Antimon Chemische Eigenschaften,Einsatz,Produktion Methoden
ERSCHEINUNGSBILD
SILBER-WEISSE, GLäNZENDE, HARTE, SPRöDE STüCKE ODER DUNKELGRAUES PULVER
PHYSIKALISCHE GEFAHREN
Staubexplosion der pulverisierten oder granulierten Substanz in Gemischen mit Luft möglich.
CHEMISCHE GEFAHREN
Beim Verbrennen Bildung von giftigen Rauchen (Antimonoxide; siehe ICSC 0012). Reagiert heftig mit Oxidationsmitteln, Säuren, Halogenen und Metallpulver. Feuer- und Explosionsgefahr. Bei Kontakt mit Säuren können giftige Gase freigesetzt werden (Stibin; siehe ICSC 0776).
ARBEITSPLATZGRENZWERTE
TLV: 0.5 mg/m?(als TWA) (ACGIH 2006).
MAK: Krebserzeugend Kategorie 2; Keimzellmutagen Kategorie 3B (DFG 2006).
AUFNAHMEWEGE
Aufnahme in den Körper durch Inhalation des Aerosols.
INHALATIONSGEFAHREN
Eine gesundheitsschädliche Partikelkonzentration in der Luft kann schnell erreicht werden durch Dispergieren.
WIRKUNGEN BEI KURZZEITEXPOSITION
WIRKUNGEN BEI KURZZEITEXPOSITION: Reizt die Augen möglicherweise mechanisch. Exposition durch Einatmen oder Verschlucken kann zu Magen-Darm-Reizungen führen.
WIRKUNGEN NACH WIEDERHOLTER ODER LANGZEITEXPOSITION
Wiederholter oder andauernder Hautkontakt kann Dermatitis hervorrufen, speziell bei Exposition gegenüber Stäuben. Möglich sind Auswirkungen auf die Lunge mit nachfolgender Staublunge.
LECKAGE
Persönliche Schutzausrüstung: Atemschutzgerät, P2-Filter für schädliche Partikel. Verschüttetes Material in abdichtbaren Behältern sammeln; falls erforderlich durch Anfeuchten Staubentwicklung verhindern.
R-Sätze Betriebsanweisung:
R34:Verursacht Verätzungen.
R51/53:Giftig für Wasserorganismen, kann in Gewässern längerfristig schädliche Wirkungen haben.
R20/22:Gesundheitsschädlich beim Einatmen und Verschlucken.
R36/37/38:Reizt die Augen, die Atmungsorgane und die Haut.
R36/38:Reizt die Augen und die Haut.
S-Sätze Betriebsanweisung:
S60:Dieses Produkt und sein Behälter sind als gefährlicher Abfall zu entsorgen.
S61:Freisetzung in die Umwelt vermeiden. Besondere Anweisungen einholen/Sicherheitsdatenblatt zu Rate ziehen.
S36/37/39:Bei der Arbeit geeignete Schutzkleidung,Schutzhandschuhe und Schutzbrille/Gesichtsschutz tragen.
S26:Bei Berührung mit den Augen sofort gründlich mit Wasser abspülen und Arzt konsultieren.
Beschreibung
Antimony (Sb) has been known since antiquity, and its early
use as a cosmetic continues even today. Often mixed with lead
or other heavy metals, this mascara-type cosmetic is known as
kohl. Believed to possess powers to shield the eye from the sun
and disease, it served purposes in both cosmetics and mysticism.
Antimony has been found in many artifacts in the Middle
East, and seems to have been used in the creation of small
personal ornamentation or vessels.
Chemische Eigenschaften
Antimony is a silvery-white metal found in the earth’s crust. It is insoluble in hot or
cold water, but soluble in hot concentrated sulfuric acid and hot nitric acid, and reacts
with oxidizing acids and halogens (fl uorine, chlorine, or bromine). It does not react with
water at room temperature, but will ignite and burn in air at higher temperatures. Ores
of antimony are mined and later mixed with other metals to form antimony alloys,
which are used in lead storage batteries, solder, sheet and pipe metal, bearings, castings, and pewter. Antimony oxide is added to textiles and plastics to prevent them from
catching fi re. It is also used in paints, ceramics, and fi reworks, and as enamels for plastics, metal, and glass. Antimony is alloyed with other metals, such as lead, to increase
its hardness and strength; its primary use is in antimonial lead, which is used in grid
metal for lead acid storage batteries. Antimony salts are used in the treatment of leishmaniasis and schistosomiasis.
