Antimony

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Not to be confused with antinomy or antiphony.
This article is about the element. For other uses, see Antimony (disambiguation).

Antimony, 51Sb
Antimony
Pronunciation
Appearancesilvery lustrous gray
Standard atomic weight Ar°(Sb)
Antimony 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
As
↑
Sb
↓
Bi
tin ← antimony → tellurium
kJ/mol
Heat of vaporization193.43 kJ/mol
Molar heat capacity25.23 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 807 876 1011 1219 1491 1858
Atomic properties
Arabic alchemists (before AD 815)
Symbol"Sb": from Latin stibium 'stibnite'
Isotopes of antimony
Main isotopes[7] Decay
abun­dance half-life (t1/2) mode pro­duct
121Sb 57.2%
stable
123Sb 42.8% stable
125Sb synth 2.7576 y
β−
125Te
 Category: Antimony
| references

Antimony is a

Latin stibium) and atomic number 51. A lustrous grey metal or metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient times and were powdered for use as medicine and cosmetics, often known by the Arabic name kohl.[8] The earliest known description of the metalloid in the West was written in 1540 by Vannoccio Biringuccio
.

China is the largest producer of antimony and its compounds, with most production coming from the Xikuangshan Mine in Hunan. The industrial methods for refining antimony from stibnite are roasting followed by reduction with carbon, or direct reduction of stibnite with iron.

The largest applications for metallic antimony are in

lead–acid batteries. Antimony trioxide is a prominent additive for halogen-containing flame retardants. Antimony is used as a dopant in semiconductor devices
.

Characteristics

Properties

allotrope
of antimony
An irregular piece of silvery stone with spots of variation in luster and shade.
Native antimony with oxidation products
Crystal structure common to Sb, AsSb and gray As

Antimony is a member of group 15 of the periodic table, one of the elements called pnictogens, and has an electronegativity of 2.05. In accordance with periodic trends, it is more electronegative than tin or bismuth, and less electronegative than tellurium or arsenic. Antimony is stable in air at room temperature, but reacts with oxygen if heated to produce antimony trioxide, Sb2O3.[9]

Antimony is a silvery, lustrous gray metalloid with a Mohs scale hardness of 3, which is too soft to mark hard objects. Coins of antimony were issued in China's Guizhou province in 1931; durability was poor, and minting was soon discontinued.[10] Antimony is resistant to attack by acids.

The only stable

exothermic
reaction occurs and white fumes are given off as metallic antimony forms; when rubbed with a pestle in a mortar, a strong detonation occurs.

Elemental antimony adopts a layered structure (space group R3m No. 166) whose layers consist of fused, ruffled, six-membered rings. The nearest and next-nearest neighbors form an irregular octahedral complex, with the three atoms in each double layer slightly closer than the three atoms in the next. This relatively close packing leads to a high density of 6.697 g/cm3, but the weak bonding between the layers leads to the low hardness and brittleness of antimony.[9]

Isotopes

Main article: Isotopes of antimony

Antimony has two stable isotopes: 121Sb with a natural abundance of 57.36% and 123Sb with a natural abundance of 42.64%. It also has 35 radioisotopes, of which the longest-lived is 125Sb with a half-life of 2.75 years. In addition, 29 metastable states have been characterized. The most stable of these is 120m1Sb with a half-life of 5.76 days. Isotopes that are lighter than the stable 123Sb tend to decay by β+ decay, and those that are heavier tend to decay by β− decay, with some exceptions.[18] Antimony is the lightest element to have an isotope with an alpha decay branch, excluding 8Be and other light nuclides with beta-delayed alpha emission.[18]

Occurrence

See also: Category:Antimonide minerals and Category:Antimonate minerals
Stibnite, China CM29287 Carnegie Museum of Natural History specimen on display in Hillman Hall of Minerals and Gems

The abundance of antimony in the

parts per million,[19] comparable to thallium at 0.5 ppm and silver at 0.07 ppm. It is the 63rd most abundant element in the crust. Even though this element is not abundant, it is found in more than 100 mineral species.[20] Antimony is sometimes found natively (e.g. on Antimony Peak), but more frequently it is found in the sulfide stibnite (Sb2S3) which is the predominant ore mineral.[19]

Compounds

See also: Category:Antimony compounds

Antimony compounds are often classified according to their oxidation state: Sb(III) and Sb(V). The +5 oxidation state is more common.[21]

Oxides and hydroxides

oxoacids
, and react with acids to form antimony salts.

