Antimony(lat. stibium), sb, a chemical element of group V of Mendeleev's periodic system; atomic number 51, atomic mass 121.75; silvery-white metal 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).
Historical reference. S. 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 was used to blacken the eyebrows. In 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 of chemical elements under the name 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 the earth's crust (clarke) 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 silver is based on the reduction of its oxides to metal. charcoal or coal dust and waste rock slagging. 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. In pyrometallurgical refining, impurities of iron and copper are removed in the form of sulfur compounds by introducing antimonite (crudum) - 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. In fluorescent lamps, sb is activated with calcium halophosphate. 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 the gastrointestinal tract. It is excreted mainly with faeces, in small quantities - with urine. Biological role S. is unknown. It is selectively concentrated in the 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. 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) .
In medical practice, S.'s preparations (solusurmin and others) 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. In 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
ANTIMONY-s; and.[Persian. surma - metal]
1. Chemical element (Sb), bluish-white metal (used in various alloys in technology, in typography). Smelting antimony. Combination of antimony with sulfur.
2. In the old days: dye for blackening hair, eyebrows, eyelashes. Bring, draw eyebrows with antimony. Traces of antimony on the face.
◁ Antimony, -th, -th (1 sign). S-th ores. C alloys. C. glitter(a lead-gray mineral containing antimony and sulfur).
antimony(lat. Stibium), a chemical element of group V of the periodic system. Forms several modifications. Ordinary antimony (the so-called gray) - bluish-white crystals; density 6.69 g / cm 3, t pl 630.5°C. It does not change in air. The most important mineral is antimonite (antimony shine). Component of alloys based on lead and tin (battery, printing, bearing, etc.), semiconductor materials.
ANTIMONYANTIMONY (lat. Stibium), Sb, (read "stibium"), a chemical element with atomic number 51, atomic mass 121.75. Natural antimony consists of two stable isotopes: 121 Sb (content by mass 57.25%) and 123 Sb (42.75%). It is located in the VA group in the 5th period of the periodic system. Electronic configuration of outer layer 5 s 2
p 3
. Oxidation states +3, +5, rarely -3 (valencies III, V). The radius of the atom is 0.161 nm. Ion radius Sb 3+ 0.090 nm (coordination numbers 4 and 6), Sb 5+ 0.062 nm (6), Sb 3– 0.208 nm (6). Sequential ionization energies 8.64, 16.6, 28.0, 37.42 and 58.8 eV. Electronegativity according to Pauling (cm. PAULING Linus) 1,9.
Historical reference
Antimony was used in the countries of the East for three thousand years BC. The Latin name of the element is associated with the mineral "stibi", from which antimony was obtained in ancient Greece. The Russian "antimony" comes from the Turkish "surme" - to blacken the eyebrows (the powder for blackening the eyebrows was prepared from the antimony shine mineral). In the 15th century, the monk Vasily Valentin described the process of obtaining antimony, from an alloy with lead for casting typographic type. Natural sulphurous antimony he called antimony glass. In the Middle Ages, antimony preparations were used for medical purposes: antimony pills, wine aged in antimony bowls (in this case, a “vomiting stone” K 1 / 2H 2 O was formed).
Being in nature
The content in the earth's crust is 5 10 _–5% by weight. Occurs naturally in nature. About 120 minerals are known containing Sb, mainly in the form of Sb 2 S 3 sulfide (antimony luster, antimonite, stibnite). The product of sulfide oxidation with air oxygen Sb 2 O 3 is white antimony ore (valentinite and senarmontite). Antimony is often found in lead, copper and silver ores (tetrahedrite Cu 12 Sb 4 S 13, jamsonite Pb 4 FeSb 6 S 14).
Receipt
Antimony is obtained by fusing Sb 2 S 3 sulfide with iron:
Sb 2 S 3 + 3Fe \u003d 2Sb + 3FeS,
by roasting the sulfide Sb 2 S 3 and reducing the resulting oxide with coal:
Sb 2 S 3 + 5O 2 \u003d Sb 2 O 4 + 3SO 2,
Sb 2 O 4 + 4C \u003d 2Sb + 4CO. Pure antimony (99.9%) is obtained by electrolytic refining. Antimony is also extracted from lead concentrates obtained during the processing of polymetallic ores.
Physical and chemical properties
Antimony is a brittle non-metal, silvery-gray with a bluish tinge. Gray antimony, Sb I, with a rhombohedral lattice ( a\u003d 0.45064 nm, a \u003d 57.1 °), stable under normal conditions. Melting point 630.5°C, boiling point 1634°C. Density 6.69 g/cm 3 . At 5.5 GPa, Sb I transforms into the cubic modification Sb II, at a pressure of 8.5 GPa - into the hexagonal modification Sb III, above 28 GPa - Sb IV.
Gray antimony has a layered structure, where each Sb atom is pyramidally bonded to three layer neighbors (interatomic distance 0.288 nm) and has three nearest neighbors in another layer (interatomic distance 0.338 nm). Three amorphous modifications of antimony are known. Yellow antimony is formed by the action of oxygen on liquid stibine SbH 3 and contains small amounts of chemically bound hydrogen (cm. HYDROGEN). When heated or illuminated, yellow antimony turns into black antimony (density 5.3 g / cm 3), which has semiconductor properties.
During the electrolysis of SbCl 3 at low current densities, explosive antimony is formed, containing small amounts of chemically bound chlorine (explodes during friction). Black antimony, when heated without air access to 400 ° C, and explosive antimony, when rubbed, turn into metallic gray antimony. Antimony metal (Sb I) is a semiconductor. The band gap is 0.12 eV. Diamagnetic. At room temperature, metallic antimony is very brittle and can be easily ground into powder in a mortar, above 310°C it is plastic, and high-purity antimony single crystals are also plastic.