Physikalische Eigenschaften
Physically, antimony's properties are related to sulfur and some of the nonmetals, butchemically, its properties are related to metals. It behaves like a metal and is often found innature along with other metals. In its pure form it is rather hard and brittle with a grayishcrystal structure.
Roughly 1/20th of the thermal conductivity
of copper. The thermal conductivity of antimony
depends on the grain size and the direction in the
crystal. Electrical resistivity at 0℃: 30.0×10
-6Ω cm; Molar susceptibility at 20℃: -99.0×10
-6.
Isotopes
There are 53 isotopes of antimony. They range from Sb-103 to Sb-139 (a fewhave two forms). Their half-lives range from 150 nanoseconds to 2.7 years. The twostable isotopes of antimony and their contribution to the natural abundance of antimonyon Earth are as follows: Sb-121 = 57.21% and Sb-123 = 42.79%.
Origin of Name
The element’s name comes from the Greek words anti and minos,
which mean “not alone,” and antimony’s symbol (Sb) is derived from the name for its
ancient source mineral, stibnium.
Occurrence
Although antimony is not a rare metal, it is not well known, despite having been knownand used for many centuries. It is the 63rd most abundant element on Earth, and it occursmainly as sulfide ores or in combination with the ores of other metals. The ore that is theprimary source of antimony is the mineral stibnite (antimony sulfide, Sb
2S
3). Antimony is alsofound in copper, silver, and lead ores. Breithauptite (NiSb) and ullmanite (NiSbS) are twoores containing nickel. Dicrasite (Ag
2Sb) and pyrargyrite (Ag
3SbS
3) are silver ores containingsome antimony.
Charakteristisch
There are two allotropes of antimony. The native metallic form is one allotrope, and theother allotrope is an amorphous grayish form. Antimony is a true metalloid that is brittle witha low melting point. And similar to nonmetals, it is a poor conductor of heat and electricity.
Antimony is unique in that when it solidifies from a molten liquid state to a solid state, itexpands, which is just the opposite of most metals. This is useful in making some typesettingcastings in which the expansion assures an accurate reproduction of the letter mold.
Verwenden
Antimony is used to make alloys such asBabbit metal, white metal, and hard lead; inbullets and fireworks; and for coating metals.
Also, it is used in lead storage batteries,solder bearings, castings and pewter. Antimonyoxide has numerous applications. It isused in paints, ceramics and fireworks andis added to textiles. The average concentrationof antimony in the urban air in USA isestimates as 0.001μg/m
3.
Definition
antimony: Symbol Sb. An elementbelonging to group 15 (formerly VB)of the periodic table; a.n. 51; r.a.m.121.75; r.d. 6.68; m.p. 630.5°C; b.p.1750°C. Antimony has several allotropes.The stable form is a bluishwhitemetal. Yellow antimony andblack antimony are unstable nonmetallicallotropes made at low temperatures.The main source isstibnite (Sb
2S
3), from which antimonyis extracted by reduction withiron metal or by roasting (to give theoxide) followed by reduction withcarbon and sodium carbonate. Themain use of the metal is as an alloyingagent in lead-accumulator plates,type metals, bearing alloys, solders,Britannia metal, and pewter. It is alsoan agent for producing pearlitic castiron. Its compounds are used inflame-proofing, paints, ceramics,enamels, glass dyestuffs, and rubbertechnology. The element will burn inair but is unaffected by water or diluteacids. It is attacked by oxidizingacids and by halogens. It was first reportedby Tholden in 1450.
Manufacturing Process
Antimony metal is recovered from ore primarily by pyrometallurgical techniques. Either antimony(III) sulfide is converted into the oxide, which is then reduced, or the ore is partially roasted and allowed to react with sulfide to form the metal and sulfur dioxide. Sulfide ores with antimony contents between 5 and 25% are roasted to give volatile Sb2O3, which is reduced directly to the metal. In many smelters mixed oxide – sulfide ores are processed in water-jacketed furnaces together with recycled material and byproducts containing antimony. Reverberatory furnaces are used mostly for reducing rich oxide materials.
Allgemeine Beschreibung
A silvery or gray solid in the form of dust. Denser than water and insoluble in water. Toxic by inhalation and by ingestion. May burn and emit toxic fumes if heated or exposed to flames. Used to make electric storage batteries and semiconductors.