Antimonous acid Sb(OH)
3 is unknown, but the conjugate base sodium antimonite ([Na
3SbO
3]
4) forms upon fusing sodium oxide and Sb
4O
6.[24] Transition metal antimonites are also known.[25]: 122  Antimonic acid exists only as the hydrate HSb(OH)
6, forming salts as the antimonate anion Sb(OH)−
6. When a solution containing this anion is dehydrated, the precipitate contains mixed oxides.[25]: 143 

The most important antimony ore is stibnite (Sb
2S
3). Other sulfide minerals include pyrargyrite (Ag
3SbS
3), zinkenite, jamesonite, and boulangerite.[26] Antimony pentasulfide is non-stoichiometric, which features antimony in the +3 oxidation state and S–S bonds.[27] Several thioantimonides are known, such as [Sb
6S
10]2−
 and [Sb
8S
13]2−
.[28]

Halides

Antimony forms two series of halides: SbX
3 and SbX
5. The trihalides SbF
3, SbCl
3, SbBr
3, and SbI
3 are all molecular compounds having trigonal pyramidal molecular geometry.

The trifluoride SbF
3 is prepared by the reaction of Sb
2O
3 with HF:[29]

Sb
2O
3 + 6 HF → 2 SbF
3 + 3 H
2O

It is

Lewis acidic and readily accepts fluoride ions to form the complex anions SbF−
4 and SbF2−
5. Molten SbF
3 is a weak electrical conductor. The trichloride SbCl
3 is prepared by dissolving Sb
2S
3 in hydrochloric acid:[30]

Sb
2S
3 + 6 HCl → 2 SbCl
3 + 3 H
2S

Arsenic sulfides are not readily attacked by the hydrochloric acid, so this method offers a route to As-free Sb.

Structure of gaseous SbF5

The pentahalides SbF
5 and SbCl
5 have trigonal bipyramidal molecular geometry in the gas phase, but in the liquid phase, SbF
5 is polymeric, whereas SbCl
5 is monomeric.[31] SbF
5 is a powerful Lewis acid used to make the superacid fluoroantimonic acid ("H2SbF7").

Oxyhalides are more common for antimony than for arsenic and phosphorus. Antimony trioxide dissolves in concentrated acid to form oxoantimonyl compounds such as SbOCl and (SbO)
2SO
4.[32]

Antimonides, hydrides, and organoantimony compounds

Compounds in this class generally are described as derivatives of Sb3−. Antimony forms antimonides with metals, such as indium antimonide (InSb) and silver antimonide (Ag
3Sb).[33] The alkali metal and zinc antimonides, such as Na3Sb and Zn3Sb2, are more reactive. Treating these antimonides with acid produces the highly unstable gas stibine, SbH
3:[34]

Sb3−
 + 3 H+
 → SbH
3

Stibine can also be produced by treating Sb3+
 salts with hydride reagents such as

thermodynamically unstable and thus antimony does not react with hydrogen directly.[35]

Organoantimony compounds are typically prepared by alkylation of antimony halides with Grignard reagents.[36] A large variety of compounds are known with both Sb(III) and Sb(V) centers, including mixed chloro-organic derivatives, anions, and cations. Examples include triphenylstibine (Sb(C6H5)3) and pentaphenylantimony (Sb(C6H5)5).[37]

History

An unshaded circle surmounted by a cross.
One of the alchemical symbols for antimony

predynastic Egypt as an eye cosmetic (kohl) as early as about 3100 BC, when the cosmetic palette was invented.[38]

