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Antimony

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From Wikipedia, the free encyclopedia
Not to be confused withantinomy orantiphony.
This article is about the element. For other uses, seeAntimony (disambiguation).

Chemical element with atomic number 51 (Sb)
Antimony, 51Sb
Antimony
Pronunciation
Appearancesilvery lustrous gray
Standard atomic weightAr°(Sb)
Antimony in theperiodic table
HydrogenHelium
LithiumBerylliumBoronCarbonNitrogenOxygenFluorineNeon
SodiumMagnesiumAluminiumSiliconPhosphorusSulfurChlorineArgon
PotassiumCalciumScandiumTitaniumVanadiumChromiumManganeseIronCobaltNickelCopperZincGalliumGermaniumArsenicSeleniumBromineKrypton
RubidiumStrontiumYttriumZirconiumNiobiumMolybdenumTechnetiumRutheniumRhodiumPalladiumSilverCadmiumIndiumTinAntimonyTelluriumIodineXenon
CaesiumBariumLanthanumCeriumPraseodymiumNeodymiumPromethiumSamariumEuropiumGadoliniumTerbiumDysprosiumHolmiumErbiumThuliumYtterbiumLutetiumHafniumTantalumTungstenRheniumOsmiumIridiumPlatinumGoldMercury (element)ThalliumLeadBismuthPoloniumAstatineRadon
FranciumRadiumActiniumThoriumProtactiniumUraniumNeptuniumPlutoniumAmericiumCuriumBerkeliumCaliforniumEinsteiniumFermiumMendeleviumNobeliumLawrenciumRutherfordiumDubniumSeaborgiumBohriumHassiumMeitneriumDarmstadtiumRoentgeniumCoperniciumNihoniumFleroviumMoscoviumLivermoriumTennessineOganesson
As

Sb

Bi
tinantimonytellurium
Atomic number(Z)51
Groupgroup 15 (pnictogens)
Periodperiod 5
Block p-block
Electron configuration[Kr] 4d10 5s2 5p3
Electrons per shell2, 8, 18, 18, 5
Physical properties
Phaseat STPsolid
Melting point903.78 K ​(630.63 °C, ​1167.13 °F)
Boiling point1908 K ​(1635 °C, ​2975 °F)
Density (at 20° C)6.694 g/cm3[3]
when liquid (at m.p.)6.53 g/cm3
Heat of fusion19.79 kJ/mol
Heat of vaporization193.43 kJ/mol
Molar heat capacity25.23 J/(mol·K)
Vapor pressure
P (Pa)1101001 k10 k100 k
at T (K)8078761011121914911858
Atomic properties
Oxidation statescommon:−3, +3, +5
−2,[4] −1,[4] 0,[5] +1,[6] +2,? +4[7]
ElectronegativityPauling scale: 2.05
Ionization energies
  • 1st: 834 kJ/mol
  • 2nd: 1594.9 kJ/mol
  • 3rd: 2440 kJ/mol
  • (more)
Atomic radiusempirical: 140 pm
Covalent radius139±5 pm
Van der Waals radius206 pm
Color lines in a spectral range
Spectral lines of antimony
Other properties
Natural occurrenceprimordial
Crystal structurerhombohedral (hR2)
Lattice constants
Rhombohedral crystal structure for antimony
a = 0.45066 nm
α = 57.112°
ah = 0.43084 nm
ch = 1.12736 nm (at 20 °C)[3]
Thermal expansion11.04×10−6/K (at 20 °C)[a]
Thermal conductivity24.4 W/(m⋅K)
Electrical resistivity417 nΩ⋅m (at 20 °C)
Magnetic orderingdiamagnetic[8]
Molar magnetic susceptibility−99.0×10−6 cm3/mol[9]
Young's modulus55 GPa
Shear modulus20 GPa
Bulk modulus42 GPa
Speed of sound thin rod3420 m/s (at 20 °C)
Mohs hardness3.0
Brinell hardness294–384 MPa
CAS Number7440-36-0
History
DiscoveryArabic alchemists (before AD 815)
Symbol"Sb": from Latinstibium 'stibnite'
Isotopes of antimony
Main isotopes[10]Decay
abun­dancehalf-life(t1/2)modepro­duct
121Sb57.2%stable
123Sb42.8%stable
125Sbsynth2.7576 yβ125Te
 Category: Antimony
| references

Antimony is achemical element; it hassymbolSb (from Latin stibium) andatomic number 51. A lustrous grey metal ormetalloid, it is found in nature mainly as thesulfide mineralstibnite (Sb2S3). Antimony compounds have been known since ancient times and were powdered for use as medicine and cosmetics, often known by the Arabic namekohl.[11] The earliest known description of this metalloid in the West was written in 1540 byVannoccio Biringuccio.

