Antimony(lat. stibium), sb, chemical element of group v periodic system Mendeleev; atomic number 51, atomic mass 121.75; silver-colored metal white color with a bluish tint. Two stable isotopes 121 sb (57.25%) and 123 sb (42.75%) are known in nature. Of the artificially produced radioactive isotopes, the most important 122 sb ( T 1/2 = 2,8 cym) , 124 sb ( t 1/2 = 60,2 cym) and 125 sb ( t 1/2 = 2 years).
History reference. S. has been known since ancient times. In the countries of the East, it was used approximately 3000 BC. e. for making vessels. AT Ancient Egypt already in the 19th century. BC e. antimony glitter powder (natural sb 2 s 3) called mesten or stem was used to blacken the eyebrows. AT Ancient Greece it was known as st i mi and st i bi, hence the Latin stibium. About 12-14 centuries. n. e. the name antimonium appeared. In 1789 A. Lavoisier included S. in the list chemical elements called antimoine (modern English antimony, Spanish and Italian antimonio, German antimon). The Russian "antimony" comes from the Turkish s u rme; he designated the powder of lead gloss pbs, which also served to blacken the eyebrows (according to other sources, "antimony" - from the Persian antimony - metal). Detailed description The properties and methods of obtaining S. and its compounds were first given by the alchemist Vasily Valentin (Germany) in 1604.
distribution in nature. The average content of S. in earth's crust(Clark) 5 ? 10–5% by weight. S. is dispersed in the magma and biosphere. From hot groundwater it is concentrated in hydrothermal deposits. Known are actually antimony deposits, as well as antimony-mercury, antimony-lead, gold-antimony, antimony-tungsten. Of the 27 minerals S., the main industrial value is antimonite(sb 2 s 3) . Owing to its affinity for sulfur, sulfur is often found as an impurity in the sulfides of arsenic, bismuth, nickel, lead, mercury, silver, and other elements.
Physical and chemical properties. S. is known in crystalline and three amorphous forms (explosive, black, and yellow). Explosive S. (density 5.64-5.97 g/cm 3) explodes on any contact: it is formed during the electrolysis of a solution of sbcl 3; black (density 5.3 g/cm 3) - at fast cooling of S.'s vapors; yellow - when oxygen is passed into liquefied sbh 3. Yellow and black S. are unstable, with low temperatures go into ordinary C. The most stable crystalline C. , crystallizes in the trigonal system, a = 4.5064 å; density 6.61-6.73 g/cm 3 (liquid - 6.55 g/cm 3) ; t pl 630.5 °C; t kip 1635-1645 °С; specific heat capacity at 20-100 °C 0.210 kJ/(kg? To ) ; thermal conductivity at 20 °C 17.6 w/m? TO . Temperature coefficient of linear expansion for polycrystalline C. 11.5? 10 -6 at 0-100 °C; for single crystal a 1 = 8.1? 10 –6 a 2 = 19.5? 10 -6 at 0-400 °C, electrical resistivity (20 °C) (43.045 × 10 -6 ohm? cm) . C. diamagnetic, specific magnetic susceptibility -0.66? 10–6. Unlike most metals, steel is brittle, easily splits along cleavage planes, wears into powder, and cannot be forged (sometimes referred to as semimetals) . Mechanical properties depend on the purity of the metal. Brinell hardness for cast metal 325-340 Mn/m 2 (32,5-34,0 kgf/mm 2) ; modulus of elasticity 285-300; tensile strength 86.0 Mn/m 2 (8,6 kgf/mm 2) . The configuration of the outer electrons of the atom is sb5s 2 5 r 3 . In compounds, it exhibits oxidation states mainly +5, +3 and –3.
Chemically, S. is inactive. It does not oxidize in air up to the melting point. It does not react with nitrogen and hydrogen. Carbon slightly dissolves in molten C. The metal actively interacts with chlorine and other halogens, forming antimony halides. It interacts with oxygen at temperatures above 630 ° C with the formation of sb 2 o 3 . When fused with sulfur, antimony sulfides, also interacts with phosphorus and arsenic. The page is steady in relation to water and the diluted acids. Concentrated hydrochloric and sulfuric acids slowly dissolve S. with the formation of chloride sbcl 3 and sulfate sb 2 (so 4) 3; concentrated Nitric acid oxidizes S. to a higher oxide, which is formed in the form of a hydrated compound xsb 2 o 5? uH 2 O. Sparingly soluble salts of antimony acid - antimonates (Mesbo 3 ? 3h 2 o, where me - na, K) and salts of non-isolated metaantimonous acid - metaantimonites (mesbo 2 ? 3H 2 O), which have reducing properties, are of practical interest. S. combines with metals, forming antimonides.