An artifact, said to be part of a vase, made of antimony dating to about 3000 BC was found at Telloh, Chaldea (part of present-day Iraq), and a copper object plated with antimony dating between 2500 BC and 2200 BC has been found in Egypt.[15] Austen, at a lecture by Herbert Gladstone in 1892, commented that "we only know of antimony at the present day as a highly brittle and crystalline metal, which could hardly be fashioned into a useful vase, and therefore this remarkable 'find' (artifact mentioned above) must represent the lost art of rendering antimony malleable."[39]

The British archaeologist Roger Moorey was unconvinced the artifact was indeed a vase, mentioning that Selimkhanov, after his analysis of the Tello object (published in 1975), "attempted to relate the metal to Transcaucasian natural antimony" (i.e. native metal) and that "the antimony objects from Transcaucasia are all small personal ornaments."[39] This weakens the evidence for a lost art "of rendering antimony malleable".[39]

The Roman scholar Pliny the Elder described several ways of preparing antimony sulfide for medical purposes in his treatise Natural History, around 77 AD.[40] Pliny the Elder also made a distinction between "male" and "female" forms of antimony; the male form is probably the sulfide, while the female form, which is superior, heavier, and less friable, has been suspected to be native metallic antimony.[41]

The Greek naturalist Pedanius Dioscorides mentioned that antimony sulfide could be roasted by heating by a current of air. It is thought that this produced metallic antimony.[40]

The Italian metallurgist Vannoccio Biringuccio described a procedure to isolate antimony.

Antimony was frequently described in alchemical manuscripts, including the Summa Perfectionis of

Basilius Valentinus in the 15th century; if it were authentic, which it is not, it would predate Biringuccio.[b][16][46]

The metal antimony was known to German chemist Andreas Libavius in 1615 who obtained it by adding iron to a molten mixture of antimony sulfide, salt and potassium tartrate. This procedure produced antimony with a crystalline or starred surface.[40]

With the advent of challenges to phlogiston theory, it was recognized that antimony is an element forming sulfides, oxides, and other compounds, as do other metals.[40]

The first discovery of naturally occurring pure antimony in the

Swedish scientist and local mine district engineer Anton von Swab in 1783; the type-sample was collected from the Sala Silver Mine in the Bergslagen mining district of Sala, Västmanland, Sweden.[47][48]

Etymology

The medieval Latin form, from which the modern languages and late

alchemists being monks, and some antimony compounds being poisonous.[50]

Another popular etymology is the hypothetical Greek word ἀντίμόνος antimonos, "against aloneness", explained as "not found as metal", or "not found unalloyed".[15] However, ancient Greek would more naturally express the pure negative as α- ("not").[51] Edmund Oscar von Lippmann conjectured a hypothetical Greek word ανθήμόνιον anthemonion, which would mean "floret", and cites several examples of related Greek words (but not that one) which describe chemical or biological efflorescence.[52]

The early uses of antimonium include the translations, in 1050–1100, by Constantine the African of Arabic medical treatises.[52] Several authorities believe antimonium is a scribal corruption of some Arabic form; Meyerhof derives it from ithmid;[53] other possibilities include athimar, the Arabic name of the metalloid, and a hypothetical as-stimmi, derived from or parallel to the Greek.[54]: 28 

The standard chemical symbol for antimony (Sb) is credited to

Jöns Jakob Berzelius, who derived the abbreviation from stibium.[55]

The ancient words for antimony mostly have, as their chief meaning, kohl, the sulfide of antimony.[citation needed]

The Egyptians called antimony mśdmt[56]: 230 [57]: 541  or stm.[58]

The Arabic word for the substance, as opposed to the cosmetic, can appear as إثمد ithmid, athmoud, othmod, or uthmod.

loan word from Arabic or from Egyptian stm.[58]