China is the largest producer of antimony and its compounds, with most production coming from theXikuangshan Mine in Hunan. The industrial methods for refining antimony from stibnite areroasting followed byreduction with carbon, or direct reduction of stibnite withiron.

The most common applications for metallic antimony are inalloys with lead andtin, which have improved properties forsolders,bullets, andplain bearings. It improves the rigidity of lead-alloy plates inlead–acid batteries.Antimony trioxide is a prominent additive forhalogen-containingflame retardants. Antimony is used as adopant insemiconductor devices.

Characteristics

[edit]

Properties

[edit]
A clear vial containing small chunks of a slightly lustrous black solid, labeled "Sb".
A vial containing the metallicallotrope of antimony
An irregular piece of silvery stone with spots of variation in luster and shade.
Native antimony withoxidation products
Crystal structure common to Sb,AsSb and gray As

Antimony is a member ofgroup 15 of theperiodic table, one of the elements calledpnictogens, and has anelectronegativity of 2.05. In accordance with periodic trends, it is more electronegative thantin orbismuth, and less electronegative thantellurium orarsenic. Antimony is stable in air at room temperature but, if heated, it reacts withoxygen to produceantimony trioxide, Sb2O3.[12]

Antimony is a silvery, lustrous gray metalloid with aMohs scale hardness of 3, which is too soft to mark hard objects. Coins of antimony were issued in China'sGuizhou in 1931; durability was poor, and minting was soon discontinued because of its softness and toxicity.[13] Antimony is resistant to attack by acids.

The only stableallotrope of antimony under standard conditions[14] is metallic,brittle, silver-white, and shiny. It crystallises in atrigonal cell,isomorphic withbismuth and the gray allotrope ofarsenic, and is formed when molten antimony is cooled slowly. Amorphous black antimony is formed upon rapid cooling of antimony vapor, and is only stable as a thin film (thickness in nanometres); thicker samples spontaneously transform into the metallic form.[15] It oxidizes in air and may ignite spontaneously. At 100 °C, it gradually transforms into the stable form. The supposed yellow allotrope of antimony, generated only by oxidation ofstibine (SbH3) at −90 °C, is also impure and not a true allotrope;[16][17] above this temperature and in ambient light, it transforms into the more stable black allotrope.[18][19][20] A rareexplosive form of antimony can be formed from the electrolysis ofantimony trichloride, but it always contains appreciable chlorine and is not really an antimony allotrope.[16] When scratched with a sharp implement, anexothermic reaction occurs and white fumes are given off as metallic antimony forms; when rubbed with apestle 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.[12]

Isotopes

[edit]
Main article:Isotopes of antimony

Antimony has two stableisotopes:121Sb with a natural abundance of 57.36% and123Sb with a natural abundance of 42.64%. It also has 35 radioisotopes, of which the longest-lived is125Sb with ahalf-life of 2.75 years. In addition, 29metastable states have been characterized. The most stable of these is120m1Sb with ahalf-life of 5.76 days. Isotopes that are lighter than the stable123Sb tend to decay byβ+ decay, and those that are heavier tend to decay byβ decay, with some exceptions.[21] Antimony is the lightest element to have an isotope with an alpha decay branch, excluding8Be and other light nuclides with beta-delayed alpha emission.[21]

Occurrence

[edit]
See also:Category:Antimonide minerals andCategory:Antimonate minerals
Stibnite, China CM29287 Carnegie Museum of Natural History specimen on display inHillman Hall of Minerals and Gems

The abundance of antimony in the Earth's crust is estimated at 0.2parts per million,[22] comparable tothallium 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.[23] Antimony is sometimes found natively (e.g. onAntimony Peak), but more frequently it is found in the sulfidestibnite (Sb2S3) which is the predominant ore mineral.[22]

Compounds

[edit]
See also:Category:Antimony compounds

Antimony compounds are often classified according to their oxidation state: Sb(III) and Sb(V). The +5oxidation state is more common.[24]

Oxides and hydroxides

[edit]

Antimony trioxide is formed when antimony is burnt in air.[25] In the gas phase, the molecule of the compound isSb
4
O
6
, but it polymerizes upon condensing.[12]Antimony pentoxide (Sb
4
O
10
) can be formed only by oxidation with concentratednitric acid.[26] Antimony also forms a mixed-valence oxide,antimony tetroxide (Sb
2
O
4
), which features both Sb(III) and Sb(V).[26] Unlike oxides ofphosphorus andarsenic, these oxides areamphoteric, do not form well-definedoxoacids, and react with acids to form antimony salts.