Receipt. C. is obtained by pyrometallurgical and hydrometallurgical processing of concentrates or ore containing 20-60% sb. Pyrometallurgical methods include precipitation and reduction melting. Sulfide concentrates serve as raw materials for precipitation smelting; the process is based on the displacement of carbon from its sulfide by iron: sb 2 s 3 + 3fe u 2sb + 3fes. Iron is introduced into the charge in the form of scrap. Melting is carried out in reverberatory or short rotating drum furnaces at 1300-1400 °C. S.'s extraction in draft metal makes more than 90%. The reduction smelting of steel is based on the reduction of its oxides to metal with charcoal or coal dust and the slagging of waste rock. Reduction melting is preceded by oxidizing firing at 550 °C with excess air. The cinder contains non-volatile C tetroxide. Electric furnaces can be used for both precipitation and reduction melts. The hydrometallurgical method of obtaining S. consists of two stages: processing of raw materials with an alkaline sulfide solution, transferring S. into a solution in the form of salts of antimony acids and sulfosalts, and separating S. by electrolysis. Rough silver, depending on the composition of the raw material and the method of its production, contains from 1.5 to 15% of impurities: fe, as, s, etc. To obtain pure silver, pyrometallurgical or electrolytic refining is used. During pyrometallurgical refining, impurities of iron and copper are removed in the form of sulfur compounds by introducing antimonite (krudum) - sb 2 s 3 into the S. melt, after which arsenic (in the form of sodium arsenate) and sulfur are removed by blowing air under soda slag. During electrolytic refining with a soluble anode, crude silver is purified from iron, copper, and other metals remaining in the electrolyte (Cu, ag, and Au remain in the sludge). The electrolyte is a solution consisting of sbf 3 , h 2 so 4 and hf. The content of impurities in refined S. does not exceed 0.5-0.8%. To obtain high-purity sulfur, zone melting is used in an inert gas atmosphere, or silver is obtained from previously purified compounds—trioxide or trichloride.
Application. S. is used mainly in the form of alloys based on lead and tin for battery plates, cable sheaths, bearings ( babbitt) , alloys used in printing ( garth) , etc. Such alloys have increased hardness, wear resistance, and corrosion resistance. AT fluorescent lamps calcium halophosphate activate sb. S. is part of semiconductor materials as an alloying addition to germanium and silicon, as well as in the composition of antimonides (for example, insb). The radioactive isotope 12 sb is used in sources of g radiation and neutrons.
O. E. Krein.
Antimony in the body. S. content (per 100 G dry matter) is 0.006 in plants mg, in marine animals 0.02 mg, in terrestrial animals 0.0006 mg. S. enters the body of animals and humans through the respiratory organs or gastrointestinal tract. It is excreted mainly with faeces, in small quantities - with urine. Biological role S. is unknown. It is selectively concentrated in thyroid gland, liver, spleen. In erythrocytes, C. accumulates mainly in the oxidation state + 3, in blood plasma - in the oxidation state + 5. The maximum allowable concentration of C. 10 -5 - 10 -7 G per 100 G dry cloth. With more high concentration this element inactivates a number of enzymes of lipid, carbohydrate and protein metabolism (possibly as a result of blocking sulfhydryl groups) .
AT medical practice S.'s preparations (solyusurmin, etc.) are used mainly for the treatment of leishmaniasis and some helminthiases (for example, schistosomiasis).
C. and its compounds are poisonous. Poisoning is possible during the smelting of antimony ore concentrate and in the production of C alloys. acute poisoning- irritation of the mucous membranes of the upper respiratory tract, eyes, and skin. Dermatitis, conjunctivitis, etc. may develop. Treatment: antidotes (unithiol), diuretics and diaphoretics, etc. Prevention: mechanization of production. processes, effective ventilation, etc.
Lit.: Shiyanov A. G., Production of antimony, M., 1961; Fundamentals of metallurgy, v. 5, M., 1968; Creation Research new technology production of antimony and its compounds, in the collection: Chemistry and technology of antimony, Fr., 1965.
ANTIMONY, Sb (from Tur. sürme, lat. Stibium * a. antimony; n. Antimon; f. antimoine; and. antimonio), is a chemical element of group V of the Mendeleev periodic system, atomic number 51, atomic mass 121.75. Natural antimony consists of a mixture of 2 stable isotopes 121 Sb (57.25%) and 123 Sb (42.75%). More than 20 artificial radioactive isotopes of Sb are known with mass numbers from 112 to 135.
Antimony has been known since ancient times (in the 3rd millennium BC, vessels were made from it in Babylon). In Egypt at the beginning of the 2nd millennium BC. antimonite powder (natural sulfide Sb 2 S 3) was used as cosmetic product. A detailed description of the properties and method of obtaining antimony and its compounds were first given by the alchemist Vasily Valentin () in 1604. The French chemist A. Lavoisier (1789) included antimony in the list of chemical elements called antimoine.
Antimony is a silvery-white substance with a bluish tint and a metallic sheen; known crystalline and 3 amorphous forms of antimony (explosive, black and yellow). Crystalline antimony (also native) has a hexagonal lattice a = 0.4506 nm; density 6618 kg/m 3 , melting point 630.9°C; boiling point 1634°C; thermal conductivity 23.0 W/(mK); specific molar heat capacity 25.23 JDmol.K); electrical resistance 41.7.10 -4 (Ohm.m); temperature coefficient of linear expansion 15.56.10 -6 K -1; diamagnetic. Antimony is brittle, easily splits along cleavage planes, wears into powder and cannot be forged. The mechanical properties of antimony depend on its purity. Antimony is conventionally classified as a metal. Explosive antimony (density 5640-5970 kg / m 3) explodes on touch; formed during the electrolysis of a solution of SbCl 3 . Black antimony (density 5300 kg / m 3) is obtained by rapidly cooling its vapors with carbon; yellow modification - when oxygen is passed through liquid SbH 3 hydride. The yellow and black modifications are metastable formations and pass into the crystalline phase over time.
