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Gallium

Chemical element with atomic number 31 (Ga)

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Gallium bar cracked open to show choncoidal fractures with scale (edited from original)
Arònel123 · CC BY 4.0

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The melting point of gallium, 29.7646 °C (85.5763 °F; 302.9146 K), is used as a temperature reference point. One of only four metal elements that is liquid at, or near, normal room temperature, gallium will melt in a person's hands at normal human body temperature of 37 °C (99 °F). Gallium alloys with low temperatures are used in thermometers as a non-toxic and environmentally friendly alternative to mercury, and can withstand higher temperatures than mercury. A melting point of −19 °C (−2 °F), well below the freezing point of water, is claimed for the alloy galinstan (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 is predominantly used in electronics. Gallium arsenide, 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 for jewelry. It 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 forms alloys with most metals. It readily diffuses into cracks or grain boundaries of some metals such as aluminium, aluminium–zinc alloys and steel, causing extreme loss of strength and ductility called liquid metal embrittlement.

Under normal conditions, gallium does not crystallize in any of the simple crystal structures. Instead, its stable phase (Ga-I) is a complex orthorhombic structure with eight 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. 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 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 [Ar]3d10 core. This phenomenon recurs with mercury with its "pseudo-noble-gas" [Xe]4f145d106s2 electron configuration, which is liquid at room temperature. 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.

The physical properties of gallium are highly anisotropic, 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.

Liquid gallium

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 (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.

Gallium is one of the four non-radioactive metals (with caesium, rubidium, and mercury) 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, 2,676 K (2,403 °C; 4,357 °F), 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. 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), 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's volume expands by 3.10% when it changes from a liquid to a solid so care must be taken when storing it in containers that may rupture when it changes state. Gallium shares the higher-density liquid state with a short list of other materials that includes water, silicon, germanium, bismuth, lead, and plutonium. In gallium, this anomalous behaviour is a result of the breaking of the Ga2 dimeric bonds present in the solid. While the covalently bonded Ga2 dimers do not persist in the liquid state, liquid gallium does exhibit an anomalous complex low-coordinated structure in which each gallium atom is surrounded by 10 others, compared to 11–12 nearest neighbors typical of most liquid metals.

Liquid Ga is known to show extreme supercooling properties, that is to say it can remain liquid below its standard solidification temperature. Micrometric Ga droplets can be undercooled at temperatures as lower as 150 K. Ga nanoparticles can be kept in the liquid state below 90 K (−183.2 °C; −297.7 °F). Seeding with a crystal helps to initiate freezing.

High pressure phases

Gallium has one of the most complex phase diagrams of all the elemental metals, with many stable and metastable phases discovered as function of temperature and pressure. Gallium exhibits a negative high-pressure melting curve, melting from the complex orthorhombic Ga-I phase when compressed to 0.5 gigapascals (5,000 bar) at room temperature. On further compression to 2 gigapascals (20,000 bar), liquid Ga crystallizes into a metastable Ga-III phase with a simple body-centred-tetragonal structure. A highly complex Ga-II phase with a 103-atom orthorhombic structure can be obtained by compressing Ga-I at temperatures below 273 K (0 °C; 32 °F). On further compression at room temperature, the Ga-II phase transforms into the Ga-V phase with a rhombohedral structure. Above pressures of 14 gigapascals (140,000 bar), the body-centered tetragonal Ga-III is stabilised. At extreme pressures of around 120 gigapascals (1,200,000 bar), the Ga-IV phase with a face-centered-cubic structure is formed. At simultaneous high-pressure and high-temperature conditions, liquid gallium experiences an increase in atomic packing towards 12 nearest-neighbours expected for a simple metallic liquid. However, while pressure causes liquid gallium to resemble a simple hard-sphere liquid, as for liquid mercury, even at very high pressures (up to around 26 gigapascals (260,000 bar)), it contains many more atomic clusters with low configurational entropy than expected for a simple liquid.

Isotopes

Gallium has 30 known isotopes, ranging in mass number from 60 to 89. 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 3.2617 days). Isotopes lighter than gallium-69 usually decay through beta plus decay (positron emission) or electron capture to isotopes of zinc, while isotopes heavier than gallium-71 decay through beta minus decay (electron emission), possibly with delayed neutron emission, to isotopes of germanium. Gallium-70 can decay both ways, to zinc-70 or to germanium-70.

Gallium-67 and gallium-68 (half-life 67.84 min) are both used for imaging in nuclear medicine (see gallium scan).

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