三硫化ニアンチモン 化学特性,用途語,生産方法
外観
灰黒色, 結晶性粉末～粉末
溶解性
水に不溶, エタノール, エーテルに可溶。水酸化ナトリウム溶液に溶け、水に難溶である。炭酸アンモニウムに難溶である(Asと相違)。
解説
三硫化二アンチモン：Sb2S3(339.72)．硫化アンチモン(Ⅲ)ともいう．天然に輝安鉱として産出する．アンチモン(Ⅲ)化合物の水溶液に硫化水素を通じて生じるものは不安定型の赤色の固体で，金属アンチモンと硫黄を融解して得られるものは黒色の金属光沢をもつ，融点550 ℃ の安定型の斜方晶系結晶である．不安定型は，二酸化炭素中で200 ℃ に加熱すると安定型になる．水にほとんど不溶．濃塩酸，濃硫酸，硝酸により分解されアンチモン(Ⅲ)塩となる．水酸化アルカリまたは硫化アルカリに溶け，それぞれ，オキソジチオアンチモン(Ⅲ)酸塩MⅠ3SbOS2またはトリチオアンチモン(Ⅲ)酸塩MⅠ3SbS3となる．また多硫化アルカリ水溶液からは，テトラチオアンチモン(Ⅴ)酸塩MⅠ3SbⅤ S4を生じる．マッチの成分，花火，顔料，色ガラス，プラスチックの着色料に用いられる．
用途
減磨剤、花火、ガラス清澄剤。
特徴
Sb3S3六角形を基本骨格とするSb2S3鎖状構造がやや長いSb−S結合により結ばれた層状構造
化学的特性
Antimony trisulfide is soluble in alkalies and in concentrated, but not dilute, hydrochloric acid. It also goes into solution if it is boiled in alkali carbonate solutions. However, it precipitates as a reddish-brown powder, of nondefinite oxygen content (kermesite), when the solution is cooled. It forms thioantimonates if it is dissolved in alkali-metal sulfides. Antimony trisulfide is a starting material for the production of antimony and antimony compounds.
物理的性質
Natural stibnite is black orthorhombic crystal; or grayish-black powder; the compound also exists as an amorphous substance in yellow-red modification; distorted octahedral arrangement; density 4.64 g/cm
3 for the natural stibnite and 4.12 g/cm
3 for the red modification; melts at 550°C; vaporizes around 1150°C; insoluble in water (1.75mg/L at 18°C) and acetic acid; soluble in hydrochloric acid and caustic soda solution; also, soluble in alcohol, ammonium hydrosulfide and potassium sulfide.
天然物の起源
Antimony trisulfide occurs in nature primarily as the mineral, stibnite, which consists of two parallel Sb4S6 chains linked together. It is used in fireworks; in certain types of safety matches; as a pigment in paints; and in the manufacture of ruby glass.
使用
Antimony(III) sulfide is used as a red dye in rubber vulcanization. It is used as catalyst, additive, anti- blushing agent, heat stabilizer and used in the production of ruby-colored glass and in plastics as a flame retardant.
製造方法
The pure sulphide is obtained from its ore. Stibnite is separated from other ores by grinding and flotation. The ore is then heated to 550-600°C in a perforated vessel. The pure molten material is collected and cooled. It is also prepared by passing hydrogen sulfide into a solution of antimony trichloride:
2 SbCl
3 + 3 H
2S → Sb
2S
3 + 6 HCl
or treating antimony trichloride solution with sodium thiosulfate.
Alternatively, heating antimony metal or antimony trioxide with sulfur forms antimony trisulfide:2 Sb + 3 S → Sb
2S
32 Sb
2O
3 + 9 S → 2 Sb
2S
3 + 3 SO
2All these above preparative methods yield amorphous antimony trisulfide.
調製方法
Ores with more than 40 – 60 % Sb2S3 and free from lead and arsenic often are beneficiated by heating. Because stibnite, Sb2S3, has an unusually low melting point, 546 – 548 ℃, it can be separated from the gangue by melting (liquation). Stibnite more than 90 % pure is obtained and is referred to as crude antimony. It can be sold as such for producing antimony compounds, or it can be converted to antimony metal.
The commercial product should have a striated crystalline structure and a metallic gloss, and its color should be that of graphite. These properties are attained only if the molten antimony(III) sulfide is cooled very slowly. Ores with less than 40 – 45% Sb2S3 are unsuitable for liquation because the large amount of gangue interferes and too much antimony is retained in the residue.
The ore is best fed in the form of walnutsized lumps (1 – 4 cm). If the ore is too fine, the molten Sb2S3 does not flow. The most suitable temperature range is 550 – 660 ℃ because the volatilization of the Sb2S3 (bp 1000 ℃) is prevented, and liquation is successful. Liquation is carried out in a reducing atmosphere in crucibles or in reverberatory furnaces. The main impurities in crude antimony are arsenic, lead, and iron sulfide.
危険性
Explosion risk in contact with oxidizing
materials. Questionable carcinogen.
安全性プロファイル
Poison by
intraperitoneal route. Human blood and
gastrointestinal system effects by inhalation.
Questionable carcinogen. See also
ANTIMONY COMPOUNDS and
SULFIDES. Spontaneously flammable
when exposed to strong oxidizers.
Flammable when exposed to heat or flame.
Moderately explosive by spontaneous
reaction with chlorates, perchlorates, Cl0,
thallic oxide. When heated to decomposition
or on contact with acid or acid fumes it
emits highly toxic fumes of oxides of sulfur
and antimony. Will react with water or
steam to produce toxic and flammable
vapors.
参考文献
P. Bayliss, W. Nowacki, Z. Krist., 135, 308 (1972), DOI: 10.1524/zkri.1972.135.3-4.308.
三硫化ニアンチモン 上流と下流の製品情報
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