Antimony(lat. stibium), sb, chemical element of group V of the periodic system of Mendeleev; atomic number 51, atomic mass 121.75; The metal is silvery-white with a bluish tint. Two stable isotopes are known in nature: 121 sb (57.25%) and 123 sb (42.75%). Of the artificially obtained radioactive isotopes, the most important are 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Historical reference.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 eyebrows. In ancient Greece it was known as st i mi and st i bi, hence the Latin stibium. Around 12-14 centuries. n. e. the name antimonium appeared. In 1789 A. Lavoisier included S. in the list of chemical elements called antimoine (modern English antimony, Spanish and Italian antimonio, German antimon). Russian “antimony” comes from the Turkish s u rme; it denoted the powder of lead glitter pbs, which was also used for blackening eyebrows (according to other sources, “antimony” - from the Persian surme - 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 S content in the earth's crust (clarke) is 5? 10–5% by weight. S. is scattered in magma and the biosphere. From hot underground waters, it is concentrated in hydrothermal deposits. Antimony deposits themselves are known, as well as antimony-mercury, antimony-lead, gold-antimony, and antimony-tungsten deposits. Of the 27 minerals of S., the main industrial value is stibnite(sb 2 s 3) . Due to its affinity for sulfur, sulfur is often found as an impurity in 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: formed during electrolysis of a solution of sbcl 3; black (density 5.3 g/cm 3) - with rapid cooling of S. vapors; yellow - when oxygen is passed into liquefied sbh 3. Yellow and black S. are unstable, with low temperatures transform into ordinary S. The most stable crystalline S. , 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 bale 1635-1645 °C; 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) . S. diamagnetic, specific magnetic susceptibility -0.66? 10 –6. Unlike most metals, sulfur is brittle, easily splits along cleavage planes, grinds into powder, and cannot be forged (sometimes it is classified 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. In air it does not oxidize up to the melting point. Does not react with nitrogen and hydrogen. Carbon dissolves slightly in molten carbon. The metal actively interacts with chlorine and other halogens, forming antimony halides. Reacts with oxygen at temperatures above 630 °C to form sb 2 o 3 . When fused with sulfur one gets antimony sulfides, also interacts with phosphorus and arsenic. S. is resistant to water and dilute acids. Concentrated hydrochloric and sulfuric acids slowly dissolve S. to form chloride sbcl 3 and sulfate sb 2 (so 4) 3; concentrated nitric acid oxidizes carbon dioxide to a higher oxide, which is formed in the form of a hydrated compound xsb 2 o 5? uH 2 O. Of practical interest are sparingly soluble salts of antimony acid - antimonates (Mesbo 3 ? 3h 2 o, where me - na, K) and salts of unisolated metaantimony acid - metaantimonites (mesbo 2 ? 3H 2 O), which have reducing properties. S. combines with metals, forming antimonides.
Receipt. S. is obtained by pyrometallurgical and hydrometallurgical processing of concentrates or ore containing 20-60% sb. Pyrometallurgical methods include precipitation and reduction smelting. The raw materials for precipitation smelting are sulfide concentrates; the process is based on the displacement of iron 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 into rough metal is more than 90%. Reduction smelting of steel is based on the reduction of its oxides to metal charcoal or coal dust and waste rock slagging. Reduction smelting is preceded by oxidative roasting at 550 °C with excess air. The cinder contains non-volatile C tetroxide. Electric furnaces can be used for both precipitation and reduction smelting. The hydrometallurgical method for producing sulfur consists of two stages: processing the raw material with an alkaline sulfide solution, transferring sulfur into solution in the form of salts of antimony acids and sulfosalts, and separating sulfur by electrolysis. Depending on the composition of the raw materials and the method of its preparation, rough steel contains from 1.5 to 15% impurities: fe, as, s, etc. To obtain pure steel, pyrometallurgical or electrolytic refining is used. During pyrometallurgical refining, iron and copper impurities are removed in the form of sulfur compounds by introducing S. stibnite (crudum) - sb 2 s 3 into the melt, after which arsenic (in the form of sodium arsenate) and sulfur are removed by blowing air under the soda slag. During electrolytic refining with a soluble anode, the rough steel 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 carbon dioxide, zone melting is used in an atmosphere of inert gas, or carbon dioxide is obtained from pre-purified compounds—trioxide or trichloride.