Antimony in compounds exhibits valency +5, +3, -3; chemically inactive, does not oxidize in air up to the melting point. Antimony interacts with oxygen only in the molten state, forming Sb2O 3 ; with hydrogen and nitrogen normal conditions does not react. Actively interacts with halogens (with the exception of F 2). Antimony slowly dissolves in hydrochloric and sulfuric acids. When combined with metals, antimony forms antimonides. Of practical interest are sparingly soluble salts of antimony acid - antimonates (V) (Me SbO 3 .3H 2 O, where Me is Na, K) and metaantimonates (III) (Me SbO 2 .3H 2 O), which have reducing properties. Antimony is toxic, MPC 0.5 mg/m 3 .
The average content of antimony in the earth's crust (clarke) is 5.10 -5%, in ultrabasic rocks 1.10 -5%, basic 1.10 -4%, acidic 2.6.10 -5%. Antimony is concentrated in hydrothermal deposits. Antimony proper, as well as antimony-mercury, antimony-lead, gold-antimony, antimony-tungsten deposits are known. From 27
Antimony (lat. Stibium; denoted by the symbol Sb) - an element of the main subgroup of the fifth group of the fifth period of the periodic system of chemical elements of D. I. Mendeleev, atomic number 51.
Atomic mass - 121.76
Density, kg/m³ - 6620
Melting point, ° С - 630.5
Heat capacity, kJ / (kg ° С) - 0.205
Electronegativity - 1.9
Covalent radius, Å - 1.40
1st ionization potential, ev - 8.64
Historical information about antimonyAlong with gold, mercury, copper and six other elements, antimony is thought to be prehistoric. The name of its discoverer has not come down to us. It is only known that, for example, in Babylon as early as 3 thousand years BC. vessels were made from it. Latin name the element "stibium" is found in the writings of Pliny the Elder. However, the Greek "στιβι", from which this name comes, originally referred not to antimony itself, but to its most common mineral, antimony luster.
In the countries of ancient Europe, only this mineral was known. In the middle of the century, they learned to smelt “antimony kinglet” from it, which was considered a semi-metal. Agricola (1494...1555), the largest metallurgist of the Middle Ages, wrote: “If a certain portion of antimony is added to lead by alloying, a typographical alloy is obtained, from which a type is made, used by those who print books.” Thus, one of the main current uses of element #51 is many centuries old.
The properties and methods of obtaining antimony, its preparations and alloys for the first time in Europe are described in detail in the famous book "The Triumphal Chariot of Antimony", published in 1604. For many years, the Benedictine alchemist Vasily Valentin, who allegedly lived at the beginning of the 15th century, was considered its author. However, back in the last century it was established that this had never happened among the monks of the Benedictine order. Scientists have come to the conclusion that "Vasily Valentin" is a pseudonym of an unknown scientist who wrote his treatise no earlier than the middle of the 16th century. ... The name “antimonium”, given by him to natural sulphurous antimony, the German historian Lipman derives from the Greek ανεμον - “flower” (by the appearance of intergrowths of needle-like crystals of antimony luster, similar to flowers of the Compositae family).
The name "antimony" both here and abroad for a long time applied only to this mineral. And at that time, metallic antimony was called the king of antimony - regulus antimoni. In 1789, Lavoisier included antimony in the list of simple substances and gave it the name antimonie, which remains the French name for element No. 51 to this day. The English and German names are close to it - antimony, Antimon.
There is, however, another version. She has fewer eminent supporters, but among them is the creator of Schweik - Yaroslav Hasek.
Between prayers and household chores, Father Leonardus, abbot of the Stahlhausen monastery in Bavaria, was looking for a philosopher's stone. In one of his experiments, he mixed in a crucible the ashes of a burned heretic with the ashes of his cat and double the amount of earth taken from the place of burning. The monk began to heat this "hellish mixture".
After evaporation, a heavy dark substance with a metallic sheen was obtained. It was unexpected and interesting; Nevertheless, Father Leonardus was annoyed: in the book that belonged to the burnt heretic, it was said that the stone of philosophers should be weightless and transparent... And Father Leonardus threw the resulting substance away from sin away - into the monastery courtyard.
After some time, he was surprised to notice that the pigs willingly lick the “stone” he threw out and at the same time quickly grow fat. And then Father Leonardus had a brilliant idea: he decided that he had discovered nutrient suitable for people. He prepared a new portion of the "stone of life", crushed it and added this powder to the porridge, which his skinny brothers in Christ ate.
The next day, all forty monks of the Stahlhausen monastery died in terrible agony. Repenting of his deed, the abbot cursed his experiments, and renamed the “stone of life” into antimonium, that is, a remedy against monks.
It is difficult to vouch for the authenticity of the details of this story, but it is this version that is presented in the story of J. Hasek "The Stone of Life".
The etymology of the word "antimony" is discussed above in some detail. It only remains to add that Russian name of this element - "antimony" - comes from the Turkish "surme", which translates as "rubbing" or "blackening of the eyebrows". Up until the 19th century. in Russia, there was an expression “to sullen eyebrows”, although they were “antimony” by no means always with antimony compounds. Only one of them - a black modification of trisulfuric antimony - was used as an eyebrow dye. It was first designated by a word, which later became the Russian name for the element.