Antimony forms antimonides with some metals: tin antimonide SnSb, nickel Ni 2 Sb 3 , NiSb, Ni 5 Sb 2 and Ni 4 Sb. Antimony does not interact with hydrochloric, hydrofluoric and sulfuric acids. With concentrated nitric acid, poorly soluble beta-antimony acid HSbO 3 is formed:
3Sb + 5HNO 3 \u003d 3HSbO 3 + 5NO + H 2 O.
The general formula of antimony acids Sb 2 O 5 n H 2 O. Antimony reacts with concentrated H 2 SO 4 to form antimony (III) sulfate Sb 2 (SO 4) 3:
2Sb + 6H 2 SO 4 \u003d Sb 2 (SO 4) 3 + 3SO 2 + 6H 2 O.
Antimony is stable in air up to 600°C. Upon further heating, it is oxidized to Sb 2 O 3:
4Sb + 3O 2 \u003d 2Sb 2 O 3.
Antimony(III) oxide has amphoteric properties and reacts with alkalis:
Sb 2 O 3 + 6NaOH + 3H 2 O \u003d 2Na 3.
and acids:
Sb 2 O 3 + 6HCl \u003d 2SbCl 3 + 3H 2 O
When Sb 2 O 3 is heated above 700 ° C in oxygen, an oxide of the composition Sb 2 O 4 is formed:
2Sb 2 O 3 + O 2 \u003d 2Sb 2 O 4.
This oxide simultaneously contains Sb(III) and Sb(V). In its structure, octahedral groups and are connected to each other. With careful dehydration of antimony acids, antimony pentoxide Sb 2 O 5 is formed:
2HSbO 3 \u003d Sb 2 O 5 + H 2 O,
exhibiting acidic properties:
Sb 2 O 5 + 6NaOH \u003d 2Na 3 SbO 4 + 3H 2 O,
and being an oxidizing agent:
Sb 2 O 5 + 10HCl \u003d 2SbCl 3 + 2Cl 2 + 5H 2 O
Antimony salts are easily hydrolyzed. Precipitation of hydroxosalts begins at pH 0.5–0.8 for Sb(III) and pH 0.1 for Sb(V). The composition of the hydrolysis product depends on the salt / water ratio and the sequence of adding reagents:
SbCl 3 + H 2 O \u003d SbOCl + 2HCl,
4SbCl 3 + 5H 2 O = Sb 4 O 5 Cl 2 + 10HCl.
With fluorine (cm. FLUORINE) antimony forms pentafluoride SbF 5 . When it interacts with hydrofluoric acid HF, a strong acid H arises. Antimony burns when its powder is added to Cl 2 to form a mixture of SbCl 5 pentachloride and SbCl 3 trichloride:
2Sb + 5Cl 2 = 2SbCl 5, 2Sb + 3Cl 2 = 2SbCl 3.
With bromine (cm. BROMINE) and iodine (cm. IOD) Sb forms origalides:
2Sb + 3I 2 = 2SbI 3 .
Under the action of hydrogen sulfide (cm. hydrogen sulfide) H 2 S on aqueous solutions of Sb (III) and Sb (V), orange-red trisulfide Sb 2 S 3 or orange pentasulfide Sb 2 S 5 are formed, which interact with ammonium sulfide (NH 4) 2 S:
Sb 2 S 3 + 3 (NH 4) 2 S \u003d 2 (NH 4) 3 SbS 3,
Sb 2 S 5 + 3(NH 4) 2 S \u003d 2(NH 4) 3 SbS 4.
Under the influence of hydrogen (cm. HYDROGEN) stibine SbH 3 gas is released on the Sb salt:
SbCl 3 + 4Zn + 5HCl = 4ZnCl 2 + SbH 3 + H 2
Stibine, when heated, decomposes into Sb and H 2 . Organic antimony compounds, stibine derivatives, for example, orimethylstibin Sb(CH 3) 3, have been obtained:
2SbCl 3 + 3Zn(CH 3) 2 = 3ZnCl 2 + 2Sb(CH 3) 3
Application
Antimony is a component of alloys based on lead and tin (for battery plates, typographic fonts, bearings, protective screens for working with sources of ionizing radiation, dishes), based on copper and zinc (for artistic casting). Pure antimony is used to obtain antimonides with semiconductor properties. Included in the composition of complex medicinal synthetic drugs. In the manufacture of rubber, antimony pentasulfide Sb 2 S 5 is used.
Physiological action
Antimony belongs to trace elements, the content in the human body is 10-6% by weight. Constantly present in living organisms, the physiological and biochemical role has not been elucidated. 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. Dust and vapors of Sb cause nosebleeds, antimony "casting fever", pneumosclerosis, affect the skin, and disrupt sexual functions. For antimony aerosols MPC in air working area 0.5 mg / m 3, in atmospheric air 0.01 mg / m 3. MAC in soil 4.5 mg/kg, in water 0.05 mg/l.
encyclopedic Dictionary. 2009 .