Production

Process

The extraction of antimony from ores depends on the quality and composition of the ore. Most antimony is mined as the sulfide; lower-grade ores are concentrated by froth flotation, while higher-grade ores are heated to 500–600 °C, the temperature at which stibnite melts and separates from the gangue minerals. Antimony can be isolated from the crude antimony sulfide by reduction with scrap iron:[60]

Sb
2S
3 + 3 Fe → 2 Sb + 3 FeS

The sulfide is converted to an oxide by roasting. The product is further purified by vaporizing the volatile antimony(III) oxide, which is recovered.[30] This sublimate is often used directly for the main applications, impurities being arsenic and sulfide.[61][62] Antimony is isolated from the oxide by a carbothermal reduction:[60][61]

2 Sb
2O
3 + 3 C → 4 Sb + 3 CO
2

The lower-grade ores are reduced in blast furnaces while the higher-grade ores are reduced in reverberatory furnaces.[60]

World antimony output in 2010[63]
World production trend of antimony

Top producers and production volumes

In 2022, according to the

US Geological Survey, China accounted for 54.5% of total antimony production, followed in second place by Russia with 18.2% and Tajikistan with 15.5%.[63]

Antimony mining in 2022[63]
Country Tonnes % of total
 China 60,000 54.5
 Russia 20,000 18.2
 Tajikistan 17,000 15.5
 Myanmar 4,000 3.6
 Australia 4,000 3.6
Top 5 105,000 95.5
Total world 110,000 100.0

Chinese production of antimony is expected to decline in the future as mines and smelters are closed down by the government as part of pollution control. Especially due to an environmental protection law having gone into effect in January 2015[64] and revised "Emission Standards of Pollutants for Stanum, Antimony, and Mercury" having gone into effect, hurdles for economic production are higher.

Reported production of antimony in China has fallen and is unlikely to increase in the coming years, according to the Roskill report. No significant antimony deposits in China have been developed for about ten years, and the remaining economic reserves are being rapidly depleted.[65]

Reserves

World antimony reserves in 2022[63]
Country Reserves
(tonnes)
 China 350,000
 Russia 350,000
 Bolivia 310,000
 Kyrgyzstan 260,000
 Myanmar 140,000
 Australia 120,000
 Turkey 100,000
 Canada 78,000
 United States 60,000
 Tajikistan 50,000
Total world >1,800,000

Supply risk

For antimony-importing regions such as Europe and the U.S., antimony is considered to be a

critical mineral for industrial manufacturing that is at risk of supply chain disruption. With global production coming mainly from China (74%), Tajikistan (8%), and Russia (4%), these sources are critical to supply.[66][67]

Applications

Approximately 48% of antimony is consumed in

lead–acid batteries, and 8% in plastics.[60]

Flame retardants

Antimony is mainly used as the

fiberglass composites for such items as light aircraft engine covers. The resin will burn in the presence of an externally generated flame, but will extinguish when the external flame is removed.[30][74]

Alloys

Antimony forms a highly useful

lead-free" solders contain 5% Sb),[78] in pewter,[79] and in hardening alloys with low tin content in the manufacturing of organ pipes
.

Other applications

InSb infrared detector manufactured by Mullard in the 1960s

Three other applications consume nearly all the rest of the world's supply.[60] One application is as a stabilizer and catalyst for the production of polyethylene terephthalate.[60] Another is as a fining agent to remove microscopic bubbles in glass, mostly for TV screens[80] – antimony ions interact with oxygen, suppressing the tendency of the latter to form bubbles.[81] The third application is pigments.[60]

In the 1990s antimony was increasingly being used in

alloy junction transistors were doped with tiny beads of a lead-antimony alloy.[83] Indium antimonide (InSb) is used as a material for mid-infrared detectors.[84][85][86]

The material Ge2Sb2Te5 is used as for phase-change memory, a type of computer memory.

Biology and medicine have few uses for antimony. Treatments containing antimony, known as

keratinized
tissues in animals.