Antimony has been known since ancient times. In the countries of the East, it was used approximately 3000 BC. e. for making vessels. In ancient Egypt already in the 19th century. BC e. antimony glitter powder (natural Sb 2 S 3) called mesten or stem used for blackening the eyebrows. In ancient Greece it was known as stimi and stibi, hence Latin stibium. About 12-14 centuries. n. e. the name appeared antimonium. In 1789 A. Lavoisier included antimony in the list of chemical elements under the name antimoine(Modern English antimony, Spanish and Italian antimonio, Deutsch Antimon). Russian "antimony" comes from Turkish surme; he designated the powder of lead shine PbS, which also served to blacken the eyebrows (according to other sources, “antimony” - from the Persian “surmium” - metal). A detailed description of the properties and methods for obtaining antimony and its compounds was first given by the alchemist Vasily Valentin (Germany) in 1604.
Finding antimony in nature
The average content of antimony in the earth's crust is 500 mg/t. Its content in igneous rocks is generally lower than in sedimentary ones. Of the sedimentary rocks, the highest concentrations of antimony are observed in shales (1.2 g/t), bauxites and phosphorites (2 g/t) and the lowest in limestones and sandstones (0.3 g/t). Elevated amounts of antimony are found in coal ash. Antimony, on the one hand, in natural compounds has the properties of a metal and is a typical chalcophile element, forming antimonite. On the other hand, it has the properties of a metalloid, manifested in the formation of various sulfosalts - bournonite, boulangerite, tetrahedrite, jamsonite, pyrargyrite, etc. Antimony can form intermetallic compounds with such metals as copper, arsenic and palladium. The ionic radius of antimony Sb 3+ is closest to the ionic radii of arsenic and bismuth, due to which there is an isomorphic substitution of antimony and arsenic in fahlore and geocronite Pb 5 (Sb, As) 2 S 8 and antimony and bismuth in cobellite Pb 6 FeBi 4 Sb 2 S 16; The volatility of antimony in a number of its compounds is relatively low. Antimony halides SbCl 3 have the highest volatility. Under supergene conditions (in near-surface layers and on the surface), antimonite undergoes oxidation approximately according to the following scheme: Sb 2 S 3 + 6O 2 = Sb 2 (SO 4) 3 . The resulting antimony oxide sulfate is very unstable and rapidly hydrolyzes, turning into antimony ochers - sideboard Sb 2 O 4, stibioconite Sb 2 O 4 nH 2 O, valentinite Sb 2 O 3, etc. Solubility in water is rather low 1.3 mg / l, but it increases significantly in solutions of alkalis and sulfurous metals with the formation of a thioacid of the Na 3 SbS 3 type. Antimonite Sb 2 S 3 (71.7% Sb) has the main industrial importance. The sulfosalts tetrahedrite Cu 12 Sb 4 S 13 , bournonite PbCuSbS 3 , boulangerite Pb 5 Sb 4 S 11 and jamsonite Pb 4 FeSb 6 S 14 are of little importance.
In the free state, it forms silvery-white crystals with a metallic sheen, density 6.68 g/cm³. Resembling metal in appearance, crystalline antimony is more brittle and less thermally and electrically conductive. Antimony is known in crystalline and three amorphous forms (explosive, black and yellow). Explosive Antimony (density 5.64-5.97 g / cm 3) explodes on any contact; formed during the electrolysis of a solution of SbCl 3 ; black (density 5.3 g / cm 3) - with rapid cooling of antimony vapor; yellow - when oxygen is passed into liquefied SbH 3 . Yellow and black antimony are unstable, at low temperatures they transform into ordinary antimony. The most stable crystalline antimony crystallizes in the trigonal system, a = 4.5064 Å; density 6.61-6.73 g / cm 3 (liquid - 6.55 g / cm 3); t pl 630.5 °C; kip t 1635-1645 °С: specific heat capacity at 20-100 °С 0.210 kJ/(kg K); thermal conductivity at 20 ° C 17.6 W / (m K) . Temperature coefficient of linear expansion for polycrystalline Antimony 11.5·10 -6 at 0-100 °C; for a single crystal a 1 = 8.1 10 -6, a 2 = 19.5 10 -6 at 0-400 ° C, electrical resistivity (20 ° C) (43.045 10 -6 cm cm). Antimony is diamagnetic, the specific magnetic susceptibility is -0.66·10 -6 . Unlike most metals, antimony is brittle, easily splits along cleavage planes, wears into powder and cannot be forged (sometimes referred to as semimetals). Mechanical properties depend on the purity of the metal. Brinell hardness for cast metal 325-340 MN / m 2 (32.5-34.0 kgf / mm 2); modulus of elasticity 285-300; ultimate strength 86.0 MN / m 2 (8.6 kgf / mm 2).
Antimony - metal or not metal?Seven metals were known to medieval metallurgists and chemists: gold, silver, copper, tin, lead, iron and mercury. Zinc, bismuth and arsenic, discovered at that time, together with antimony, were isolated in special group"semimetals": they were worse forged, and malleability was considered the main feature of the metal. In addition, according to alchemical ideas, each metal was associated with some celestial body. And seven such bodies were known: the Sun (gold was associated with it), the Moon (silver), Mercury (mercury), Venus (copper), Mars (iron), Jupiter (tin) and Saturn (lead).
There was not enough celestial body for antimony, and on this basis, the alchemists did not want to recognize it as an independent metal. But, oddly enough, they were partially right, which is not difficult to confirm by analyzing the physical and chemical properties of antimony.