Antimonous acidSb(OH)
3
is unknown, but the conjugate base sodium antimonite ([Na
3
SbO
3
]
4
) forms upon fusingsodium oxide andSb
4
O
6
.[27] Transition metal antimonites are also known.[28]: 122  Antimonic acid exists only as the hydrateHSb(OH)
6
, forming salts as the antimonate anionSb(OH)
6
. When a solution containing this anion is dehydrated, the precipitate contains mixed oxides.[28]: 143 

The most important antimony ore isstibnite (Sb
2
S
3
). Other sulfide minerals includepyrargyrite (Ag
3
SbS
3
),zinkenite,jamesonite, andboulangerite.[29]Antimony pentasulfide isnon-stoichiometric, which features antimony in the +3oxidation state and S–S bonds.[30] Several thioantimonides are known, such as[Sb
6
S
10
]2−
and[Sb
8
S
13
]2−
.[31]

Halides

[edit]

Antimony forms two series ofhalides:SbX
3
andSbX
5
. The trihalidesSbF
3
,SbCl
3
,SbBr
3
, andSbI
3
are all molecular compounds havingtrigonal pyramidal molecular geometry.

The trifluorideSbF
3
is prepared by the reaction ofSb
2
O
3
withHF:[32]

Sb
2
O
3
+ 6 HF → 2SbF
3
+ 3H
2
O

It isLewis acidic and readily accepts fluoride ions to form the complex anionsSbF
4
andSbF2−
5
. MoltenSbF
3
is a weakelectrical conductor. The trichlorideSbCl
3
is prepared by dissolvingSb
2
S
3
inhydrochloric acid:[33]

Sb
2
S
3
+ 6 HCl → 2SbCl
3
+ 3H
2
S

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 pentahalidesSbF
5
andSbCl
5
havetrigonal bipyramidal molecular geometry in the gas phase, but in the liquid phase,SbF
5
ispolymeric, whereasSbCl
5
is monomeric.[34]SbF
5
is a powerful Lewis acid used to make thesuperacidfluoroantimonic acid ("H2SbF7").

Oxyhalides are more common for antimony than for arsenic and phosphorus.Antimony trioxide dissolves in concentrated acid to form oxoantimonyl compounds such asSbOCl and(SbO)
2
SO
4
.[35]

Antimonides, hydrides, and organoantimony compounds

[edit]

Compounds in this class generally are described as derivatives of Sb3−. Antimony formsantimonides with metals, such asindium antimonide (InSb) and silver antimonide (Ag
3
Sb
).[36] The alkali metal and zinc antimonides, such as Na3Sb and Zn3Sb2, are more reactive. Treating these antimonides with acid produces the highly unstable gasstibine,SbH
3
:[37]

Sb3−
+ 3H+
SbH
3

Stibine can also be produced by treatingSb3+
salts with hydride reagents such assodium borohydride. Stibine decomposes spontaneously at room temperature. Because stibine has a positiveheat of formation, it isthermodynamically unstable and thus antimony does not react withhydrogen directly.[38]

Organoantimony compounds are typically prepared by alkylation of antimony halides withGrignard reagents.[39] A large variety of compounds are known with both Sb(III) and Sb(V) centers, including mixed chloro-organic derivatives, anions, and cations. Examples includetriphenylstibine (Sb(C6H5)3) andpentaphenylantimony (Sb(C6H5)5).[40]

History

[edit]
An unshaded circle surmounted by a cross.
One of thealchemical symbols for antimony

Antimony(III) sulfide, Sb2S3, was recognized inpredynastic Egypt as an eye cosmetic (kohl) as early as about3100 BC, when thecosmetic palette was invented.[41]

An artifact, said to be part of a vase, made of antimony dating to about 3000 BC was found atTelloh,Chaldea (part of present-dayIraq), and a copper object plated with antimony dating between 2500 BC and 2200 BC has been found inEgypt.[18] Austen, at a lecture byHerbert 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."[42]

The British archaeologistRoger 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."[42] This weakens the evidence for a lost art "of rendering antimony malleable".[42]

The Roman scholarPliny the Elder described several ways of preparing antimony sulfide for medical purposes in his treatiseNatural History, around 77 AD.[43] 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.[44]

The Greek naturalistPedanius Dioscorides mentioned that antimony sulfide could be roasted by heating by a current of air. It is thought that this produced metallic antimony.[43]

The Italian metallurgistVannoccio Biringuccio described a procedure to isolate antimony.