Application. S. is used mainly in the form of lead- and tin-based alloys for battery plates, cable sheaths, and 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 a dopant for 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. Crane.
Antimony in the body. Contents of pages (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 in feces, and in small quantities in urine. Biological role S. unknown. It is selectively concentrated in the thyroid gland, liver, and spleen. In erythrocytes, C accumulates predominantly in the oxidation state + 3, in blood plasma - in the oxidation state + 5. The maximum permissible concentration of C is 10 –5 - 10 –7 G by 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. preparations (solyusurmin, etc.) are used mainly for the treatment of leishmaniasis and some helminthiases (for example, schistosomiasis).
S. and its compounds are poisonous. Poisoning is possible during the smelting of antimony ore concentrate and in the production of S 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, efficient ventilation, etc.
Lit.: Shiyanov A.G., Antimony production, M., 1961; Fundamentals of Metallurgy, vol. 5, M., 1968; Research into creation new technology production of antimony and its compounds, in the collection: Chemistry and technology of antimony, France, 1965.
Antimony
ANTIMONY-s; and.[Persian. surma - metal]
1. Chemical element (Sb), bluish-white metal (used in various alloys in technology, in printing). Antimony smelting. A compound of antimony and sulfur.
2. In the old days: dye for blackening hair, eyebrows, eyelashes. Draw and draw eyebrows with antimony. Traces of antimony on the face.
◁ Antimony, -aya, -oe (1 sign). C ores. C alloys. S. shine(a lead-gray mineral containing antimony and sulfur).
antimony(lat. Stibium), chemical element of group V of the periodic table. Forms several modifications. Ordinary antimony (so-called gray) is bluish-white crystals; density 6.69 g/cm 3, t mp 630.5°C. Does not change in air. The most important mineral is stibnite (antimony luster). Component of alloys based on lead and tin (battery, printing, bearing, etc.), semiconductor materials.
ANTIMONYANTIMONY (lat. Stibium), Sb, (read “stibium”), chemical element with atomic number 51, atomic mass 121.75. Natural antimony consists of two stable isotopes: 121 Sb (mass content 57.25%) and 123 Sb (42.75%). Located in group VA in the 5th period of the periodic table. Electronic configuration of outer layer 5 s 2
p 3
. Oxidation states +3, +5, rarely –3 (valency III, V). Atomic radius 0.161 nm. The radius of the Sb 3+ ion is 0.090 nm (coordination numbers 4 and 6), Sb 5+ 0.062 nm (6), Sb 3– 0.208 nm (6). (The sequential ionization energies are 8.64, 16.6, 28.0, 37.42 and 58.8 eV. Electronegativity according to Pauling cm. 1,9.
PAULING Linus)
Historical reference
Antimony was used in Eastern countries 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 eyebrows (the powder for blackening eyebrows was prepared from the mineral antimony shine). In the 15th century, the monk Vasily Valentin described the process of obtaining antimony from an alloy with lead for casting typographic fonts. He called natural antimony sulphide antimony glass. In the Middle Ages, antimony preparations were used for medical purposes: antimony pills, wine kept in antimony bowls (this formed “tartar emetic” K·1/2H 2 O).
Being in nature
The content in the earth's crust is 5·10_–5% by mass. Occurs in nature in a native state. About 120 minerals containing Sb are known, mainly in the form of sulfide Sb 2 S 3 (antimony luster, stibnite, 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, jamesonite Pb 4 FeSb 6 S 14).
Receipt
Antimony is obtained by fusing Sb 2 S 3 sulfide with iron:
Sb 2 S 3 +3Fe=2Sb+3FeS,
by roasting Sb 2 S 3 sulfide and reducing the resulting oxide with coal:
Sb 2 S 3 +5O 2 =Sb 2 O 4 +3SO 2,
Sb 2 O 4 +4C=2Sb+4CO. Pure antimony (99.9%) is obtained by electrolytic refining. Antimony is also extracted from lead concentrates obtained from the processing of polymetallic ores.
Antimony is a silver-gray with a bluish tint and a brittle non-metal. Gray antimony, Sb I, with a rhombohedral lattice ( a=0.45064 nm, a=57.1°), stable under normal conditions. Melting point 630.5°C, boiling point 1634°C. Density 6.69 g/cm3. 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, and above 28 GPa into Sb IV.
