Indium

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Not to be confused with Iridium.

Indium, 49In
Indium
Pronunciation/ˈɪndiəm/ ​(IN-dee-əm)
Appearancesilvery lustrous gray
Standard atomic weight Ar°(In)
Indium in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
Ga
↑
In
↓
Tl
cadmium ← indium → tin
kJ/mol
Heat of vaporization231.8 kJ/mol
Molar heat capacity26.74 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1196 1325 1485 1690 1962 2340
Atomic properties
Discovery
Ferdinand Reich and Hieronymous Theodor Richter (1863)
First isolationHieronymous Theodor Richter (1864)
Isotopes of indium
Main isotopes[9] Decay
abun­dance half-life (t1/2) mode pro­duct
111In synth 2.8 d ε
111Cd
113In 4.28%
stable
115In 95.7% 4.41×1014 y
β−
115Sn
 Category: Indium
| references

Indium is a

spectroscopic methods and named for the indigo blue line in its spectrum.[11]

Indium is a

alloys such as solders and soft-metal high-vacuum seals. It is produced exclusively as a by-product during the processing of the ores of other metals, chiefly from sphalerite and other zinc sulfide ores.[16]

Indium has no biological role and its compounds are toxic when inhaled or injected into the bloodstream, although they are poorly absorbed following ingestion.[17][18]

Etymology

The name comes from the Latin word indicium meaning violet or indigo.[19]

Properties

Physical

Indium wetting the glass surface of a test tube

Indium is a shiny silvery-white, highly

Mohs hardness 1.2) that it can be cut with a knife and leaves a visible line like a pencil when rubbed on paper.[21] It is a member of group 13 on the periodic table and its properties are mostly intermediate between its vertical neighbors gallium and thallium. Like tin, a high-pitched cry is heard when indium is bent – a crackling sound due to crystal twinning.[20] Like gallium, indium is able to wet glass. Like both, indium has a low melting point, 156.60 °C (313.88 °F); higher than its lighter homologue, gallium, but lower than its heavier homologue, thallium, and lower than tin.[22] The boiling point is 2072 °C (3762 °F), higher than that of thallium, but lower than gallium, conversely to the general trend of melting points, but similarly to the trends down the other post-transition metal groups because of the weakness of the metallic bonding with few electrons delocalized.[23]

The density of indium, 7.31 g/cm3, is also greater than gallium, but lower than thallium. Below the

face-centered cubic structure, where each indium atom has four neighbours at 324 pm distance and eight neighbours slightly further (336 pm).[24] Indium has greater solubility in liquid mercury than any other metal (more than 50 mass percent of indium at 0 °C).[25] Indium displays a ductile viscoplastic response, found to be size-independent in tension and compression. However it does have a size effect in bending and indentation, associated to a length-scale of order 50–100 µm,[26]
significantly large when compared with other metals.

Chemical

Indium has 49 electrons, with an electronic configuration of [

inert pair effect, in which relativistic effects stabilize the 5s-orbital, observed in heavier elements. Thallium (indium's heavier homolog) shows an even stronger effect, causing oxidation to thallium(I) to be more probable than to thallium(III),[27] whereas gallium (indium's lighter homolog) commonly shows only the +3 oxidation state. Thus, although thallium(III) is a moderately strong oxidizing agent, indium(III) is not, and many indium(I) compounds are powerful reducing agents.[28] While the energy required to include the s-electrons in chemical bonding is lowest for indium among the group 13 metals, bond energies decrease down the group so that by indium, the energy released in forming two additional bonds and attaining the +3 state is not always enough to outweigh the energy needed to involve the 5s-electrons.[29] Indium(I) oxide and hydroxide are more basic and indium(III) oxide and hydroxide are more acidic.[29]

A number of standard electrode potentials, depending on the reaction under study,[30] are reported for indium, reflecting the decreased stability of the +3 oxidation state:[24]

In2+ + e− ⇌ In+ E0 = −0.40 V
In3+ + e− ⇌ In2+ E0 = −0.49 V
In3+ + 2 e− ⇌ In+ E0 = −0.443 V
In3+ + 3 e− ⇌ In E0 = −0.3382 V
In+ + e− ⇌ In E0 = −0.14 V

Indium metal does not react with water, but it is oxidized by stronger oxidizing agents such as

amphoteric characteristics, and unlike its lighter homologs aluminium and gallium, it is insoluble in aqueous alkaline solutions.[31]

Isotopes

Main article: Isotopes of indium

Indium has 39 known

age of the Universe and nearly 30,000 times greater than half life of thorium-232.[32] The half-life of 115In is very long because the beta decay to 115Sn is spin-forbidden.[33] Indium-115 makes up 95.7% of all indium. Indium is one of three known elements (the others being tellurium and rhenium) of which the stable isotope is less abundant in nature than the long-lived primordial radioisotopes.[34]