Antimony was frequently described in alchemical manuscripts, including theSumma Perfectionis ofPseudo-Geber, written around the 14th century.[45] A description of a procedure for isolating antimony is later given in the 1540 bookDe la pirotechnia byVannoccio Biringuccio,[46] predating the more famous 1556 book byAgricola,De re metallica. In this context Agricola has been often incorrectly credited with the discovery of metallic antimony. The bookCurrus Triumphalis Antimonii (The Triumphal Chariot of Antimony), describing the preparation of metallic antimony, was published in Germany in 1604. It was purported to be written by aBenedictine monk, writing under the nameBasilius Valentinus in the 15th century; if it were authentic, which it is not, it would predate Biringuccio.[b][19][49]

The metal antimony was known to German chemistAndreas Libavius in 1615 who obtained it by adding iron to a molten mixture of antimony sulfide, salt and potassiumtartrate. This procedure produced antimony with a crystalline or starred surface.[43]

With the advent of challenges tophlogiston theory, it was recognized that antimony is an element forming sulfides, oxides, and other compounds, as do other metals.[43]

The first discovery of naturally occurring pure antimony in theEarth's crust was described by theSwedish scientist and local mine district engineerAnton von Swab in 1783; thetype-sample was collected from theSala Silver Mine in the Bergslagen mining district ofSala,Västmanland, Sweden.[50][51]

Etymology

[edit]

The medieval Latin form, from which the modern languages and lateByzantine Greek take their names for antimony, isantimonium.[52] The origin of that is uncertain, and all suggestions have some difficulty either of form or interpretation. Thepopular etymology, from ἀντίμοναχόςanti-monachos or Frenchantimoine, would mean "monk-killer", which is explained by the fact that many earlyalchemists were monks, and some antimony compounds were poisonous.[53]

Another popular etymology is the hypothetical Greek word ἀντίμόνοςantimonos, "against aloneness", explained as "not found as metal", or "not found unalloyed".[18] However,ancient Greek would more naturally express the pure negative asα- ("not").[54]Edmund Oscar von Lippmann conjectured a hypothetical Greek word ανθήμόνιονanthemonion, which would mean "floret", and cites several examples of related Greek words (but not that one) which describe chemical or biologicalefflorescence.[55]

The early uses ofantimonium include the translations, in 1050–1100, byConstantine the African of Arabic medical treatises.[55] Several authorities believeantimonium is a scribal corruption of some Arabic form; Meyerhof derives it fromithmid;[56] other possibilities includeathimar, the Arabic name of the metalloid, and a hypotheticalas-stimmi, derived from or parallel to the Greek.[57]: 28 

The standard chemical symbol for antimony (Sb) is credited toJöns Jakob Berzelius, who derived the abbreviation fromstibium.[58]

The ancient words for antimony mostly have, as their chief meaning,kohl, the sulfide of antimony.[59]

The Egyptians called antimonymśdmt[60]: 230 [61]: 541  orstm.[62]

The Arabic word for the substance, as opposed to the cosmetic, can appear asإثمدithmid, athmoud, othmod, oruthmod.Littré suggests the first form, which is the earliest, derives fromstimmida, an accusative forstimmi.[57][63] The Greek word στίμμι (stimmi) is used byAttictragic poets of the 5th century BC, and is possibly aloan word from Arabic or from Egyptianstm.[62]

Production

[edit]

Process

[edit]

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 byfroth flotation, while higher-grade ores are heated to 500–600 °C, the temperature at which stibnite melts and separates from thegangue minerals. Antimony can be isolated from the crude antimony sulfide by reduction with scrap iron:[64]

Sb
2
S
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.[33] This sublimate is often used directly for the main applications, impurities being arsenic and sulfide.[65][66] Antimony is isolated from the oxide by a carbothermal reduction:[64][65]

2Sb
2
O
3
+ 3 C → 4 Sb + 3CO
2

The lower-grade ores are reduced inblast furnaces while the higher-grade ores are reduced inreverberatory furnaces.[64]

World antimony output in 2010[67]
World production trend of antimony

Top producers and production volumes

[edit]

In 2022, according to theUS 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%.[67]

Antimony mining in 2022[67]
CountryTonnes% of total
 China60,00054.5
 Russia20,00018.2
 Tajikistan17,00015.5
 Myanmar4,0003.6
 Australia4,0003.6
Top 5105,00095.5
Total world110,000100.0

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[68] 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.[69]

Reserves

[edit]
World antimony reserves in 2022[67]
CountryReserves
(tonnes)
 China350,000
 Russia350,000
 Bolivia310,000
 Kyrgyzstan260,000
 Myanmar140,000
 Australia120,000
 Turkey100,000
 Canada78,000
 United States60,000
 Slovakia60,000
 Tajikistan50,000
Total world>1,800,000

Supply risk

[edit]

For antimony-importing regions, such as Europe and the U.S., antimony is considered to be acritical 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.[70][71]