Gray antimony has a layered structure, where each Sb atom is pyramidally bonded to three neighbors in the layer (interatomic distance 0.288 nm) and has three nearest neighbors in the other 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 (The sequential ionization energies are 8.64, 16.6, 28.0, 37.42 and 58.8 eV. Electronegativity according to Pauling HYDROGEN). When heated or illuminated, yellow antimony transforms into black antimony (density 5.3 g/cm3), 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 upon friction). Black antimony, when heated without access to air to 400°C, and explosive antimony, when ground, 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 easily ground into powder in a mortar; above 310°C it is plastic; high-purity antimony single crystals are also plastic.
With some metals, antimony forms antimonides: tin antimonide SnSb, nickel antimonide 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 = 3HSbO 3 + 5NO + H 2 O.
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 = Sb 2 (SO 4) 3 + 3SO 2 + 6H 2 O.
Antimony is stable in air up to 600°C. With further heating, it oxidizes to Sb 2 O 3:
4Sb + 3O 2 = 2Sb 2 O 3.
Antimony(III) oxide has amphoteric properties and reacts with alkalis:
Sb 2 O 3 + 6NaOH + 3H 2 O = 2Na 3.
and acids:
Sb 2 O 3 + 6HCl = 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 = 2Sb 2 O 4.
This oxide simultaneously contains Sb(III) and Sb(V). In its structure, octahedral groups and are connected to each other. When antimony acids are carefully dehydrated, antimony pentoxide Sb 2 O 5 is formed:
2HSbO 3 = Sb 2 O 5 + H 2 O,
exhibiting acidic properties:
Sb 2 O 5 + 6NaOH = 2Na 3 SbO 4 + 3H 2 O,
and being an oxidizing agent:
Sb 2 O 5 + 10HCl = 2SbCl 3 + 2Cl 2 + 5H 2 O
Antimony salts are easily hydrolyzed. The precipitation of hydroxo salts 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 reagent addition:
SbCl 3 + H 2 O = SbOCl + 2HCl,
4SbCl 3 + 5H 2 O = Sb 4 O 5 Cl 2 + 10HCl.
With fluoride (The sequential ionization energies are 8.64, 16.6, 28.0, 37.42 and 58.8 eV. Electronegativity according to Pauling FLUORINE) Antimony forms pentafluoride SbF 5. When it interacts with hydrofluoric acid HF, a strong acid H appears. 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 (The sequential ionization energies are 8.64, 16.6, 28.0, 37.42 and 58.8 eV. Electronegativity according to Pauling BROMINE) and iodine (The sequential ionization energies are 8.64, 16.6, 28.0, 37.42 and 58.8 eV. Electronegativity according to Pauling IOD) Sb forms orihalides:
2Sb + 3I 2 = 2SbI 3.
Under the influence of hydrogen sulfide (The sequential ionization energies are 8.64, 16.6, 28.0, 37.42 and 58.8 eV. Electronegativity according to Pauling HYDROGEN Sulfide) H 2 S into 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 react with ammonium sulfide (NH 4) 2 S:
Sb 2 S 3 + 3(NH 4) 2 S = 2(NH 4) 3 SbS 3,
Sb 2 S 5 + 3(NH 4) 2 S = 2(NH 4) 3 SbS 4.
Under the influence of hydrogen (The sequential ionization energies are 8.64, 16.6, 28.0, 37.42 and 58.8 eV. Electronegativity according to Pauling HYDROGEN) on Sb salts the gas stibine SbH 3 is released:
SbCl 3 + 4Zn + 5HCl = 4ZnCl 2 + SbH 3 + H 2
When heated, stibine decomposes into Sb and H 2 . Organic antimony compounds, stibine derivatives, for example, orimethylstibine Sb(CH 3) 3, were 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 complex medicinal synthetic preparations. In the manufacture of rubber, antimony pentasulfide Sb 2 S 5 is used.
Physiological action
Antimony is a microelement; its content in the human body is 10–6% by weight. Constantly present in living organisms, the physiological and biochemical role is not clear. 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 there are hydrolyzed to form poorly soluble products. Dust and Sb vapors cause nosebleeds, antimony "foundry fever", pneumosclerosis, affect the skin, and disrupt sexual functions. For antimony aerosols, maximum permissible concentrations in the air working area 0.5 mg/m3, in atmospheric air 0.01 mg/m3. MPC in soil is 4.5 mg/kg, in water 0.05 mg/l.
encyclopedic Dictionary. 2009 .