Antimony-based drugs, such as

domestic animals. Besides having low therapeutic indices, the drugs have minimal penetration of the bone marrow, where some of the Leishmania amastigotes reside, and curing the disease – especially the visceral form – is very difficult.[90] Elemental antimony as an antimony pill was once used as a medicine. It could be reused by others after ingestion and elimination.[91]

Antimony-124 is used together with beryllium in neutron sources; the gamma rays emitted by antimony-124 initiate the photodisintegration of beryllium.[96][97] The emitted neutrons have an average energy of 24 keV.[98] Natural antimony is used in startup neutron sources
.

Historically, the powder derived from crushed antimony (kohl) has been applied to the eyes with a metal rod and with one's spittle, thought by the ancients to aid in curing eye infections.[99] The practice is still seen in Yemen and in other Muslim countries.[100]

Precautions

Antimony and many of its compounds are

toxic, and the effects of antimony poisoning are similar to arsenic poisoning. The toxicity of antimony is far lower than that of arsenic; this might be caused by the significant differences of uptake, metabolism and excretion between arsenic and antimony. The uptake of antimony(III) or antimony(V) in the gastrointestinal tract is at most 20%. Antimony(V) is not quantitatively reduced to antimony(III) in the cell (in fact antimony(III) is oxidised to antimony(V) instead[101]
).

Since methylation of antimony does not occur, the excretion of antimony(V) in urine is the main way of elimination.[102] Like arsenic, the most serious effect of acute antimony poisoning is cardiotoxicity and the resulting myocarditis; however, it can also manifest as Adams–Stokes syndrome, which arsenic does not. Reported cases of intoxication by antimony equivalent to 90 mg antimony potassium tartrate dissolved from enamel has been reported to show only short term effects. An intoxication with 6 g of antimony potassium tartrate was reported to result in death after three days.[103]

Inhalation of antimony dust is harmful and in certain cases may be fatal; in small doses, antimony causes headaches, dizziness, and depression. Larger doses such as prolonged skin contact may cause dermatitis, or damage the kidneys and the liver, causing violent and frequent vomiting, leading to death in a few days.[104]

Antimony is incompatible with strong

halogen acids, chlorine, or fluorine. It should be kept away from heat.[105]

Antimony

fruit juice concentrates (for which no guidelines are established) produced in the UK were found to contain up to 44.7 μg/L of antimony, well above the EU limits for tap water of 5 μg/L.[108]
The guidelines are:

The tolerable daily intake (TDI) proposed by WHO is 6 μg antimony per kilogram of body weight.[109] The immediately dangerous to life or health (IDLH) value for antimony is 50 mg/m3.[112]

Toxicity

Certain compounds of antimony appear to be toxic, particularly antimony trioxide and antimony potassium tartrate.[113] Effects may be similar to arsenic poisoning.[114] Occupational exposure may cause respiratory irritation, pneumoconiosis, antimony spots on the skin, gastrointestinal symptoms, and cardiac arrhythmias. In addition, antimony trioxide is potentially carcinogenic to humans.[115]

Adverse health effects have been observed in humans and animals following inhalation, oral, or dermal exposure to antimony and antimony compounds.

dental decay.[116]

Notes

  1. ^ The thermal expansion is anisotropic: the parameters (at 20 °C) for each crystal axis are αah = 8.24×10−6/K, αch = 16.62×10−6/K, and αaverage = αV/3 = 11.04×10−6/K.[3]
  2. Johann Thölde (c. 1565 – c. 1624). Professional historians now agree the Currus Triumphalis ... was written after the middle of the 16th century and Thölde was likely its author.[44] Harold Jantz was perhaps the only modern scholar to deny Thölde's authorship, but he too agrees the work dates from after 1550.[45]

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  54. ^
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  59. LSJ, s.v., vocalisation, spelling, and declension vary
  60. Celsus, 6.6.6 ff
  61. Pliny Natural History 33.33
  62. Lewis and Short: Latin Dictionary
  63. OED, s. "antimony"
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    External links

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