Synonyms:See what "antimony" is in other dictionaries:
Antimony, uh... Russian word stress
- (pers. sourme). A metal found in nature in combination with sulfur; used in medicine as an emetic. Dictionary of foreign words included in the Russian language. Chudinov A.N., 1910. ANTIMONIUM, gray metal; beats V. 6.7;… … Dictionary of foreign words of the Russian language
Antimony, antimony, antimony, antimony, antimony, antimony, antimony, antimony, antimony, antimony, antimony, antimony, antimony (Source: "Full accentuated paradigm according to A. A. Zaliznyak") ... Forms of words
Surma, for example, old. expression: she furrowed her eyebrows (Habakkuk 259). From tour., Crimea. tat. sürmä antimony from sür to paint, tat. sørmä antimony (Radlov 4, 829 ff.); see Mi. TEl. 2, 161; Ryasyanen, Neuphil. Mitt. , 1946, p. 114; Zayonchkovsky, JP 19, 36;… … Etymological Dictionary of the Russian Language by Max Fasmer
- (symbol Sb), a poisonous semi-metallic element of the fifth group of the periodic table. The most common ore is antimony sulfide, Sb2S3. Antimony is used in some alloys, especially to harden lead used in ... ... Scientific and technical encyclopedic dictionary
- (lat. Stibium) Sb, a chemical element of group V of the periodic system, atomic number 51, atomic mass 121.75. Forms several modifications. Ordinary antimony (so-called gray) bluish-white crystals; density 6.69 g/cm³, mp 630.5°C. On the… … Big Encyclopedic Dictionary
ANTIMONY, antimony, pl. no, female (Persian surma metal). 1. The chemical element is a hard and brittle silvery-white metal, used. in various alloys in technology, in typography for the manufacture of gart. 2. The same as antimony. Dictionary… … Explanatory Dictionary of Ushakov
- (paint used in cosmetics). A sign of beauty. Tatar, Turkic, Muslim female names. Glossary of terms ... Dictionary of personal names
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 , German 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 by a critical analysis of a number of books by Vasily Valentin, they were 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 identified as 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 of celestial bodies (the Sun, the 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, really had no right to complain that it was in the category of “semimetals”
Judge for yourself. In appearance, crystalline, or gray, antimony (this is its main modification) is a typical metal gray white with a slight bluish tint, which is 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. Yes and in chemical reactions antimony exhibits such duality
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. In the upper parts of the ore bodies, near the surface of the earth, the antimony sheen 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 a 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-
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 a cosmetic. A detailed description of the properties and method of obtaining antimony and its compounds was 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 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 ; does not react with hydrogen and nitrogen under normal conditions. 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 is a chemical element (French Antimoine, English Antimony, German Antimon, Latin Stibium, from where the symbol is Sb, or Regulus antimonii; atomic weight = 120, if O = 16) is a shiny silvery-white metal with a coarse-plate crystalline broken or granular, depending on the speed of solidification from the molten state. Antimony crystallizes in blunt rhombohedrons, very close to a cube, like bismuth (see), and has ud. weight 6.71-6.86. Native antimony occurs in the form of scaly masses, usually containing silver, iron and arsenic; beats its weight is 6.5-7.0. It is the most brittle of metals, easily pulverized in an ordinary porcelain mortar. S. melts at 629.5 ° [According to the latest definitions (Heycock and Neville. 1895).] and distilled at white heat; even its vapor density was determined, which at 1640 ° turned out to be somewhat higher than required for the adoption of two atoms in a particle - Sb 2 [It was W. Meyer and G. Biltz who found in 1889 for the vapor density of S. with respect to air the following values: 10.743 at 1572° and 9.781 at 1640°, which indicates the ability of the particle to dissociate when heated. Since the density of 8.3 is calculated for the Sb 2 particle, the found densities seem to indicate the inability of this "metal" to be in the simplest state, in the form of a monatomic Sb 3 particle, which distinguishes it from real metals. The same authors investigated the vapor densities of bismuth, arsenic, and phosphorus. Only one bismuth was able to produce a Bi 1 particle; the following densities were found for it: 10.125 at 1700° and 11.983 at 1600°, and the densities calculated for Bi 1 and Bi 2 are 7.2 and 14.4. Particles of phosphorus P 4 (at 515 ° - 1040 °) and arsenic As 4 (at 860 °) dissociate from heating with difficulty, especially P 4: at 1700 ° from 3P 4 only one particle - one might think - turns into 2P 2, and As4 at the same time, it undergoes an almost complete transformation into As2. Thus, the most metallic of these elements, which make up one of the subgroups of the periodic system, is bismuth, judging by the vapor density; the properties of a non-metal belong to the greatest extent to phosphorus, characterizing at the same time arsenic and, to a lesser extent, to C.]]. S. can be distilled in a stream of dry gas, for example. hydrogen, since it is easily oxidized not only in air, but also in water vapor at a high temperature, turning into an oxide, or, what is the same, into antimony anhydride:
2Sb + 3H 2 O \u003d Sb2 O3 + 3H 2;
if you melt a piece of S. on a coal in front of a blowpipe and throw it from a certain height onto a sheet of paper, you get a mass of hot balls that roll, forming white oxide smoke. At ordinary temperatures, C. does not change in air. According to the forms of compounds and all chemical relations, S. belongs to the fifth group of the periodic system of elements, namely to its less metallic subgroup, which also contains phosphorus, arsenic and bismuth; it relates to the last two elements in the same way as tin in group IV relates to germanium and lead. The most important types of compounds S. two - SbX 3 and SbX 5, where it is trivalent and pentavalent; it is very probable that these types are at the same time the only ones. The halogen compounds of S. in particular clearly confirm what has just been said about the forms of the compounds. Trichloride
Sb2 S3 + 3HgCl2 = 2SbCl3 + 3HgS
moreover, volatile mercury sulphide remains more difficult in the retort, and SbCl 3 is distilled in the form of a colorless liquid, which solidifies in the receiver into a mass similar to cow butter (Butyrum Antimonii). Until 1648 the volatile product was believed to contain mercury; this year, Glauber showed the wrongness of this assumption. With strong heating of the residue in the retort, it also evaporates and gives a crystalline sublimation of cinnabar (Cinnabaris Antimonii) HgS. The easiest way is to prepare SbCl 3 from metallic S., acting on it with a slow current of chlorine while heating Sb + 1 ½ Cl2 \u003d SbCl3, and upon the disappearance of the metal, a liquid product is obtained containing a certain amount of S. pentachloride, which is very easy to get rid of by adding powdered S .:
3SbCl5 + 2Sb = 5SbCl3;
Finally, SbCl 3 is distilled. By heating sulfurous sulfur with strong hydrochloric acid in excess, a solution of SbCl 3 is obtained, during which hydrogen sulfide develops:
Sb2 S3 + 6HCl = 2SbCl3 + 3H2 S.