  • European Union: Antimony is considered a critical raw material for defense, automotive, construction and textiles. The E.U. sources are 100% imported, coming mainly from Turkey (62%), Bolivia (20%) and Guatemala (7%).[70]
  • United Kingdom: TheBritish Geological Survey's 2015 risk list ranks antimony second highest (afterrare earth elements) on the relative supply risk index.[72][73]
  • United States: Antimony is a mineral commodity considered critical to the economic and national security.[74][71] In 2022, no antimony was mined in the U.S.[75]

Applications

[edit]

Approximately 48% of antimony is consumed inflame retardants, 33% inlead–acid batteries, and 8% in plastics.[64]

Flame retardants

[edit]

Antimony is mainly used as thetrioxide forflame-proofing compounds, always in combination with halogenated flame retardants except in halogen-containing polymers. The flame retarding effect of antimony trioxide is produced by the formation of halogenated antimony compounds,[76] which react with hydrogen atoms, and probably also with oxygen atoms and OH radicals, thus inhibiting fire.[77] Markets for these flame-retardants include children's clothing, toys, aircraft, and automobile seat covers. They are also added topolyester resins infiberglasscomposites 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.[33][78]

Alloys

[edit]

Antimony forms a highly usefulalloy with lead, increasing its hardness and mechanical strength. When casting it increases fluidity of the melt and reduces shrinkage during cooling.[79] For most applications involving lead, varying amounts of antimony are used as alloying metal. Inlead–acid batteries, this addition improves plate strength and charging characteristics.[33][80] For sailboats, lead keels are used to provide righting moment, ranging from 600 lbs to over 200 tons for the largest sailing superyachts; to improve hardness and tensile strength of the lead keel, antimony is mixed with lead between 2% and 5% by volume. Antimony is used in antifriction alloys (such asBabbitt metal),[81] in bullets andlead shot,electrical cable sheathing,type metal (for example, forlinotype printing machines[82]),solder (some "lead-free" solders contain 5% Sb),[83] inpewter,[84] and in hardening alloys with lowtin content in the manufacturing oforgan pipes.

Other applications

[edit]
InSb infrared detector manufactured byMullard in the 1960s

Three other applications consume nearly all the rest of the world's supply.[64] One application is as a stabilizer and catalyst for the production ofpolyethylene terephthalate.[64] Another is as a fining agent to remove microscopic bubbles in glass, mostly for TV screens[85] – antimony ions interact with oxygen, suppressing the tendency of the latter to form bubbles.[86] The third application is pigments.[64]

In the 1990s antimony was increasingly being used insemiconductors as adopant inn-typesiliconwafers[87] fordiodes,infrared detectors, andHall-effect devices. In the 1950s, the emitters and collectors of n-p-nalloy junction transistors were doped with tiny beads of a lead-antimony alloy.[88]Indium antimonide (InSb) is used as a material for mid-infrared detectors.[89][90][91]

The materialGe2Sb2Te5 is used as forphase-change memory, a type ofcomputer memory.

Biology and medicine have few uses for antimony. Treatments containing antimony, known asantimonials, are used asemetics.[92] Antimony compounds are used asantiprotozoan drugs.Potassium antimonyl tartrate, or tartar emetic, was once used as an anti-schistosomal drug from 1919 on. It was subsequently replaced bypraziquantel.[93] Antimony and its compounds are used in severalveterinary preparations, such as anthiomaline and lithium antimony thiomalate, as a skin conditioner inruminants.[94] Antimony has a nourishing or conditioning effect onkeratinized tissues in animals.

Antimony-based drugs, such asmeglumine antimoniate, are also considered the drugs of choice for treatment ofleishmaniasis. Early treatments used antimony(III) species (trivalent antimonials), but in 1922Upendranath Brahmachari invented a much safer antimony(V) drug, and since then so-calledpentavalent antimonials have been the standard first-line treatment. However,Leishmania strains inBihar and neighboring regions have developed resistance to antimony.[95] Elemental antimony as anantimony pill was once used as a medicine. It could be reused by others after ingestion and elimination.[96]

Antimony(III) sulfide is used in the heads of somesafety matches.[97][98] Antimony sulfides help to stabilize the friction coefficient in automotive brake pad materials.[99] Antimony is used in bullets, bullet tracers,[100] paint, glass art, and as anopacifier inenamel.Antimony-124 is used together withberyllium inneutron sources; thegamma rays emitted by antimony-124 initiate thephotodisintegration of beryllium.[101][102] The emitted neutrons have an average energy of 24 keV.[103] Natural antimony is used instartup neutron sources.