Chemical properties of antimony
The configuration of the outer electrons of the Sb atom is 5s 2 5p 3 . In compounds, it exhibits oxidation states mainly +5, +3 and -3. In chemical terms, it is inactive. It does not oxidize in air up to the melting point. It does not react with nitrogen and hydrogen. Carbon slightly dissolves in molten antimony. The metal actively interacts with chlorine and other halogens, forming antimony halides. It interacts with oxygen at temperatures above 630 ° C with the formation of Sb 2 O 3. When fused with sulfur, antimony sulfides are obtained, it also interacts with phosphorus and arsenic. Antimony is resistant to water and dilute acids. Concentrated hydrochloric and sulfuric acids slowly dissolve Antimony with the formation of chloride SbCl 3 and sulfate Sb 2 (SO 4) 3 ; concentrated nitric acid oxidizes antimony to a higher oxide, which is formed in the form of a hydrated compound xSb 2 O 5 yH 2 O. Slightly soluble salts of antimony acid - antimonates (MeSbO 3 3H 2 O, where Me - Na, K) and salts not isolated metaantimony acid - metaantimonites (MeSbO 2 ·3H 2 O), which have reducing properties. Antimony combines with metals to form antimonides.
A detailed analysis of the chemical properties of antimony also did not make it possible to finally remove it from the "neither this nor that" section. The outer, electronic layer of the antimony atom consists of five valence electrons s 2 p 3 . Three of them ( p-electrons) - unpaired and two ( s-electrons) are paired. The former more easily break away from the atom and determine the valency 3+ characteristic of antimony. With the manifestation of this valency, a pair of unshared valence electrons s 2 is in stock. When this reserve is used up, antimony becomes pentavalent. In short, it exhibits the same valencies as its counterpart in the group, the non-metal phosphorus.
Let's see how antimony behaves in chemical reactions with other elements, such as oxygen, and what is the nature of its compounds.
When heated in air, antimony easily turns into oxide Sb 2 O 3 - a white solid, almost insoluble in water. In the literature, this substance is often called antimony anhydride, but this is incorrect. After all, anhydride is an acid-forming oxide, and in Sb (OH) 3, Sb 2 O 3 hydrate, basic properties clearly predominate over acid ones. The properties of the lower oxide of antimony indicate that antimony is a metal. But the highest oxide of antimony Sb 2 O 5 is really an anhydride with pronounced acidic properties. So antimony is still a non-metal?
There is also a third oxide - Sb 2 O 4. In it, one antimony atom is three-, and the other is pentavalent, and this oxide is the most stable. In its interaction with other elements - the same duality, and the question of antimony metal or non-metal remains open. Why, then, in all reference books does it appear among metals? Mainly for the sake of classification: you have to put it somewhere, but outwardly it looks more like metal ...
In medieval books, antimony was denoted by the figure of a wolf with an open mouth. Probably, such a “predatory” symbol of this metal is explained by the fact that antimony dissolves (“devours”) almost all other metals.
Technology for obtaining antimony
The metal is obtained by pyrometallurgical and hydrometallurgical processing of concentrates or ore containing 20-60% Sb. Pyrometallurgical methods include precipitation and reduction melting. Raw materials for precipitation smelting are sulfide concentrates; the process is based on the displacement of antimony from its sulfide by iron: Sb 2 S 3 + 3Fe => 2Sb + 3FeS. Iron is introduced into the charge in the form of scrap. Melting is carried out in reverberatory or short rotating drum furnaces at 1300-1400 °C. The extraction of antimony into crude metal is more than 90%. The reduction smelting of antimony is based on the reduction of its oxides to metal with charcoal or coal dust and the slagging of waste rock. Reduction melting is preceded by oxidizing firing at 550 °C with excess air. The cinder contains non-volatile antimony oxide. Electric furnaces can be used for both precipitation and reduction melts. The hydrometallurgical method of obtaining Antimony consists of two stages: treatment of raw materials with an alkaline sulfide solution with the transfer of Antimony into a solution in the form of antimony acid salts and sulfosalts and the isolation of Antimony by electrolysis. Rough Antimony, depending on the composition of the raw material and the method of its production, contains from 1.5 to 15% of impurities: Fe, As, S and others. To obtain pure antimony, pyrometallurgical or electrolytic refining is used. In pyrometallurgical refining, iron and copper impurities are removed in the form of sulfur compounds by introducing antimonite (crudum) - Sb 2 S 3 into the antimony melt, after which arsenic (in the form of sodium arsenate) and sulfur are removed by blowing air under soda slag. During electrolytic refining with a soluble anode, crude antimony is purified from iron, copper and other metals remaining in the electrolyte (Cu, Ag, Au remain in the sludge). The electrolyte is a solution consisting of SbF 3 , H 2 SO 4 and HF. The content of impurities in refined Antimony does not exceed 0.5-0.8%. To obtain high purity Antimony, zone melting in an inert gas atmosphere is used, or Antimony is obtained from previously purified compounds - oxide (III) or trichloride.
Application of antimonyDue to its brittleness, metallic antimony is rarely used. However, since antimony increases the hardness of other metals (tin, lead) and does not oxidize under normal conditions, metallurgists often introduce it into the composition of various alloys. The number of alloys in which the element is included is close to 200.
Antimony is mainly used in the form of alloys based on lead and tin for battery plates, cable sheaths, bearings (babbit), alloys used in printing (hart), etc. Such alloys have increased hardness, wear resistance, and corrosion resistance. In fluorescent lamps, calcium halophosphate activates Sb. Antimony is included in the composition of semiconductor materials as an alloying addition to germanium and silicon, as well as in the composition of antimonides (for example, InSb). The radioactive isotope 122 Sb is used in sources of γ-radiation and neutrons.