The same solution is also obtained by dissolving S.'s oxide in hydrochloric acid. During the distillation of an acidic solution, first of all, water and excess hydrochloric acid are distilled off, and then SbCl 3 is distilled - usually yellowish in the first portions (due to the presence of ferric chloride) and then colorless. S. trichloride is a crystalline mass that melts at 73.2° and boils at 223.5°, forming a colorless vapor, the density of which fully corresponds to the formula SbCl 3, namely, 7.8 relative to air. It attracts moisture from the air, spreading into a clear liquid, from which it can be isolated again in crystalline form when standing in a desiccator over sulfuric acid. In terms of its ability to dissolve in water (in small quantities), SbCl 3 is quite similar to other, real salts of hydrochloric acid, but large amounts of water decompose SbCl 3, turning it into one or another chloroxide, according to the equation:
SbCl3 + 2H 2 O \u003d (HO) 2 SbCl + 2HCl \u003d OSbCl + H 2 O + 2HCl
and 4SbCl 3 + 5Н 2 O = O5 Sb4 Cl2 + 10HCl
which represent the extreme limits of the incomplete action of water (there are oxychlorides of intermediate composition); a large excess of water leads to the complete removal of chlorine from the antimony compound. Water precipitates a white powder similar to C. chloroxides, but some SbCl 3 may remain in solution and precipitate with more water. By adding hydrochloric acid, the precipitate can be dissolved again, turning it into a solution of SbCl 3 . Obviously, S.'s oxide (see below) is a weak base, like bismuth oxide, and therefore water - in excess - is able to take away acid from it, turning average S.'s salts into basic salts, or, in this case, into chloroxide; the addition of hydrochloric acid is analogous to a decrease in the amount of reacting water, which is why oxychlorides are converted into SbCl 3 in this case. The white precipitate formed by the action of water on SbCl 3 is called Algorot powder named after a Verona doctor who used it (at the end of the 16th century) for medical purposes.
If molten sodium chloride trichloride is saturated with chlorine, then sodium pentachloride is obtained:
SbCl3 + Cl2 = SbCl5
discovered by G. Rose (1835). It can also be obtained from metal S., the powder of which, when poured into a vessel with chlorine, burns in it:
Sb + 2 ½ Cl2 = SbCl5.
It is a colorless or slightly yellowish liquid that smokes in the air and has a nasty odor; in the cold, it crystallizes in the form of needles and melts at -6 °; it is volatile SbCl 3, but partly decomposes during distillation:
SbCl5 = SbCl3 + Cl2;
under a pressure of 22 mm, it boils at 79 ° - without decomposition (under these conditions, the boiling point of SbCl 3 \u003d 113.5 °). The vapor density at 218° and under a pressure of 58 mm is 10.0 relative to air, which corresponds to the above partial formula (for SbCl 5 the calculated vapor density is 10.3). With the calculated amount of water at 0 ° SbCl 5 gives a crystalline hydrate SbCl 5 + H 2 O, soluble in chloroform and melting at 90 °; with a large amount of water, a transparent solution is obtained, which, when evaporated over sulfuric acid, gives another crystalline hydrate SbCl 5 + 4H 2 O, no longer soluble in chloroform (Anschütz and Evans, Weber). SbCl 5 refers to hot water as an acid chloride, giving its acidic hydrate in excess (see below). S. pentachloride easily converts to trichloride if substances are present that can add chlorine, as a result of which it is often used in organic chemistry for chlorination; it is a "chlorine transmitter". S. trichloride is capable of forming crystalline compounds, double salts with certain metal chlorides; similar compounds are produced by antimony pentachloride with various compounds and oxides. Antimony compounds are also known with other halides, namely SbF 3 and SbF 5 , SbBr3 , SbJ3 and SbJ 5 .
, or antimony anhydride, belongs to the type of trichloride C. and therefore can be represented by the formula Sb 2 O3, but the determination of the vapor density (at 1560 °, W. Meyer, 1879), which was found to be 19.9 with respect to air, showed that this oxide should be given double formula Sb 4 O6, similarly with arsenic and phosphorous anhydrides. Oxide S. occurs in nature in the form of valentinite, forming white, shiny rhombic prisms, beats. weight 5.57, and less often - senarmontite - colorless or gray octahedrons, with beats. weight. 5.2-5.3, and also sometimes covers in the form of an earthy coating - antimony ocher - various ores of S. The oxide is also obtained by firing sulfurous S. and occurs as the final product of the action of water on SbCl 3 in crystalline form and in amorphous - when treatment of metallic or sulfuric sulfur with dilute nitric acid when heated. S. oxide has a white color, turns yellow when heated, melts at a higher temperature, and, finally, volatilizes at white heat. When the molten oxide is cooled, it is obtained in a crystalline form. If oxygen oxide is heated in the presence of air, it absorbs oxygen, turning into the non-volatile oxide SbO 2 , or, more likely, Sb 2 O4 (see below). The basic properties of S.'s oxide are very weak, which has already been indicated above; its salts are most often basic. Of the mineral oxygen acids, almost one sulfuric acid is capable of producing sulfur salts; the average salt Sb 2 (SO4) 3 is obtained when a metal or oxide is heated with concentrated sulfuric acid, in the form of a white mass and crystallizes from somewhat diluted sulfuric acid in long, silky-shine needles; water decomposes it into a soluble acidic and insoluble basic salt. There are salts with organic acids, for example. the basic antimony-potassium salt of tartaric acid, or emetic stone KO-CO-CH (OH) -CH (OH) -CO-O-SbO + ½ H2 O (Tartarus emeticus), quite soluble in water (12.5 wt. frequent at 21°). S. oxide, on the other hand, has weak anhydride properties, which is easy to verify if a solution of caustic potash or sodium is added to a solution of SbCl 3: the resulting white precipitate dissolves in an excess of the reagent, just as it occurs for solutions of aluminum salts. Salts of antimonous acid are known mainly for potassium and sodium, for example, from a boiling solution of Sb 2 O3 in caustic soda, it crystallizes sodium antimony NaSbO2 + 3H2 O, in shiny octahedra; such salts are also known - NaSbO 2 + 2HSbO2 and KSbO 2 + Sb2 O3 [Perhaps this salt can be considered as the main double salt, potassium-antimony, orthoantimonous acid -
]. The corresponding acid, i.e. metaacid (similar to the names of phosphoric acids), HSbO 2 , however, is unknown; ortho- and pyroacids are known: H 3 SbO3 is obtained in the form of a thin white powder by the action of nitric acid on a solution of the mentioned double salt of tartaric acid and has this composition after drying at 100 °; H 4 Sb2 O5 is formed if an alkaline solution of trisulfuric acid is exposed to copper sulfate in such an amount that the filtrate stops giving an orange precipitate with acetic acid - the precipitate then turns white and has the indicated composition.
