potential methodologies for
carbon capture Carbon capture may refer to: * Carbon capture and utilization, where the captured carbon dioxide is used * Carbon sequestration, where the captured carbon dioxide is stored ** Carbon capture and storage, referring to carbon sequestration from point ...
and possibly
carbon removal Carbon dioxide removal (CDR), also known as negative emissions, is a process in which carbon dioxide gas () is removed from the atmosphere and sequestered for long periods of time. Similarly, greenhouse gas removal (GGR) or negative greenho ...
. Because gallium wets glass or porcelain, gallium can be used to create brilliant mirrors. When the wetting action of gallium-alloys is not desired (as in
Galinstan Galinstan (R) is a brand name for a alloy composed of gallium, indium, and tin which melts at and is thus liquid at room temperature. However, it is not a eutectic alloy but a near eutectic alloy. In scientific literature, galinstan is also used ...
glass thermometers), the glass must be protected with a transparent layer of gallium(III) oxide. The plutonium used in nuclear weapon pits is stabilized in the δ phase and made machinable by alloying with gallium.


Biomedical applications

Although gallium has no natural function in biology, gallium ions interact with processes in the body in a manner similar to
iron(III) In chemistry, iron(III) refers to the chemical element, element iron in its +3 oxidation number, oxidation state. In salt (chemistry), ionic compounds (salts), such an atom may occur as a separate cation (positive ion) denoted by Fe3+. The adjec ...
. Because these processes include inflammation, a marker for many disease states, several gallium salts are used (or are in development) as
pharmaceuticals A medication (also called medicament, medicine, pharmaceutical drug, medicinal drug or simply drug) is a drug used to diagnose, cure, treat, or prevent disease. Drug therapy (pharmacotherapy) is an important part of the medical field and rel ...
and radiopharmaceuticals in medicine. Interest in the anticancer properties of gallium emerged when it was discovered that 67Ga(III) citrate injected in tumor-bearing animals localized to sites of tumor. Clinical trials have shown gallium nitrate to have antineoplastic activity against non-Hodgkin's lymphoma and urothelial cancers. A new generation of gallium-ligand complexes such as tris(8-quinolinolato)gallium(III) (KP46) and gallium maltolate has emerged. Gallium nitrate (brand name Ganite) has been used as an intravenous pharmaceutical to treat
hypercalcemia Hypercalcemia, also spelled hypercalcaemia, is a high calcium (Ca2+) level in the blood serum. The normal range is 2.1–2.6 mmol/L (8.8–10.7 mg/dL, 4.3–5.2 mEq/L), with levels greater than 2.6 mmol/L defined as hypercalcemi ...
associated with tumor metastasis to bones. Gallium is thought to interfere with osteoclast function, and the therapy may be effective when other treatments have failed.
Gallium maltolate Gallium maltolate is a coordination complex consisting of a trivalent gallium cation coordinated to three maltolate ligands. The compound is a potential therapeutic agent for cancer, infectious disease, and inflammatory disease. A cosmetic skin ...
, an oral, highly absorbable form of gallium(III) ion, is an anti-proliferative to pathologically proliferating cells, particularly cancer cells and some bacteria that accept it in place of ferric iron (Fe3+). Researchers are conducting clinical and preclinical trials on this compound as a potential treatment for a number of cancers, infectious diseases, and inflammatory diseases. When gallium ions are mistakenly taken up in place of iron(III) by bacteria such as '' Pseudomonas'', the ions interfere with respiration, and the bacteria die. This happens because iron is redox-active, allowing the transfer of electrons during respiration, while gallium is redox-inactive. A complex amine- phenol Ga(III) compound MR045 is selectively toxic to parasites resistant to chloroquine, a common drug against malaria. Both the Ga(III) complex and chloroquine act by inhibiting crystallization of
hemozoin Haemozoin is a disposal product formed from the digestion of blood by some blood-feeding parasites. These hematophagous organisms such as malaria parasites (''Plasmodium spp.''), ''Rhodnius'' and ''Schistosoma'' digest haemoglobin and release high ...
, a disposal product formed from the digestion of blood by the parasites.