It is used in the semiconductor industry in the production of diodes, infrared detectors, Hall effect devices. It is a component of lead alloys, increasing their hardness and mechanical strength. The scope includes:
- batteries
- antifriction alloys
- printing alloys
- small arms and tracer bullets
- cable sheaths
- matches
- medicines, antiprotozoal drugs
- soldering - some lead-free solders contain 5% Sb
- use in linotype printing presses
Together with tin and copper, antimony forms a metal alloy - babbitt, which has antifriction properties and is used in plain bearings. Sb is also added to metals intended for thin castings.
Antimony compounds in the form of oxides, sulfides, sodium antimonate and antimony trichloride are used in the production of refractory compounds, ceramic enamels, glass, paints and ceramic products. Antimony trioxide is the most important of the antimony compounds and is mainly used in flame retardant compositions. Antimony sulfide is one of the ingredients in match heads.
The natural sulfide of antimony, stibnite, was used in biblical times in medicine and cosmetics. Stibnite is still used in some developing countries as a medicine.
Antimony compounds such as meglumine antimoniate (glucantim) and sodium stibogluconate (pentostam) are used in the treatment of leishmaniasis.
The effect of antimony on the human bodyThe content of antimony (per 100 g of dry matter) is 0.006 mg in plants, 0.02 mg in marine animals, and 0.0006 mg in terrestrial animals. Antimony enters the body of animals and humans through the respiratory organs or the gastrointestinal tract. It is excreted mainly with faeces, in small quantities - with urine. Antimony is selectively concentrated in the thyroid gland, liver, and spleen. Antimony accumulates predominantly in erythrocytes in the +3 oxidation state, in blood plasma - in the oxidation state. +5. The maximum allowable concentration of Antimony is 10 -5 - 10 -7 g per 100 g of dry tissue. At a higher concentration, this element inactivates a number of enzymes of lipid, carbohydrate and protein metabolism (possibly as a result of blocking sulfhydryl groups).
Antimony exhibits an irritating and cumulative effect. Accumulates in the thyroid gland, inhibits its function and causes endemic goiter. However, getting into digestive tract, antimony compounds do not cause poisoning, since Sb (III) salts are hydrolyzed there with the formation of sparingly soluble products. At the same time, antimony (III) compounds are more toxic than antimony (V). Dust and vapors of Sb cause nosebleeds, antimony "casting fever", pneumosclerosis, affect the skin, and disrupt sexual functions. The taste perception threshold in water is 0.5 mg/l. Lethal dose for an adult - 100 mg, for children - 49 mg. For antimony aerosols MPC in the air of the working area is 0.5 mg/m³, in the atmospheric air 0.01 mg/m³. MPC in soil 4.5 mg/kg. AT drinking water antimony belongs to the 2nd hazard class, has a MPC of 0.005 mg/l, established according to the sanitary-toxicological LPV. In natural waters, the content standard is 0.05 mg/l. In industrial waste water discharged to treatment facilities with biofilters, the content of antimony should not exceed 0.2 mg/l.
Antimony (English Antimony, French Antimoine, German Antimon) has long been known to man both in the form of a metal and in the form of some compounds. Berthelot describes a fragment of a vase made of metal antimony, found in Tello (southern Babylonia) and related to early III in. BC e. Other objects made of metallic antimony have also been found, in particular in Georgia, dating back to the 1st millennium BC. h. Antimony bronze, which was used during the period of the ancient Babylonian kingdom, is well known; bronze contained copper and additives - tin, lead and significant amounts of antimony. Alloys of antimony with lead were used to make a variety of products. It should be noted, however, that in antiquity, metallic antimony, apparently, was not considered an individual metal, it was taken for lead. Among antimony compounds in Mesopotamia, India, Central Asia and other Asian countries, sulfide antimony (Sb 2 S 3), or the mineral "antimony shine" was known. The mineral was made into a fine, shiny black powder, which was used for cosmetic purposes, especially for making up the eyes "eye ointment". However, despite all these data on the long-standing distribution of antimony and its compounds, the well-known researcher in the field of archaeological chemistry Lucas claims that antimony was almost unknown in ancient Egypt. There, he writes, only one case of the use of metallic antimony and few cases of the use of antimony compounds have been established. In addition, according to Lucas, in all archaeological metal objects, antimony is present only in the form of impurities; sulphurous antimony, at least until the time of the New Kingdom, was not used at all for make-up, as evidenced by the coloring of mummies. Meanwhile, in the III millennium BC. e. in Asian countries, and even in Egypt itself, there was a cosmetic product called stem, place or stimmi (stimmi); in the II millennium BC. e. the Indian word antimony appears; but all these names were used, however, mainly for lead sulphide (lead luster). In Syria and Palestine, long before the beginning of our era. black makeup was called not only stimmy, but also kahkhal or kogol, which in all three cases meant any fine dry or ointment-like powder. Later writers (around the beginning of our era), such as Pliny, called stimmy and stibi - cosmetic and pharmaceutical products for make-up and eye treatment. In the Greek literature of the Alexandrian period, these words also mean a black cosmetic (black powder). These names pass into Arabic literature with some variations. So, in Avicenna's "Canon of Medicine", along with stimmy, itmid, or atemid, is a powder or precipitate (paste) of lead. Later, the words al-kahkhal (make-up), alkool, alkofol appear in the indicated literature, referring mainly to the lead luster. It was believed that cosmetic and therapeutic products for the eyes contain a certain mysterious spirit, hence, probably, volatile liquids began to be called alcohol. The alchemists called the antimony, as well as the lead