The highest oxide of the type of pentachloride C. is antimony anhydride Sb2 O5 . It is obtained by the action of vigorously boiling nitric acid on S.'s powder or on its oxide; the resulting powder is then subjected to gentle heating; it usually contains an admixture of a lower oxide. In its pure form, anhydride can be obtained from solutions of antimony acid salts by decomposing them with nitric acid and subjecting the washed precipitate to heating until the water elements are completely removed; it is a yellowish powder, insoluble in water, however, giving it the ability to turn blue litmus paper red. In nitric acid, the anhydride is completely insoluble, while in hydrochloric (strong) it dissolves, albeit slowly, completely; when heated with ammonia, it can volatilize. Three hydrates of antimony anhydride are known, having a composition corresponding to hydrates of phosphoric anhydride. Orthoantimony acid H3 SbO4 is obtained from potassium metaantimony by treating it with dilute nitric acid and is of proper composition after washing and drying at 100°; at 175° it turns into the metaacid HSbO3; both hydrates are white powders, soluble in solutions of caustic potash and difficult in water; when heated more strongly, they turn into an anhydride. Pyrosantimonic acid(Fremi called it a metaacid) is obtained by the action of hot water on S. pentachloride in the form of a white precipitate, which, after drying in air, has the composition H 4 Sb2 O7 + 2H 2 O, and at 100 ° turns into an anhydrous acid, which at 200 ° ( and even just standing under water - over time) turns into a metaacid. A pyroacid is more soluble in water than an orthoacid; it can also dissolve in cold ammonia, which orthoacid is not capable of. Salts are known only for meta- and pyroacids, which probably gives the right to give orthoacid the formula HSbO 3 + H 2 O, to consider it a metaacid hydrate. Sodium and potassium metasalts are obtained by fusion with the corresponding nitrate powder of metallic sulfur (or from sulfur sulfur). With KNO 3, after washing with water, a white powder is obtained, soluble in a noticeable amount in water and capable of crystallization; the salt isolated from the solution and dried at 100° contains water 2KSbO3 + 3H2 O; at 185° it loses one particle of water and turns into KSbO 3 + H2 O. The corresponding sodium salt has the composition 2NaSbO3 + 7H2 O, which at 200° loses 2H 2 O and becomes anhydrous only at red heat. Even carbonic acid is capable of decomposing these salts: if CO 2 is passed through a potassium salt solution, then a sparingly soluble precipitate of such an acid salt 2K 2 O ∙ 3Sb2 O5 + 7H2 O is obtained (this is after drying at 100 °, after drying at 350 ° there is still 2H 2 O). If a metaacid is dissolved in a hot ammonia solution, then the ammonium salt (NH 4 )SbO3 crystallizes upon cooling, which is hardly soluble in the cold. Oxidizing S. oxide, dissolved in caustic potash (antimony-acid potassium), with a chameleon and then evaporating the filtrate, one obtains acid pyroantimony potassium K 2 H2 Sb2 O7 + 4H 2 O; this salt is quite soluble in water (at 20 ° - 2.81 hours of anhydrous salt in 160 hours of water) and serves as a reagent in a qualitative analysis for sodium salts (in an average solution), since the corresponding crystalline salt Na 2 H2 Sb2 O7 + 6H2O is very sparingly soluble in water. It can be said to be the most difficultly soluble sodium salt, especially in the presence of some alcohol; when only 0.1% of the sodium salt is in the solution, then in this case a crystalline precipitate of the pyrosalt also appears. Since the antimony salts of lithium, ammonium and alkaline earth metals also form precipitates, it is clear that these metals must be removed first. Salts of other metals are hardly soluble or insoluble in water; they can be obtained through double decomposition in the form of crystalline precipitates and are converted by weak acids into acid salts, while strong acids completely displace antimony acid. Almost all antimoniates are soluble in hydrochloric acid.
With strong heating in air of each of the described S. oxides, another oxide is obtained, namely Sb 2 O4:
Sb2 O5 \u003d Sb2 O4 + ½O2 and Sb 2 O3 + ½O2 \u003d Sb2 O4.
This oxide can be considered as containing trivalent and pentavalent C., i.e. in this case it would be the average salt of orthoantimony acid Sb "" SbO4 or the main one - OSb-SbO 3 metaacids. This oxide is the most stable at high temperatures and represents an analogy with red lead (see Lead) and in particular with the corresponding bismuth oxide Bi 2 O4 (see Bismuth). Sb 2 O4 is a non-volatile white powder, very sparingly soluble in acids and obtained together with Sb 2 O3 by firing natural sulphide C. - Sb2 O4 has the ability to combine with alkalis; when fused with potash, after washing with water, a white product is obtained, soluble in hot water and having the composition K 2 SbO5; this salt-like substance is perhaps the double antimony-potassium salt of orthoantimony acid (OSb)K 2 SbO4 . Hydrochloric acid precipitates from a solution of such a salt an acidic salt K 2 Sb4 O9, which can be considered as a double salt of pyroantimony acid, namely (OSb) 2 K2 Sb2 O7 . In nature, there are similar double (?) salts for calcium and for copper: romeite (OSb)CaSbO4 and ammyolite (OSb)CuSbO4. In the form of Sb 2 O4, S. can be weighed in quantitative analysis; it is only necessary to ignite the washed oxygen compound of the metal with good access to air (in an open crucible) and carefully take care that combustible gases from the flame do not enter the crucible.