The stablest

isomeric transition. The indium isotopes lighter than 113In predominantly decay through electron capture or positron emission to form cadmium isotopes, while the indium isotopes heavier than 113In predominantly decay through beta-minus decay to form tin isotopes.[32]

Compounds

See also: Indium chalcogenides and Category:Indium compounds

Indium(III)

InCl3
(structure pictured) is a common compound of indium.

alumina and is amphoteric, that is able to react with both acids and bases. Indium reacts with water to reproduce soluble indium(III) hydroxide
, which is also amphoteric; with alkalis to produce indates(III); and with acids to produce indium(III) salts:

In(OH)3 + 3 HCl → InCl3 + 3 H2O

The analogous sesqui-chalcogenides with

Lewis acids, somewhat akin to the better known aluminium trihalides. Again like the related aluminium compound, InF3 is polymeric.[37]

Direct reaction of indium with the pnictogens produces the gray or semimetallic III–V semiconductors. Many of them slowly decompose in moist air, necessitating careful storage of semiconductor compounds to prevent contact with the atmosphere. Indium nitride is readily attacked by acids and alkalis.[38]

Indium(I)

Indium(I) compounds are not common. The chloride, bromide, and iodide are deeply colored, unlike the parent trihalides from which they are prepared. The fluoride is known only as an unstable gaseous compound.[39] Indium(I) oxide black powder is produced when indium(III) oxide decomposes upon heating to 700 °C.[35]

Other oxidation states

Less frequently, indium forms compounds in oxidation state +2 and even fractional oxidation states. Usually such materials feature In–In bonding, most notably in the halides In2X4 and [In2X6]2−,[40] and various subchalcogenides such as In4Se3.[41] Several other compounds are known to combine indium(I) and indium(III), such as InI6(InIIICl6)Cl3,[42] InI5(InIIIBr4)2(InIIIBr6),[43] and InIInIIIBr4.[40]

Organoindium compounds

Organoindium compounds feature In–C bonds. Most are In(III) derivatives, but cyclopentadienylindium(I) is an exception. It was the first known organoindium(I) compound,[44] and is polymeric, consisting of zigzag chains of alternating indium atoms and cyclopentadienyl complexes.[45] Perhaps the best-known organoindium compound is trimethylindium, In(CH3)3, used to prepare certain semiconducting materials.[46][47]

History

In 1863, the German chemists

color-blind, employed Richter as an assistant for detecting the colored spectral lines. Knowing that ores from that region sometimes contain thallium, they searched for the green thallium emission spectrum lines. Instead, they found a bright blue line. Because that blue line did not match any known element, they hypothesized a new element was present in the minerals. They named the element indium, from the indigo color seen in its spectrum, after the Latin indicum, meaning 'of India'.[48][11][49][50]

Richter went on to isolate the metal in 1864.[51] An ingot of 0.5 kg (1.1 lb) was presented at the World Fair 1867.[52] Reich and Richter later fell out when the latter claimed to be the sole discoverer.[50]

Occurrence

yellow squares with red and blue arrows
The s-process acting in the range from silver to antimony

Indium is created by the long-lasting (up to thousands of years)

quadrillion years, this cannot account for all indium-113.[54][55]

Indium is the

ppb. This is similar to the crustal abundance of silver, bismuth and mercury. It very rarely forms its own minerals, or occurs in elemental form. Fewer than 10 indium minerals such as roquesite (CuInS2) are known, and none occur at sufficient concentrations for economic extraction.[56] Instead, indium is usually a trace constituent of more common ore minerals, such as sphalerite and chalcopyrite.[57][58] From these, it can be extracted as a by-product during smelting.[16] While the enrichment of indium in these deposits is high relative to its crustal abundance, it is insufficient, at current prices, to support extraction of indium as the main product.[56]

Different estimates exist of the amounts of indium contained within the ores of other metals.[59][60] However, these amounts are not extractable without mining of the host materials (see Production and availability). Thus, the availability of indium is fundamentally determined by the rate at which these ores are extracted, and not their absolute amount. This is an aspect that is often forgotten in the current debate, e.g. by the Graedel group at Yale in their criticality assessments,[61] explaining the paradoxically low depletion times some studies cite.[62][16]

Production and availability

World production trend[63]

Indium is produced exclusively as a by-product during the processing of the ores of other metals. Its main source material are sulfidic zinc ores, where it is mostly hosted by sphalerite.[16] Minor amounts are also extracted from sulfidic copper ores. During the roast-leach-electrowinning process of zinc smelting, indium accumulates in the iron-rich residues. From these, it can be extracted in different ways. It may also be recovered directly from the process solutions. Further purification is done by electrolysis.[64] The exact process varies with the mode of operation of the smelter.[20][16]