Radiogallium salts

Gallium-67 Natural gallium (31Ga) consists of a mixture of two stable isotopes: gallium-69 and gallium-71. The most commercially important radioisotopes are gallium-67 and gallium-68. Gallium-67 (half-life 3.3 days) is a gamma-emitting isotope (the gamma ...
salts such as gallium citrate and gallium
nitrate Nitrate is a polyatomic ion A polyatomic ion, also known as a molecular ion, is a covalent bonded set of two or more atoms, or of a metal complex, that can be considered to behave as a single unit and that has a net charge that is not zer ...
are used as radiopharmaceutical agents in the nuclear medicine imaging known as
gallium scan A gallium scan is a type of nuclear medicine test that uses either a gallium-67 (67Ga) or gallium-68 (68Ga) radiopharmaceutical to obtain images of a specific type of tissue, or disease state of tissue. Gallium salts like gallium citrate and galli ...
. The radioactive isotope 67Ga is used, and the compound or salt of gallium is unimportant. The body handles Ga3+ in many ways as though it were Fe3+, and the ion is bound (and concentrates) in areas of inflammation, such as infection, and in areas of rapid cell division. This allows such sites to be imaged by nuclear scan techniques. Gallium-68, a positron emitter with a half-life of 68 min, is now used as a diagnostic radionuclide in PET-CT when linked to pharmaceutical preparations such as DOTATOC, a
somatostatin Somatostatin, also known as growth hormone-inhibiting hormone (GHIH) or by several other names, is a peptide hormone that regulates the endocrine system and affects neurotransmission and cell proliferation via interaction with G protein-couple ...
analogue used for neuroendocrine tumors investigation, and DOTA-TATE, a newer one, used for neuroendocrine metastasis and lung neuroendocrine cancer, such as certain types of '' microcytoma''. Gallium-68's preparation as a pharmaceutical is chemical, and the radionuclide is extracted by elution from germanium-68, a
synthetic radioisotope A synthetic radioisotope is a radionuclide that is not found in nature: no natural process or mechanism exists which produces it, or it is so unstable that it decays away in a very short period of time. Examples include technetium-95 and prometh ...
of
germanium Germanium is a chemical element with the symbol Ge and atomic number 32. It is lustrous, hard-brittle, grayish-white and similar in appearance to silicon. It is a metalloid in the carbon group that is chemically similar to its group neighbors s ...
, in gallium-68 generators.


Other uses

Neutrino detection: Gallium is used for neutrino detection. Possibly the largest amount of pure gallium ever collected in a single location is the Gallium-Germanium Neutrino Telescope used by the SAGE experiment at the Baksan Neutrino Observatory in Russia. This detector contains 55–57 tonnes (~9 cubic metres) of liquid gallium. Another experiment was the
GALLEX GALLEX or Gallium Experiment was a radiochemical neutrino detection experiment that ran between 1991 and 1997 at the Laboratori Nazionali del Gran Sasso (LNGS). This project was performed by an international collaboration of French, German, Itali ...
neutrino detector operated in the early 1990s in an Italian mountain tunnel. The detector contained 12.2 tons of watered gallium-71. Solar neutrinos caused a few atoms of 71Ga to become radioactive 71 Ge, which were detected. This experiment showed that the solar neutrino flux is 40% less than theory predicted. This deficit was not explained until better solar neutrino detectors and theories were constructed (see SNO). Ion source: Gallium is also used as a liquid metal ion source for a
focused ion beam Focused ion beam, also known as FIB, is a technique used particularly in the semiconductor industry, materials science and increasingly in the biological field for site-specific analysis, deposition, and ablation of materials. A FIB setup is a s ...
. For example, a focused gallium-ion beam was used to create the world's smallest book, '' Teeny Ted from Turnip Town''."Nano lab produces world's smallest book"
. Simon Fraser University. 11 April 2007. Retrieved 31 January 2013.
Lubricants: Gallium serves as an additive in glide wax for skis and other low-friction surface materials. Flexible electronics: Materials scientists speculate that the properties of gallium could make it suitable for the development of flexible and wearable devices. Hydrogen generation: Gallium disrupts the protective oxide layer on aluminium, allowing water to react with the aluminium in AlGa to produce hydrogen gas. Humor: A well-known
practical joke A practical joke, or prank, is a mischievous trick played on someone, generally causing the victim to experience embarrassment, perplexity, confusion, or discomfort.Marsh, Moira. 2015. ''Practically Joking''. Logan: Utah State University Press. ...
among chemists is to fashion gallium spoons and use them to serve tea to unsuspecting guests, since gallium has a similar appearance to its lighter homolog aluminium. The spoons then melt in the hot tea.