The powder derived from crushed antimony sulfide (kohl) has been used for millennia as an eye cosmetic. Historically it was applied to the eyes with a metal rod and with one's spittle, and was thought by the ancients to aid in curing eye infections.[104] The practice is still seen inYemen and in other Muslim countries.[105]

Precautions

[edit]
Antimony
Hazards
GHS labelling:
GHS06: ToxicGHS07: Exclamation markGHS08: Health hazardGHS09: Environmental hazard
Danger
H301,H332,H351,H373,H411
P203,P260,P264,P270,P273,P280,P301+P316,P304+P340,P318,P321,P330,P391,P405
Chemical compound

Antimony and many of its compounds aretoxic, and the effects of antimony poisoning are similar toarsenic 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[106]).

Sincemethylation of antimony does not occur, the excretion of antimony(V) in urine is the main way of elimination.[107] Like arsenic, the most serious effect of acute antimony poisoning iscardiotoxicity and the resultingmyocarditis; however, it can also manifest asAdams–Stokes syndrome, which arsenic does not. Reported cases of intoxication by antimony equivalent to 90 mgantimony 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.[108]

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.[109]

Antimony is incompatible with strongoxidizing agents,strong acids,halogen acids,chlorine, orfluorine. It should be kept away from heat.[110]

Antimonyleaches frompolyethylene terephthalate (PET) bottles into liquids.[111] While levels observed forbottled water are belowdrinking water guidelines,[112]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 fortap water of 5 μg/L.[113] The guidelines are:

Thetolerable daily intake (TDI) proposed by WHO is 6 μg antimony per kilogram of body weight.[114] Theimmediately dangerous to life or health (IDLH) value for antimony is 50 mg/m3.[117]

Toxicity

[edit]

Certain compounds of antimony appear to be toxic, particularly antimony trioxide and antimony potassium tartrate.[118] Effects may be similar toarsenic poisoning.[119] 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.[120]

Adverse health effects have been observed in humans and animals following inhalation, oral, or dermal exposure to antimony and antimony compounds.[118] Antimony toxicity typically occurs either due to occupational exposure, during therapy or from accidental ingestion. It is unclear if antimony can enter the body through the skin.[118] The presence of low levels of antimony in saliva may also be associated withdental decay.[121]

Notes

[edit]
  1. ^The thermal expansion isanisotropic: 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. ^Already in 1710 Wilhelm Gottlob Freiherr vonLeibniz, after careful inquiry, concluded the work was spurious, there was no monk named Basilius Valentinus, and the book's author was its ostensible editor,Johann Thölde (c. 1565 – c. 1624). Professional historians now agree theCurrus Triumphalis ... was written after the middle of the 16th century and Thölde was likely its author.[47] Harold Jantz was perhaps the only modern scholar to deny Thölde's authorship, but he too agrees the work dates from after 1550.[48]