Reaktivität anzeigen
ANTIMONY is spontaneously flammable in fluorine, chlorine, and bromine. With iodine, the reaction produces heat, which can cause flame or even an explosion if the quantities are great enough [Mellor 9:379 1946-47]. Even at 10° C. bromine trifluoride reacts with antimony incandescently. Bromine trifluoride reacts similarly with arsenic, boron, bromine, iodine, phosphorus, and sulfur [Mellor 2:113 1946-47]. Bromoazide explodes on contact with antimony, arsenic, phosphorus, silver foil, or sodium. Antimony is very shock sensitive. Explosions of chloric acid have been due to the formation of unstable compounds with antimony, bismuth, ammonia, and organic matter [Chem. Abst. 46:2805e 1952]. The reaction of finely divided antimony and nitric acid can be violent [Pascal 10:504 1931-34]. Powdered antimony mixed with potassium nitrate explodes when heated [Mellor 9:282 1946-47]. When antimony or arsenic and solid potassium permanganate are ground together, the metals ignite [Mellor 12:322 1946-47]. Sodium peroxide oxidizes antimony, arsenic, copper, potassium, tin, and zinc with incandescence [Mellor 2:490-93 1946-47].
Hazard
The powder and dust of antimony are toxic and can cause damage to the lungs. The fumesof antimony halogens (chlorides and fluorides) are especially dangerous when inhaled or incontact the skin.
Many of the salts of antimony are carcinogenic and can cause lung cancer if inhaled, as wellas other cancers if ingested. This is a major hazard with the radioisotopes of antimony used inindustry. Some of its sulfide compounds are explosive.
Health Hazard
The toxicity of antimony is of low order,much less poisonous than arsenic. The symptoms of acute poisoning include weightloss, loss of hair, eosinophilia, and congestionof heart, liver, and kidney. GI disorder(vomiting and diarrhea) and respiratory distressmay arise from high doses. Chronic oralexposure may cause disorder in blood andliver. The toxic routes are primarily inhalationof its dusts or fumes, skin absorption oringestion of contaminated food.
Brandgefahr
May react violently or explosively on contact with water. Some are transported in flammable liquids. May be ignited by friction, heat, sparks or flames. Some of these materials will burn with intense heat. Dusts or fumes may form explosive mixtures in air. Containers may explode when heated. May re-ignite after fire is extinguished.
Pharmazeutische Anwendungen
Antimony presents itself
in a metallic grey form. Antimony is obtained from stibnite (Sb
2S
3) after reduction with iron.
Industrielle Verwendung
Antimony is a bluish-white metal, symbol Sb,with a crystalline scalelike structure that exhibitspoor electrical and heat conductivity. It isbrittle and easily reduced to powder. It is neithermalleable nor ductile and is used only in alloysor in its chemical compounds. Like arsenic andbismuth, it is sometimes referred to as a metalloid,but in mineralogy it is called a semimetal.The element is available commercially in99.999+% purity and is finding increasing usein semiconductor technology.
Antimony is produced either by roasting thesulfide with iron, or by roasting the sulfide andreducing the sublimate of Sb4O6 thus producedwith carbon; high-purity antimony is producedby electrolytic refining. Antimony is one of thefew elements that exhibits the unique propertyof expanding on solidification. Antimony isordinarily stable and not readily attacked by airor moisture. Under controlled conditions it willreact with O2 to form oxides. The chief uses ofantimony are in alloys, particularly for hardeninglead-base alloys.
Antimony imparts hardness and a smoothsurface to soft-metal alloys, and alloys containingantimony expand on cooling, thus reproducingthe fine details of the mold. This propertymakes it valuable for type metals. When alloyedwith lead, tin, and copper, it forms the babbittmetals used for machinery bearings. It is alsomuch used in white alloys for pewter utensils.Its compounds are used widely for pigments.
Sicherheitsprofil
An experimental poison
by intraperitoneal route. Questionable
carcinogen with experimental carcinogenic
data. Moderate fire and explosion hazard in
the forms of dust and vapor when exposed
to heat or flame. See also POWDERED
METALS. When heated or on contact with
acid it emits toxic fumes of SbH3.