According to the method of formation of sulfur compounds, sulfur, like arsenic, can be ranked among real metals with more right than, for example, chromium. All compounds of trivalent S. in acidic solutions (preferably in the presence of hydrochloric acid) under the action of hydrogen sulfide are converted into an orange-red precipitate of trisulfide S., Sb 2 S3, which, in addition, also contains water. Compounds of pentavalent S., also in the presence of hydrochloric acid, with hydrogen sulfide give a yellowish-red powder of pentasulfuric S. Sb 2 S5, usually containing an admixture of Sb 2 S3 and free sulfur; pure Sb 2 S5 is obtained when an excess of hydrogen sulfide water is added at ordinary temperature to an acidified solution of antimony salt (Bunsen); in a mixture with Sb 2 S3 and sulfur, it is obtained if hydrogen sulfide is passed into a heated acidic solution; the lower the temperature of the precipitated solution and the faster the flow of hydrogen sulfide, the less Sb 2 S3 and sulfur are obtained and the purer the precipitated Sb 2 S5 (Bosêk, 1895). On the other hand, Sb 2 S3 and Sb 2 S5, like the corresponding arsenic compounds, have the properties of anhydrides; these are thioanhydrides; combining with ammonium sulfide or potassium sulfide, sodium, barium, etc., they give thiosalts, for example. Na 3 SbS4 and Ba 3 (SbS4) 2 or KSbS 2 and so on. These salts are obviously analogous to the oxygen salts of the elements of the phosphorus group; they contain divalent sulfur instead of oxygen and are usually called sulfosalts, which leads to confusion of concepts, reminiscent of salts of organic sulfonic acids, which it would be best to always call sulfonic acids [In the same way, the names of sulfo anhydrides (SnS 2, As2 S5, etc.) and sulfo bases (N 2 S, BaS, etc.) should be replaced by thio anhydrides and thio bases.]. Trisulphuric C. Sb 2 S3 under the name antimony gloss represents the most important ore of S.; it is quite common among crystalline and older layered rocks; found in Cornwallis, Hungary, Transylvania, Westphalia, Black Forest, Bohemia, Siberia; in Japan it is found in the form of especially large well-formed crystals, and in Borneo there are significant deposits. Sb 2 S3 crystallizes in prisms and usually forms radiant-crystalline, grayish-black masses with a metallic sheen; beats weight 4.62; fusible and easily crushed into a powder that stains fingers like graphite and has long been used as a cosmetic product for eyebrow liner; under the name "antimony" it was used and is probably still used for this purpose in our country. Black sulphurous sulfur in trade (Antimonium crudum) is smelted ore; this material in a fracture presents a gray color, a metallic luster and a crystalline composition. In nature, in addition, there are numerous salt-like compounds Sb 2 S3 with various sulfurous metals (thio bases), for example: berthierite Fe (SbS2) 2, wolfsbergite CuSbS2, boulangerite Pb3 (SbS3) 2, pyrargyrite, or red silver ore, Ag 3 SbS3, etc. Ores containing, in addition to Sb 2 S3, sulphurous zinc, copper, iron and arsenic, are the so-called. pale ores. If molten trisulphurous sulfur is subjected to rapid cooling to solidification (poured into water), then it is obtained in an amorphous form and then has a lower sp. weight, namely 4.15, has a lead-gray color, in thin layers it shines through hyacinth-red and in the form of a powder has a red-brown color; it does not conduct electricity, which is characteristic of crystalline modification. From the so-called antimony liver(hepar antimontii), which is obtained by fusing crystalline Sb 2 S3 with caustic potash or potash and contains a mixture of thioantimonite and potassium antimonite [Solutions of such a liver are very capable of absorbing atmospheric oxygen. Another type of liver, which is prepared from a powdered mixture of Sb 2 S3 and saltpeter (in equal amounts), and the reaction starts from a hot coal thrown into the mixture, and proceeds very vigorously with the gradual addition of the mixture, contains, in addition to KSbS 2 and KSbO 2, more K 2 SO4, as well as some antimony acid (K-salt).]:
2Sb2S3 + 4KOH = 3KSbS2 + KSbO2 + 2H2O
in the same way, amorphous trisulfuric acid can be obtained, for which the liver is removed with water and the filtered solution is decomposed with sulfuric acid, or crystalline Sb 2 S3 is treated with a boiling solution of KOH (or K 2 CO 3 ), and then the filtrate is decomposed with acid; in both cases, the precipitate is washed with strongly diluted acid (tartaric acid at the end) and water, and dried at 100°. It turns out a light red-brown, easily soiled powder of sulfurous sulfur, soluble in hydrochloric acid, caustic and carbonic alkalis much more easily than crystalline Sb 2 S3. Similar preparations of sulphurous sulfur, only not quite pure, have long been known under the name of "mineral kermes" and have been used in medicine and as a paint. The orange-red precipitate of Sb 2 S3 hydrate, which is obtained by the action of hydrogen sulfide on acidic solutions of sulfur oxide, loses (washed) water at 100°–130° and turns into a black modification at 200°; under a layer of dilute hydrochloric acid in a current of carbon dioxide, this transformation takes place already during boiling (Mitchell's lecture experiment, 1893). If you add hydrogen sulfide water to a solution of emetic stone, you get an orange-red (in transmitted light) solution of colloidal Sb 2 S3, which precipitates when calcium chloride and some other salts are added. Heating in a stream of hydrogen leads Sb 2 S3 to the complete reduction of the metal, while in a nitrogen atmosphere it only sublimates. Crystalline Sb 2 S3 is used for the preparation of other S. compounds, and is also used as a combustible substance in a mixture with Bertolet salt and other oxidizing agents for pyrotechnic purposes, is part of the heads of Swedish matches and is used for other ignition devices, and also has medicinal value - as a laxative for animals (horses). S. pentasulfur can be obtained as above, or through the decomposition with dilute acid of the mentioned soluble thiosalts:
2K H SbS4 + 6HCl = Sb2 S5 + 6KCl + 3H2 S.