shine, antimonium (Antimonium). Ruland's dictionary (1612) explains this word as alcohol, a stone from lead ore veins, marcasite, Saturn, antimony (Stibium), and stibium, or stimmie, as black sulfur or a mineral that the Germans call spiesglass (Spiesglas), later Bpiesglanz (probably derived from stibium). However, despite this confusion of names, it was during the alchemical period in Western Europe that antimony and its compounds were finally distinguished from lead and its compounds. Already in alchemical literature, as well as in the writings of the Renaissance, metallic and sulphurous antimony is usually described quite accurately. Starting from the XVI century. antimony began to be used for a variety of purposes, in particular in gold metallurgy, for polishing mirrors, and later in printing and medicine. The origin of the word antimony, which appeared after 1050, is explained in various ways. There is a story of Vasily Valentin about how one monk, who discovered the strong laxative effect of antimony sulphide on a pig, recommended it to his brothers. The result of this medical advice was deplorable - after taking the remedy, all the monks died. Therefore, as if antimony received a name derived from "anti-monachium" (a remedy against monks). But this is all more of an anecdote. The word "antimony", most likely, is simply a transformed itmid, or atemid, of the Arabs. There are, however, other explanations. So, some authors believe that "antimony" is the result of the reduction of the Greek. anthos ammonos, or the flower of the god Amon (Jupiter); so allegedly called antimony shine. Others produce "antimony" from the Greek. anti-monos (opponent of seclusion), emphasizing that natural antimony is always compatible with other minerals. The Russian word antimony is of Turkic origin; the original meaning of this word is make-up, ointment, ointment. This name has been preserved in many oriental languages (Parsian, Uzbek, Azerbaijani, Turkish, etc.) to our times. Lomonosov considered the element a "semimetal" and called it antimony. Along with antimony, the name antimony is also found. Russian literature of the early 19th century. the words antimony (Zakharov, 1810), antimony, antimony, antimony beetle and antimony are used.
Antimony (lat. Stibium ), Sb , chemical element V groups of the periodic system of Mendeleev; atomic number 51, atomic mass 121.75; a silvery-white metal with a bluish tint in nature, two stable isotopes 121 are known Sb (57.25%) and 123 Sb (42,75%).
Antimony has been known since ancient times. In the countries of the East, it was used approximately 3000 BC. for making vessels. In ancient Egypt, already in the 19th century BC. antimony powder ( Sb 2 S 3 ) entitled mesten or stem used for blackening the eyebrows. In ancient Greece it was known as stimi and stibi , hence Latin stibium .about 12-14 centuries. AD the name appeared antimonium . In 1789, A. Louvazier included antimony in the list of chemical elements under the name antimoine (Modern English antimony , Spanish and Italian antimonio , Deutsch antimon ). The Russian "antimony" comes from the Turkish surme ; they designated a powder of lead luster PbS , which also served to blacken the eyebrows (according to other sources, “antimony” - from the Persian antimony - metal).
The first book known to us, in which the properties of antimony and its compounds are described in detail, is “The Triumphal Chariot of Antimony”, published in 1604. its author entered the history of chemistry under the name of the German Benedictine monk Vasily Valentin. It was not possible to establish who is hiding under this pseudonym, but even in the last century it was proved that brother Vasily Valentin was never listed in the lists of monks of the Benedictine order. There is, however, evidence that XV century in the Erfurt monastery there lived a monk named Vasily, very well versed in alchemy; some manuscripts belonging to him were found after his death in a box along with powdered gold. But to identify him with the author of the "Triumphal Chariot of Antimony", apparently, is impossible. Most likely, as shown critical analysis a number of books by Vasily Valentin, they are written different persons, and not earlier than the second half XVI century.
Even medieval metallurgists and chemists noticed that antimony is forged worse than “classical” metals, and therefore, together with zinc, bismuth and arsenic, it was singled out in a special group - “semimetals”. There were other “weighty” reasons for this: according to alchemical concepts, each metal was associated with one or another celestial body “Seven metals created light according to the number of seven planets,” one of the most important postulates of alchemy said. At some stage, people really knew seven metals and the same number celestial bodies(Sun, Moon and five planets, not counting the Earth). Only complete laymen and ignoramuses could fail to see in this the deepest philosophical regularity. A coherent alchemical theory said that gold represented the Sun in heaven, silver is a typical Moon, copper is undoubtedly related to Venus, iron clearly gravitates towards Mars, mercury, respectively, Mercury, tin represents Jupiter, and lead represents Saturn. For other elements, not a single vacancy remained in the series of metals.
If for zinc and bismuth such discrimination caused by a shortage of celestial bodies was clearly unfair, then antimony, with its peculiar physical and chemical properties and really had no right to complain about the fact that she was in the category of “semimetals”
Judge for yourself. By appearance crystalline, or gray, antimony (this is its main modification) is a typical gray-white metal with a slight bluish tint, which is the stronger, the more impurities (three amorphous modifications are also known: yellow, black and the so-called explosive). But appearances, as you know, can be deceiving, and antimony confirms this. Unlike most metals, it is, firstly, very brittle and easily abraded into powder, and secondly, it conducts electricity and heat much worse. And in chemical reactions, antimony exhibits such a dual
ness, which does not allow an unambiguous answer to the question: is it a metal or not a metal.