Electrolysis of acid sulfides and stirred Sb
halide yields explosive Sb. It can react
violently with NH4NO3, halogens, BrN3,
BrF3, HClO3, Cl0, ClF3, HNO3, m03,
KMn04, K2O2, NaNO3, oxidants.
mögliche Exposition
Exposure to antimony may occur during
mining, smelting or refining; alloy and abrasive manufacture;
and typesetting in printing. Antimony is widely
used in the production of alloys, imparting increased hardness,
mechanical strength, corrosion resistance, and a low
coefficient of friction. Some of the important alloys are
Babbitt, pewter, white metal, Britannia metal and bearing
metal (which are used in bearing shells), printing-type,
metal, storage battery plates, cable sheathing, solder, ornamental
castings, and ammunition. Pure antimony compounds
are used as abrasives, pigments, flame-proofing
compounds, plasticizers, and catalysts in organic synthesis;
they are also used in the manufacture of tartar emetic,
paints, lacquers, glass, pottery, enamels, glazes, pharmaceuticals,
pyrotechnics, matches, and explosives. In addition,
they are used in dyeing, for blueing steel; and in coloring
aluminum pewter; and zinc. A highly toxic gas, stibine,
may be released from the metal under certain conditions.
Carcinogenicity
Existing experimental data suggest that antimony may be an animal carcinogen, but there is
lack of data on the possible carcinogenic properties of antimony and antimony compounds for human exposures. The ACGIH refers to unpublished data on a large antimony smelter in the United Kingdom in the 1960s where workers were exposed to antimony trioxide ranging from 0.5 to 40mg/m
3. The data may indicate increased mortality in lung cancer among the heavily exposed workers, but the workers were also exposed to zirconium making the data cited dif?cult to interpret.
Environmental Fate
The toxicity of Sb is a function of the water solubility and the
oxidation state of the Sb species under consideration. Antimony(
III) is generallymore toxic than antimony(V) and inorganic
forms are thought to be more toxic than organic forms. Stibane
gas (SbH3) when inhaled is the most toxic. Antimony toxicity
often parallels that of arsenic, although antimony salts are less
readily absorbed than arsenic. It is presumed that antimony, like
arsenic, complexes with sulfhydryl groups of essential enzymes
and other proteins. By analogy, antimony can uncouple oxidative
phosphorylation, which would inhibit the production of energy
necessary for cellular functions. Antimony’s trivalent compounds
are more toxic than its pentavalent compounds.
Versand/Shipping
UN2871 Antimony powder, Hazard Class: 6.1;
Labels: 6.1-Poisonous materials.
Structure and conformation
The space lattice of most stable metallic antimony (often called gray antimony) belongs to the hexagonal system, and its arsenic type structure (two atoms within a unit cell) has a lattice constant of a=0.449762 nm, a=57°6.6', u=0.233. Black antimony and yellow antimony are known, but these are unstable and transform to metallic antimony
Inkompatibilitäten
Pyrophoric. Finely dispersed powder
may form explosive mixture in air. Strong oxidizers; strong
acids , produce a violent
reaction, and deadly stibine gas (antimony hydride). Heat
forms stibine gas. Mixtures with nitrates or halogenated
compounds may cause combustion. Forms an explosive
mixture with chloric and perchloric acid. Note: Stibine is
formed when antimony is exposed to nascent (freshly
formed) hydrogen.
Waste disposal
Recovery and recycling is an
option to disposal which should be considered for scrap antimony
and spent catalysts containing antimony. Dissolve
spilled material in minimum amount of concentrated HCl.
Add water, until white precipitate appears. Then acidify to dissolve
again. Saturate with H2S. Filter, wash and dry
the precipitate and return to supplier. Consult with environmental
regulatory agencies for guidance on acceptable disposal
practices. Generators of waste containing this contaminant
(≥100 kg/mo) must conform with EPA regulations governing
storage, transportation, treatment, and waste disposal.
Vorsichtsmaßnahmen
Antimony trioxide is incompatible with bromine trifl uoride, strong acids, strong bases,
reducing agents, perchloric acid, and chlorinated rubber. The release of the deadly gas,
stibine, and its inhalation cause adverse effects on the respiratory, gastrointestinal, and
cardiovascular systems. Workers must wear impervious protective clothing, including
boots, gloves, laboratory coat, apron or coveralls, as appropriate, to prevent skin contact.
Antimon Upstream-Materialien And Downstream Produkte
Upstream-Materialien
Downstream Produkte