References

[edit]
  1. ^"Standard Atomic Weights: Antimony".CIAAW. 1993.
  2. ^Prohaska, Thomas; Irrgeher, Johanna; Benefield, Jacqueline; Böhlke, John K.; Chesson, Lesley A.; Coplen, Tyler B.; Ding, Tiping; Dunn, Philip J. H.; Gröning, Manfred; Holden, Norman E.; Meijer, Harro A. J. (4 May 2022)."Standard atomic weights of the elements 2021 (IUPAC Technical Report)".Pure and Applied Chemistry.doi:10.1515/pac-2019-0603.ISSN 1365-3075.
  3. ^abcArblaster, John W. (2018).Selected Values of the Crystallographic Properties of Elements. Materials Park, Ohio: ASM International.ISBN 978-1-62708-155-9.
  4. ^abSb(−2) and Sb(−1) has been observed in [Sb2]4− and1[Sbn]n−, respectively; seeBoss, Michael; Petri, Denis; Pickhard, Frank; Zönnchen, Peter; Röhr, Caroline (2005). "Neue Barium-Antimonid-Oxide mit den Zintl-Ionen [Sb]3−, [Sb2]4− und1[Sbn]n− / New Barium Antimonide Oxides containing Zintl Ions [Sb]3−, [Sb2]4− and1[Sbn]n−".Zeitschrift für Anorganische und Allgemeine Chemie (in German).631 (6–7):1181–1190.doi:10.1002/zaac.200400546.
  5. ^Anastas Sidiropoulos (2019)."Studies of N-heterocyclic Carbene (NHC) Complexes of the Main Group Elements"(PDF). p. 39.doi:10.4225/03/5B0F4BDF98F60.S2CID 132399530.
  6. ^Sb(I) have been observed inorganoantimony compounds; seeŠimon, Petr; de Proft, Frank; Jambor, Roman; Růžička, Aleš; Dostál, Libor (2010). "Monomeric Organoantimony(I) and Organobismuth(I) Compounds Stabilized by an NCN Chelating Ligand: Syntheses and Structures".Angewandte Chemie International Edition.49 (32):5468–5471.doi:10.1002/anie.201002209.PMID 20602393.
  7. ^Sb(IV) has been observed in[SbCl6]2−, seeNobuyoshi Shinohara; Masaaki Ohsima (2000). "Production of Sb(IV) Chloro Complex by Flash Photolysis of the Corresponding Sb(III) and Sb(V) Complexes in CH3CN and CHCl3".Bulletin of the Chemical Society of Japan.73 (7):1599–1604.doi:10.1246/bcsj.73.1599.
  8. ^Lide, D. R., ed. (2005). "Magnetic susceptibility of the elements and inorganic compounds".CRC Handbook of Chemistry and Physics(PDF) (86th ed.). Boca Raton (FL): CRC Press.ISBN 0-8493-0486-5.
  9. ^Weast, Robert (1984).CRC, Handbook of Chemistry and Physics. Boca Raton, Florida: Chemical Rubber Company Publishing. pp. E110.ISBN 0-8493-0464-4.
  10. ^Kondev, F. G.; Wang, M.; Huang, W. J.; Naimi, S.; Audi, G. (2021)."The NUBASE2020 evaluation of nuclear properties"(PDF).Chinese Physics C.45 (3): 030001.doi:10.1088/1674-1137/abddae.
  11. ^David Kimhi's Commentary on Isaiah 4:30 and I Chronicles 29:2; Hebrew:פוך/כְּחֻל, Aramaic:כּוּחְלִי/צדידא; Arabic:كحل, and which can also refer toantimony trisulfide. See also Z. Dori,Antimony and Henna (Heb.הפוך והכופר), Jerusalem 1983 (Hebrew).
  12. ^abcWiberg and Holleman, p. 758
  13. ^"Metals Used in Coins and Medals". ukcoinpics.co.uk. Archived fromthe original on 26 December 2010. Retrieved16 October 2009.
  14. ^Ashcheulov, A. A.; Manyk, O. N.; Manyk, T. O.; Marenkin, S. F.; Bilynskiy-Slotylo, V. R. (2013). "Some Aspects of the Chemical Bonding in Antimony".Inorganic Materials.49 (8):766–769.doi:10.1134/s0020168513070017.
  15. ^Shen, Xueyang; Zhou, Yuxing; Zhang, Hanyi; Derlinger, Volker L.; Mazzarello, Riccardo; Zhang, Wei (2023). "Surface effects on the crystallization kinetics of amorphous antimony".Nanoscale.15 (37):15259–15267.doi:10.1039/D3NR03536K.PMID 37674458.
  16. ^abLide, D. R., ed. (2001).CRC Handbook of Chemistry and Physics (82nd ed.). Boca Raton, Florida: CRC Press. p. 4-4.ISBN 0-8493-0482-2.
  17. ^Krebs, H.; Schultze-Gebhardt, F.; Thees, R. (1955). "Über die Struktur und die Eigenschaften der Halbmetalle. IX: Die Allotropie des Antimons".Zeitschrift für anorganische und allgemeine Chemie (in German).282 (1–6):177–195.doi:10.1002/zaac.19552820121.
  18. ^abc"Antimony" inKirk-Othmer Encyclopedia of Chemical Technology, 5th ed. 2004.ISBN 978-0-471-48494-3
  19. ^abWang, Chung Wu (1919)."The Chemistry of Antimony"(PDF).Antimony: Its History, Chemistry, Mineralogy, Geology, Metallurgy, Uses, Preparation, Analysis, Production and Valuation with Complete Bibliographies. London, United Kingdom: Charles Geiffin and Co. Ltd. pp. 6–33.Archived(PDF) from the original on 9 October 2022.
  20. ^Norman 1998,pp. 50–51
  21. ^abAudi, Georges; Bersillon, Olivier; Blachot, Jean;Wapstra, Aaldert Hendrik (2003)."The NUBASE evaluation of nuclear and decay properties".Nuclear Physics A.729:3–128.Bibcode:2003NuPhA.729....3A.doi:10.1016/j.nuclphysa.2003.11.001.
  22. ^abGreenwood and Earnshaw, p. 548
  23. ^Antimony minerals. mindat.org
  24. ^Greenwood and Earnshaw, p. 553