Gallium in the ocean

Advances in trace element testing have allowed scientists to discover traces of dissolved gallium in the Atlantic and Pacific Oceans In recent years, dissolved gallium concentrations have presented in the Beaufort Sea. These reports reflect the possible profiles of the Pacific and Atlantic Ocean waters. For the Pacific Oceans, typical dissolved gallium concentrations are between 4–6 pmol/kg at depths <~150 m. In comparison, for Atlantic waters 25–28 pmol/kg at depths >~350 m. Gallium has entered oceans mainly through aeolian input, but having gallium in our oceans can be used to resolve aluminium distribution in the oceans. The reason for this is that gallium is geochemically similar to aluminium, just less reactive. Gallium also has a slightly larger surface water residence time than aluminium. Gallium has a similar dissolved profile similar to that of aluminium, due to this gallium can be used as a tracer for aluminium. Gallium can also be used as a tracer of aeolian inputs of iron. Gallium is used as a tracer for iron in the northwest Pacific, south and central Atlantic Oceans. For example, in the northwest Pacific, low gallium surface waters, in the subpolar region suggest that there is low dust input, which can subsequently explain the following
high-nutrient, low-chlorophyll High-nutrient, low-chlorophyll (HNLC) regions are regions of the ocean where the abundance of phytoplankton is low and fairly constant despite the availability of macronutrients. Phytoplankton rely on a suite of nutrients for cellular function. Ma ...
environmental behavior.


Precautions

Metallic gallium is not toxic. However, exposure to gallium halide complexes can result in acute toxicity. The Ga3+ ion of soluble gallium salts tends to form the insoluble hydroxide when injected in large doses; precipitation of this hydroxide resulted in nephrotoxicity in animals. In lower doses, soluble gallium is tolerated well and does not accumulate as a poison, instead being excreted mostly through urine. Excretion of gallium occurs in two phases: the first phase has a biological half-life of 1 hour, while the second has a biological half-life of 25 hours.


References


Bibliography

*


External links


Gallium
at '' The Periodic Table of Videos'' (University of Nottingham) *
Safety data sheet A safety data sheet (SDS), material safety data sheet (MSDS), or product safety data sheet (PSDS) is a document that lists information relating to occupational safety and health for the use of various substances and products. SDSs are a widely ...
a
acialloys.com

High-resolution photographs of molten gallium, gallium crystals and gallium ingots under Creative Commons licence





Price development of gallium 1959–1998

Gallium: A Smart Metal
United States Geological Survey
Thermal conductivity

Physical and thermodynamical properties of liquid gallium
(doc pdf) {{Subject bar , commons=y , wikt=y , wikt-search=gallium , b=y , b-search=General Chemistry/Chemistries of Various Elements/Group 13#Others , v=y , v-search=Gallium atom , portal1=Chemistry Chemical elements predicted by Dmitri Mendeleev Chemical elements Coolants Post-transition metals Articles containing video clips Materials that expand upon freezing Chemical elements with primitive orthorhombic structure