It does not occur in nature, but has been known for a long time; Glauber described (in 1654) its production from slag, which is formed during the preparation of metallic silver from antimony luster when it is fused with tartar and saltpeter, by the action of acetic acid and recommended as a laxative (panacea antimonialis seu sulfur purgans universale). This sulfur compound has to be dealt with in the analysis: hydrogen sulfide precipitates metals of the 4th and 5th analytical groups from an acidified solution; among the latter is S.; it usually precipitates in the form of a mixture of Sb 2 S5 and Sb 2 S3 (see above) or only in the form of Sb 2 S 3 (when there were no compounds of the type SbX 5 in the precipitated solution) and then separated by the action of ammonium polysulphide from sulfide metals of the 4th groups that remain in the sediment; Sb 2 S3 is converted by ammonium polysulfur into Sb 2 S5, and then all of the S. is in solution in the form of an ammonium thiosalt of a higher type, from which, after filtration, it is precipitated by acid together with each other. sulfurous metals of the 5th group, if there were any in the test substance. S. pentasulfur is insoluble in water, easily soluble in aqueous solutions of caustic alkalis, their carbonic salts and alkali metal sulfides, also in ammonium sulfide and in a hot solution of ammonia, but not ammonium carbonate. When Sb 2 S5 is exposed to sunlight or heated under water at 98 °, and also without water, but in the absence of air, then it decays according to the equation:
Sb2 S5 = Sb2 S3 + 2S
as a result, when heated with strong hydrochloric acid, it gives sulfur, hydrogen sulfide and SbCl 3. Nampium thioantimonate, or "Salt of Schlippe", which crystallizes in large regular tetrahedra, colorless or yellowish, of the composition Na 3 SbS4 + 9H 2 O, can be obtained by dissolving a mixture of Sb 2 S3 and sulfur in a solution of caustic soda of a certain concentration or by fusing anhydrous sodium sulfate and Sb 2 S3 with charcoal and boiling then aqueous solution the resulting alloy with sulfur. Solutions of this salt have an alkaline reaction and a salty, cooling and at the same time bitter metallic taste. The potassium salt can be obtained in a similar way, and the barium salt arises when Sb 2 S5 is dissolved in a BaS solution; these salts form crystals of the composition K3 SbS4 + 9H2 O and Ba 3 (SbS4) 2 + 6H 2 O. Pentasulfur S. is used in the vulcanization of rubber (see) and gives it a well-known brown-red color. Antimony hydrogen
2SbH3 + 6S = Sb2 S Z + 3H2 S
whereby the orange-red modification of Sb 2 S3 is obtained; in a decomposing way, even in the dark, hydrogen sulfide, which itself decomposes at the same time:
2SbH3 + 3H 2 S \u003d Sb2 S3 + 6H 2.
If you skip SbH 3 (with H 2) into a solution of silver nitrate, you get a black precipitate, which is antimony silver with an admixture of metallic silver:
SbH3 + 3AgNO3 = Ag3 Sb + 3HNO3 ;
this compound S. is also found in nature - dyscrasite. Solutions of caustic alkalis dissolve SbH 3 , acquiring a brown color and the ability to absorb oxygen from the air. Similar relationships characterize arsenic hydrogen; both hydrogen compounds do not show in the least the ability to give derivatives of the ammonium type; they are rather reminiscent of hydrogen sulfide and exhibit the properties of acids. Other hydrogen compounds of S., poorer in hydrogen, judging by analogies, are not known with certainty; metallic silver, obtained by electrolysis and having the ability to explode, contains hydrogen; perhaps a similar hydrogen compound is present here, which is explosive, like acetylene or nitrous acid depleted in hydrogen. The existence of a volatile, even gaseous, hydrogenous compound for S. makes it especially possible to classify it as a non-metal; and its non-metallicity is probably due to the ability to produce various alloys with metals. Organometallic compounds
WITH . find very significant application; the presence of silver in them causes an increase in the brilliance and hardness, and in significant quantities, the brittleness of the metals fused with it. An alloy consisting of lead and S. (usually 4 hours and 1 hour) is used for casting typographic letters, for which alloys are often prepared containing, in addition, a significant amount of tin (10-25%), and sometimes also a little copper (about 2%). So called. "British metal" is an alloy of 9 hours of tin, 1 hour of C. and contains copper (up to 0.1%); it is used to make teapots, coffee pots, etc. utensils. "White, or anti-friction, metal" - alloys used for bearings; such alloys contain about 10% C. and up to 85% tin, which is sometimes replaced by almost half lead (Babbit's metall), in addition, up to 5% copper, the amount of which falls in favor of C. up to 1.5%, if in lead is found in the alloy, 7 hours C. with 3 hours of iron form a "Réaumur alloy" at white heat, which is very hard and gives sparks when processed with a file. Two crystalline compounds with zinc are known (Cooke jr.) Zn3 Sb2 and Zn 2 Sb2 and purple alloy with copper composition Cu 2 Sb (Regulus Veneris).Alloys with sodium or potassium, which are prepared by alloying S. with carbonic alkali metals and coal, as well as incandescent S. oxide with tartar, in a continuous state are quite constant in air, but in the form of powders and with a significant content of alkali metal, they are capable of self-igniting in air, and with water they emit hydrogen, give caustic alkali in solution and antimony powder in the precipitate.An alloy that is obtained by white heat of a close mixture of 5 parts of cream of tartar and 4 parts of C. , contains up to 12% potassium and is used to obtain organometallic compounds S. (see. also Alloys).