  25. ^Reger, Daniel L.; Goode, Scott R. & Ball, David W. (2009).Chemistry: Principles and Practice (3rd ed.). Cengage Learning. p. 883.ISBN 978-0-534-42012-3.
  26. ^abHouse, James E. (2008).Inorganic chemistry. Academic Press. p. 502.ISBN 978-0-12-356786-4.
  27. ^Wiberg and Holleman, p. 763
  28. ^abGodfrey, S. M.; McAuliffe, C. A.; Mackie, A. G. & Pritchard, R. G. (1998). Norman, Nicholas C. (ed.).Chemistry of arsenic, antimony, and bismuth. Springer.ISBN 978-0-7514-0389-3.
  29. ^Wiberg and Holleman, p. 757
  30. ^Long, G.; Stevens, J. G.; Bowen, L. H.; Ruby, S. L. (1969). "The oxidation number of antimony in antimony pentasulfide".Inorganic and Nuclear Chemistry Letters.5: 21.doi:10.1016/0020-1650(69)80231-X.
  31. ^Lees, R.; Powell, A.; Chippindale, A. (2007). "The synthesis and characterisation of four new antimony sulphides incorporating transition-metal complexes".Journal of Physics and Chemistry of Solids.68 (5–6): 1215.Bibcode:2007JPCS...68.1215L.doi:10.1016/j.jpcs.2006.12.010.
  32. ^Wiberg and Holleman, pp. 761–762
  33. ^abcdGrund, Sabina C.; Hanusch, Kunibert; Breunig, Hans J.; Wolf, Hans Uwe (2006) "Antimony and Antimony Compounds" inUllmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim.doi:10.1002/14356007.a03_055.pub2
  34. ^Wiberg and Holleman, p. 761
  35. ^Wiberg and Holleman, p. 764
  36. ^Wiberg and Holleman, p. 760
  37. ^Kahlenberg, Louis (2008).Outlines of Chemistry – A Textbook for College Students. READ BOOKS. pp. 324–325.ISBN 978-1-4097-6995-8.
  38. ^Greenwood and Earnshaw, p. 558
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  40. ^Greenwood and Earnshaw, p. 598
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  43. ^abcdMellor, Joseph William (1964)."Antimony".A comprehensive treatise on inorganic and theoretical chemistry. Vol. 9. p. 339.
  44. ^Pliny,Natural history, 33.33; W.H.S. Jones, theLoeb Classical Library translator, supplies a note suggesting the identifications.
  45. ^Filella, Montserrat, ed. (2021).Antimony. De Gruyter. p. 4.doi:10.1515/9783110668711.ISBN 978-3-11-066871-1.
  46. ^Vannoccio Biringuccio,De la Pirotechnia (Venice (Italy): Curtio Navo e fratelli, 1540), Book 2, chapter 3:Del antimonio & sua miniera, Capitolo terzo (On antimony and its ore, third chapter), pp. 27–28. [Note: Only every second page of this book is numbered, so the relevant passage is to be found on the 74th and 75th pages of the text.] (in Italian)
  47. ^Priesner, Claus; Figala, Karin, eds. (1998).Alchemie. Lexikon einer hermetischen Wissenschaft (in German). München: C.H. Beck.ISBN 3406441068.
  48. ^Harold Jantz Collection of German Baroque Literature Reel Listing.
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  54. ^"Antimony".Oxford English Dictionary (Online ed.).Oxford University Press. (Subscription orparticipating institution membership required.), which considers the derivation a "popular etymology".
  55. ^abvon Lippmann, Edmund Oscar (1919) Entstehung und Ausbreitung der Alchemie, teil 1. Berlin: Julius Springer (in German). pp. 642–5
  56. ^Meyerhof as quoted inSarton 1935, asserts thatithmid orathmoud became corrupted in the medieval "traductions barbaro-latines". TheOED asserts some Arabic form is the origin, and ifithmid is the root, positsathimodium, atimodium, atimonium as intermediates.
  57. ^abEndlich, F. M. (1888)."On Some Interesting Derivations of Mineral Names".The American Naturalist.22 (253):21–32.Bibcode:1888ANat...22...21E.doi:10.1086/274630.JSTOR 2451020.
  58. ^Jöns Jacob Berzelius, "Essay on the cause of chemical proportions, and on some circumstances relating to them: together with a short and easy method of expressing them,"Annals of Philosophy, vol. 2, pages 443–454 (1813) and vol. 3, pages 51–62, 93–106, 244–255, 353–364 (1814). Onp. 52, Berzelius lists the symbol for antimony as "St"; however, starting fromp. 248, Berzelius consistently uses the symbol "Sb" instead.
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  63. ^
    • LSJ,s.v., vocalisation, spelling, and declension vary
    • Celsus, 6.6.6 ff
    • PlinyNatural History 33.33
    • Lewis and Short:Latin Dictionary
    • OED, s. "antimony"
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  65. ^abNorman 1998,p. 45
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Cited sources

[edit]
  • Greenwood, N. N.; Earnshaw, A. (1997).Chemistry of the Elements (2nd ed.). Oxford: Butterworth-Heinemann.ISBN 0-7506-3365-4.
  • Wiberg, Egon; Wiberg, Nils & Holleman, Arnold Frederick (2001).Inorganic chemistry. Academic Press.ISBN 978-0-12-352651-9.

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