アンチモン 化学特性,用途語,生産方法
外観
銀白色の粒状
性質
銀白色の金属アンチモンは半金属の性質をもつ。黄色や黒色の同素体は非金属的性質を示し、黄色アンチモン、黒色アンチモンなどとよばれる。黄色アンチモンは－90℃以上では不安定で黒色アンチモンとなる。高純度の金属塊は表面にきれいな星形の結晶模様がみられ、スターアンチモンとよばれる。常温では空気中で安定であるが、融点以上に熱すると酸化アンチモンとなる。塩素とは常温でも激しく反応して塩化物となる。塩酸には溶けないが、濃硫酸とは二酸化硫黄(いおう)と硫酸塩を生じて溶ける。濃硝酸とはアンチモン酸をつくる。
溶解性
王水及び硝酸を含む塩酸に溶け、水にほとんど溶けない。
解説
Sb．原子番号51の元素．電子配置[Kr]4d105s25p3の周期表15族元素．原子量121.760(1)．質量数121(57.21(5)％)と123(42.79(5)％)の安定同位体と，104～134の30種の放射性同位体が知られる．元素記号は，古くから知られている輝安鉱Sb2S3のstibniteのラテン名stibiumから．元素名は，俗説では，中世ドイツの僧院で薬として食事にまぜたところ，死者が続出したことからとされるが，鉱物のアラビア名からとも，ギリシア語のαντιμονοζ(孤独の敵，単独で産出しないこと)からともいわれる．宇田川榕菴は天保8年(1837年)出版の「舎密開宗」で，私知彪母(スチビウム)と記載している．地殻中の存在度0.2 ppm で乏しい元素であるが，鉱脈中には濃縮されて存在する．2006年の中国の産出量は11万t で世界の産出量の85％ を占める．全埋蔵量の60％ 強も中国．日本はほぼ全量を地金として中国から輸入している．硫化物から鉄で，または酸化物にかえてから炭素で還元して金属を得る．3種類の準安定相が知られるが，通常は，りょう面体構造の片状銀白色の固体．密度6.691 g cm－3．融点630.7 ℃，沸点1750 ℃．固化の際に体積が膨張するので，鋳造に適する．典型的両性元素で半金属元素．森北出版「化学辞典（第2版）
主な性質
- アンチモンは常温で、銀白色の金属光沢。通常の希酸やアルカリには溶けないが、加熱すると青い炎を出して燃える。
- アンチモンはヒ素、ビスマスと共に、半金属とも呼ばれて、半導体に近い性質を持っている。
- インジウムやガリウムと合金をつくり、半導体として使われる。
- 他の金属との合金は、硬度が増し耐摩耗性が向上し、体積を減少させる性質がある。
- 二酸化アンチモンは各種の合成樹脂、合成繊維、ゴムなどの耐火性向上の難燃助材として使用。
用途
化合物製造原料。
用途
金属標準液、半導体、メッキ、合金材料。
存在&製法
地殻中の存在度は小さいが、鉱物としてまとまって産するので採取しやすい。輝安鉱Sb2S3が鉱物としてもっとも重要である。高品位鉱では、粉砕した輝安鉱を鉄屑(てつくず)とともに黒鉛るつぼ中で熱すると鉄によって還元され、金属アンチモンが遊離する。また低品位鉱では、鉱石を焼いて酸化物にしたのち、コークスと共熱して還元する。このようにして得られる粗アンチモンは純度87～94％程度で、これに融剤を加えて融解精製するか（95％）、電解精錬により精製する（99.8％）。最近では半導体製造に用いるため、高純度のものが要求され、帯融解法で純度99.99％以上のものが得られる。アンチモン塩の水溶液に亜鉛を加えると黒色アンチモンが得られ、水素化アンチモンに－90℃で空気を通ずると黄色アンチモンが得られる。
用途
単体としての用途はないが、鉛蓄電池の電極（数％のアンチモンを含む鉛）や活字合金（融点が低く凝固時に膨張する。鉛80％、アンチモン17％、スズ3％などの合金）として利用されている。硫化アンチモンはゴムの加硫などに、このほか色素や触媒に用いる化合物も多い。また、半導体材料として最近その需要が大きい。単体、化合物ともに有毒であり、アンチモン中毒の症状はヒ素中毒に似ている。手当てとしては早く毒物を体外に排出させ、解毒剤としてタンニンを用いるとよい。通常酸化数ⅢとⅤの化合物が存在する。見かけ上、酸化数Ⅳの化合物は酸化数ⅢとⅤの共存する化合物である。
主な用途
- 鉛蓄電池の成分（自動車用）
- 硬鉛鋳物（化学装置）
- 難燃助材（合成樹脂、合成繊維）
- 添加剤（プラスチック、ガラス、光ディスク）
- その他（潤滑剤、電線?ケーブル）
使用上の注意
純度は金属ベースで差数法によって算出したもので、重量又は容量分析等の化学的方法によるものではありません。使用目的により、正確な含量が必要な場合は、それらの方法によって測定する必要があります。
説明
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.
化学的特性
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.
物理的性質
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.
同位体
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%.
名前の由来
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.
天然物の起源
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.
特性
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.
使用
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.
定義
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.
一般的な説明
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.
反応プロフィール
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].
危険性
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.
健康ハザード
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.
火災危険
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.
応用例（製薬）
Antimony presents itself
in a metallic grey form. Antimony is obtained from stibnite (Sb
2S
3) after reduction with iron.
工業用途
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.
安全性プロファイル
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.
職業ばく露
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.
特性
銀白色の金属光沢を有し、
脆くて展性は乏しい
他金属と合金にすると硬度
を増し、耐摩耗性を向上させ
る
ヒ素、ビスマスとともに半金
属とされる
発がん性
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.
環境運命予測
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.
輸送方法
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
不和合性
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.
廃棄物の処理
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.
予防処置
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.
アンチモン 上流と下流の製品情報
原材料
準備製品