2SbCl3 + 3ZnR2 = 2SbR З + 3ZnCl2 ,
where R \u003d CH 3 or C 2 H5, etc., as well as in the interaction of RJ, iodine alcohol radicals, with the above-mentioned S. alloy with potassium. Trimethylstibine Sb(CH3 )3 boils at 81°, sp. weight 1.523 (15°); triethylstibine boils at 159°, sp. weight 1.324 (16°). These are almost water-insoluble, onion-scented liquids that ignite spontaneously in air. Connecting with RJ, stibins give stibonium iodide R4 Sb-J, from which - quite similarly to ammonium iodide, phosphonium and arsonium four-substituted hydrocarbon radicals - you can get basic hydrates of oxides of substituted stiboniums R 4 Sb-OH, which have the properties of caustic alkalis. But, in addition, stibines are very similar in their relations with divalent electropositive metals; they not only easily combine with chlorine, sulfur and oxygen, forming salt-like compounds, for example. (CH 3 )3 Sb=Cl2 and (CH 3 )3 Sb=S, and oxides, for example (CH 3 )3 Sb=O, but even displace hydrogen from acids, like zinc, for example:
Sb (C2 H 5) 3 + 2ClH \u003d (C 2 H5) 3 Sb \u003d Cl 2 + H 2.
Sulfurous stibines are precipitated from salt solutions sulfurous metals, turning into the corresponding salts, for example:
(C2 H5 )3 Sb = S + CuSO4 = CuS + (C2 H5 )3 Sb=SO4 .
A solution of its oxide can be obtained from stibine sulfate by precipitating sulfuric acid with caustic barite:
(C2 H5) 3 Sb \u003d SO 4 + Ba (OH) 2 \u003d (C 2 H5) 3 Sb \u003d O + BaSO 4 + H 2 O.
Such oxides are also obtained by the careful action of air on stibines; they are soluble in water, neutralize acids and precipitate true metal oxides. In composition and structure, stibine oxides are completely similar to those of phosphines and arsines, but differ from them in strongly pronounced basic properties. Triphenylstibin Sb (C6 H5) 3, which is obtained by the action of sodium on a benzene solution of a mixture of SbCl 3 with phenyl chloride and crystallizes in transparent tablets, melting at 48 °, is able to combine with halides, but not with sulfur or CH 3 J: the presence of negative phenyls lowers, next, the metallic properties of stibins; this is all the more interesting because the corresponding ratios of analogous compounds of more metallic bismuth are completely reversed: bismuthines Β iR3 containing limiting radicals are not capable of additions at all, and Β i(C6 Η 5 )3 gives (C 6 H5 )3 Bi=Cl2 and (C 6 H5 )3 Bi=Br 2 (see Bismuth). It is as if the electropositive character of Bi needs to be weakened by electronegative phenyls in order to obtain a compound similar to a metallic divalent atom. S. S. Kolotov.
Encyclopedic Dictionary F.A. Brockhaus and I.A. Efron. - St. Petersburg: Brockhaus-Efron. - GOLD (lat. Aurum), Au (read "aurum"), a chemical element with atomic number 79, atomic mass 196.9665. Known since ancient times. In nature, one stable isotope is 197Au. The configuration of the outer and pre-outer electron shells ... ... encyclopedic Dictionary
- (French Chlore, German Chlor, English Chlorine) an element from the group of halides; its sign is Cl; atomic weight 35.451 [According to Clarke's calculation of Stas's data.] at O = 16; a particle of Cl 2, which corresponds well to its densities found by Bunsen and Regnault with respect to ... ...
- (chem.; Phosphore French, Phosphor German, Phosphorus English and Latin, from where the designation P, sometimes Ph; atomic weight 31 [In recent times, the atomic weight of F. found (van der Plaats) is: 30.93 by restoration of a certain weight F. metal ... ... Encyclopedic Dictionary F.A. Brockhaus and I.A. Efron
Encyclopedic Dictionary F.A. Brockhaus and I.A. Efron
- (Soufre French, Sulfur or Brimstone English, Schwefel German, θετον Greek, Latin Sulfur, whence the symbol S; atomic weight 32.06 at O=16 [Determined by Stas from the composition of silver sulfide Ag 2 S]) belongs among the most important non-metallic elements. Encyclopedic Dictionary F.A. Brockhaus and I.A. Efron
- (Platine French, Platina or um English, Platin German; Pt = 194.83, if O = 16 according to K. Seibert). P. is usually accompanied by other metals, and those of these metals that adjoin it in their chemical properties, got the name ... ... Encyclopedic Dictionary F.A. Brockhaus and I.A. Efron
- (Soufre French, Sulphur or Brimstone English, Schwefel German, θετον Greek, Latin Sulfur, whence the symbol S; atomic weight 32.06 at O=16 [Determined by Stas from the composition of silver sulfide Ag2S]) belongs to the number the most important non-metallic elements. She… … Encyclopedic Dictionary F.A. Brockhaus and I.A. Efron
s; and. [Persian. surma metal] 1. Chemical element (Sb), bluish-white metal (used in various alloys in engineering, in typography). Smelting antimony. Combination of antimony with sulfur. 2. In the old days: dye for blackening hair, eyebrows, eyelashes. ... ... encyclopedic Dictionary
- (pers. sourme). A metal found in nature in combination with sulfur; used in medicine as an emetic. Dictionary of foreign words included in the Russian language. Chudinov A.N., 1910. ANTIMONIUM, gray metal; beats V. 6.7;… … Dictionary of foreign words of the Russian language
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