Its by-product status means that indium production is constrained by the amount of sulfidic zinc (and copper) ores extracted each 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).[65] Reserves and resources are not relevant for by-products, since they cannot be extracted independently from the main-products.[16] Recent estimates put the supply potential of indium at a minimum of 1,300 t/yr from sulfidic zinc ores and 20 t/yr from sulfidic copper ores.[16] These figures are significantly greater than current production (655 t in 2016).[66] Thus, major future increases in the by-product production of indium will be possible without significant increases in production costs or price. The average indium price in 2016 was US$240/kg, down from US$705/kg in 2014.[67]

China is a leading producer of indium (290 tonnes in 2016), followed by South Korea (195 t), Japan (70 t) and Canada (65 t).[66] The Teck Resources refinery in Trail, British Columbia, is a large single-source indium producer, with an output of 32.5 tonnes in 2005, 41.8 tonnes in 2004 and 36.1 tonnes in 2003.

The primary consumption of indium worldwide is

UNEP, indium's end-of-life recycling rate is less than 1%.[68]

Applications

A magnified image of an LCD screen showing RGB pixels. Individual transistors are seen as white dots in the bottom part.

In 1924, indium was found to have a valued property of stabilizing

non-ferrous metals, and that became the first significant use for the element.[69] The first large-scale application for indium was coating bearings in high-performance aircraft engines during World War II, to protect against damage and corrosion; this is no longer a major use of the element.[64] New uses were found in fusible alloys, solders, and electronics. In the 1950s, tiny beads of indium were used for the emitters and collectors of PNP alloy-junction transistors. In the middle and late 1980s, the development of indium phosphide semiconductors and indium tin oxide thin films for liquid-crystal displays (LCD) aroused much interest. By 1992, the thin-film application had become the largest end use.[70][71]

Indium(III) oxide and

infrared radiation is reflected back into the lamp, which increases the temperature within the tube and improves the performance of the lamp.[71]

Indium has many

CIGS solar cells, a type of second-generation thin-film solar cell.[76] Indium is used in PNP bipolar junction transistors with germanium: when soldered at low temperature, indium does not stress the germanium.[64]

Ductile indium wire
A video on indium lung, an illness caused by indium exposure

Indium wire is used as a vacuum seal and a thermal conductor in cryogenics and ultra-high-vacuum applications, in such manufacturing applications as gaskets that deform to fill gaps.[77] Owing to its great plasticity and adhesion to metals, Indium sheets are sometimes used for cold-soldering in microwave circuits and waveguide joints, where direct soldering is complicated. Indium is an ingredient in the gallium–indium–tin alloy galinstan, which is liquid at room temperature and replaces mercury in some thermometers.[78] Other alloys of indium with bismuth, cadmium, lead, and tin, which have higher but still low melting points (between 50 and 100 °C), are used in fire sprinkler systems and heat regulators.[64]

Indium is one of many substitutes for mercury in

dental amalgam alloys to decrease the surface tension of the mercury and allow for less mercury and easier amalgamation.[80]

Indium's high neutron-capture cross-section for thermal neutrons makes it suitable for use in

nuclear reactors, typically in an alloy of 80% silver, 15% indium, and 5% cadmium.[81] In nuclear engineering, the (n,n') reactions of 113In and 115In are used to determine magnitudes of neutron fluxes.[82]

In 2009, Professor

YInMn blue, the first new inorganic blue pigment discovered in 200 years.[83]

Biological role and precautions

Indium
Hazards
GHS labelling:
GHS07: Exclamation mark
Warning
H302, H312, H315, H319, H332, H335
P261, P280, P305+P351+P338[84]
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
2
0
0

Indium has no

white blood cells in the body.[86][87] Indium compounds are mostly not absorbed upon ingestion and are only moderately absorbed on inhalation; they tend to be stored temporarily in the muscles, skin, and bones before being excreted, and the biological half-life of indium is about two weeks in humans.[88]

People can be exposed to indium in the workplace by inhalation, ingestion, skin contact, and eye contact. Indium lung is a lung disease characterized by pulmonary alveolar proteinosis and pulmonary fibrosis, first described by Japanese researchers in 2003. As of 2010, 10 cases had been described, though more than 100 indium workers had documented respiratory abnormalities.[17] The National Institute for Occupational Safety and Health has set a recommended exposure limit (REL) of 0.1 mg/m3 over an eight-hour workday.[89]

See also

Notes

  1. ^ The thermal expansion is anisotropic: the parameters (at 20 °C) for each crystal axis are αa = 53.2×10−6/K, αc = −9.75×10−6/K, and αaverage = αV/3 = 32.2×10−6/K.[3]

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Sources

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