As if in retaliation for being reluctant to accept metals into their ranks, molten antimony dissolves almost all metals. This was known in antiquity, and it is no coincidence that in many alchemical books that have come down to us, antimony and its compounds were depicted in the form of a wolf with an open mouth. In the treatise of the German alchemist Mikhail Meyer “Running Atlanta”, published in 1618, for example, such a picture was placed: in the foreground, a wolf devours a king lying on the ground, and in the background, that king, safe and sound, approaches the shore of a lake, where there is a boat that should deliver him to the palace on the opposite bank. Symbolically, this drawing depicted a method of purifying gold (king) from impurities of silver and copper using antimonite (wolf) - natural antimony sulfide, and gold formed a compound with antimony, which then with a stream of air - antimony volatilized in the form of three oxides, and pure gold was obtained. This method existed before XVIII century.
The content of antimony in the earth's crust is 4 * 10 -5 wt%. World reserves of antimony, estimated at 6 million tons, are concentrated mainly in China (52% of world reserves). The most common mineral is antimony luster, or stibine (antimonite) Sb 2 S 3 , lead-gray with a metallic sheen, which crystallizes in a rhombic system with a density of 4.52-4.62 g / cm 3 and hardness 2. In the main mass, antimony shine is formed in hydrothermal deposits, where its accumulations create deposits of antimony ore in the form of veins and sheet-like bodies. AT upper parts ore bodies, near the surface of the earth, antimony shine undergoes oxidation, forming a number of minerals, namely: senarmontite and valentite Sb2O3 ; sideboard Sb2O4 ; stibiocanite Sb2O4H2O ; kermisite 3Sb2S3Sb2O . In addition to our own antimony ores, there are also ores in which antimony is in the form of complex compounds with copper, lead
mercury and zinc (fahlore).
Significant deposits of antimony minerals are located in China, the Czech Republic, Slovakia, Bolivia, Mexico, Japan, the USA, and in a number of African countries. In pre-revolutionary Russia, antimony was not mined at all, and its deposits were not known (at the beginning XX century, Russia annually imported from abroad almost a thousand tons of antimony). True, back in 1914, as the prominent Soviet geologist academician D.I. Shcherbakov wrote in his memoirs, he discovered signs of antimony ores in the Kadamdzhai ridge (Kyrgyzstan). But then it was not up to antimony. Geological searches, continued by the scientist almost two decades later, were crowned with success, and already in 1934 trisulfuric antimony began to be obtained from Kadamdzhai ores, and a year later the first domestic metallic antimony was smelted at the pilot plant. By 1936, there was no need to buy it abroad.
PHYSICAL AND CHEMICAL
PROPERTIES.
For antimony, one crystalline form and several amorphous ones are known (the so-called yellow, black and explosive antimony). Under ordinary conditions, only crystalline antimony is stable; it is silvery white with a bluish tinge. Pure metal upon slow cooling under a layer of slag forms needle-like crystals on the surface, resembling the shape of stars. The crystal structure is rhombohedral, a=4.5064 A, a=57.10.
Density of crystalline antimony 6.69, liquid 6.55 g / cm 3. Melting point 630.5 0 С, boiling point 1635-1645 0 С, melting heat 9.5 kcal / g-atom, heat of vaporization 49.6 kcal / g-atom. Specific heat(cal / d deg): 0.04987(20 0); 0.0537(3500); 0.0656(650-950 0). Thermal conductivity (cal / em.sec.deg):
0.045,(0 0); 0.038(2000); 0.043(400 0); 0.062(650 0). Antimony is brittle, easily rubbed into powder; viscosity (poise); 0.015(630.50); 0.082(1100 0). Brinell hardness for cast antimony 32.5-34kg / mm 2 , for high purity antimony (after zone melting) 26kg / mm 2 . Modulus of elasticity 7600kg / mm 2, tensile strength 8.6kg / mm 2, compressibility 2.43 10 -6 cm 2 / kg.
Yellow antimony is obtained by passing oxygen or air into antimony hydrogen liquefied at -90 0; already at –50 0 it passes into ordinary (crystalline) antimony.
Black antimony is formed during the rapid cooling of antimony vapor, at about 400 0 it transforms into ordinary antimony. The density of black antimony is 5.3. Explosive antimony - a silvery shiny metal with a density of 5.64-5.97, is formed during the electrical production of antimony from a hydrochloric acid solution of antimony chloride (17-53% SbCl2 in hydrochloric acid d 1.12), at a current density ranging from 0.043 to 0.2 a / dm 2 . The resulting antimony passes into ordinary antimony with an explosion caused by friction, scratching or touching the heated metal; the explosion is caused by an exothermic process of transition from one form to another.
In air under normal conditions, antimony ( Sb ) does not change, it is insoluble neither in water nor in organic solvents, but with many metals it easily forms alloys. In a series of voltages, antimony is located between hydrogen and copper. It, antimony, does not displace hydrogen from acids and in dilute HCl and H2SO4 does not dissolve. However, strong sulfuric acid, when heated, converts antimony into sulfates E 2 (SO 4) 3 . Strong nitric acid oxidizes antimony to acids H3 EO 4 . Alkali solutions by themselves do not act on antimony, but in the presence of oxygen they slowly destroy it.
When heated in air, antimony burns with the formation of oxides; it also easily combines with ha-
Loading...