Synonyms:See what “antimony” is in other dictionaries:
Antimony, s... Russian word stress
- (pers. sourme). A metal found in nature in combination with sulfur; used medicinally as an emetic. Dictionary of foreign words included in the Russian language. Chudinov A.N., 1910. ANTIMONY antimony, gray metal; beat 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: “Complete accentuated paradigm according to A. A. Zaliznyak”) ... Forms of words
Surma, for example, is old. expression: furrowed eyebrows (Habakkuk 259). From Tur., Crimea. tat. sürmä antimony from sür to paint, tat. sørmä antimony (Radlov 4, 829 et seq.); see Mi. TEl. 2, 161; Räsänen, Neuphil. Mitt. , 1946, p. 114; Zayonchkovsky, JР 19, 36;… … Etymological Dictionary of the Russian Language by Max Vasmer
- (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, chemical element of group V of the periodic system, atomic number 51, atomic mass 121.75. Forms several modifications. Ordinary antimony (so-called gray) is bluish-white crystals; density 6.69 g/cm³, melting point 630.5 °C. On the… … Big Encyclopedic Dictionary
ANTIMONY, antimony, pl. no, female (pers. surma metal). 1. Chemical element, hard and brittle, silver-white metal, used. in various alloys in technology, in printing for the manufacture of garth. 2. The same as antimony. Dictionary… … Ushakov's Explanatory Dictionary
- (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; metal of silvery-white color with a bluish tint; two stable isotopes 121 are known in nature 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 glitter powder ( Sb 2 S 3 ) entitled mesten or stem used for blackening 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. Louvasier included antimony in the list of chemical elements called antimoine (modern English antimony , Spanish and Italian antimonio , German antimon ). Russian “antimony” comes from Turkish surme ; it denoted lead glitter powder PbS , which also served for blackening eyebrows (according to other sources, “antimony” - from the Persian surme - metal).
The first book known to us, which describes in detail the properties of antimony and its compounds, 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 proven that Brother Vasily Valentin was never listed in the lists of monks of the Benedictine Order. There is, however, information that allegedly XV century, in the Erfurt monastery there lived a monk named Basil, very knowledgeable in alchemy; some manuscripts belonging to him were found after his death in a box along with gold powder. But it is apparently impossible to identify him with the author of “The Triumphal Chariot of Antimony”. Most likely, as a critical analysis of a number of books by Vasily Valentin showed, they were written by different persons, and not earlier than the second half XVI century.
Even medieval metallurgists and chemists noticed that antimony was forged worse than “classical” metals, and therefore, together with zinc, bismuth and arsenic, it was placed in a special group - “semi-metals”. There were other “compelling” reasons for this: according to alchemical concepts, each metal was associated with one or another celestial body. “Seven metals were created by light according to the number of seven planets,” said one of the most important postulates of alchemy. At some stage, people actually 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 the deepest philosophical pattern in this. A harmonious alchemical theory stated that gold represented the Sun in the heavens, silver was the typical Moon, copper was undoubtedly related to Venus, iron clearly gravitated towards Mars, mercury corresponding to Mercury, tin personified Jupiter, and lead Saturn. For other elements, there was not a single vacancy left in the series of metals.
If for zinc and bismuth such discrimination caused by the shortage of celestial bodies was clearly unfair, then antimony with its unique physical and chemical properties really had no right to complain that it ended up in the category of “semi-metals.”
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 there are (three amorphous modifications are also known: yellow, black and the so-called explosive). But appearances, as we know, can be deceiving, and antimony confirms this. Unlike most metals, it is, firstly, very fragile and easily abraded into powder, and secondly, it conducts electricity and heat much worse. Yes and in chemical reactions antimony exhibits such duality
ity, which does not allow us to unambiguously answer the question: is it metal or not metal.
As if to retaliate against the metals for being reluctant to accept them into their ranks, molten antimony dissolves almost all metals. They knew about this back in the old days, 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 Michael Meyer “Running Atlanta”, published in 1618, there was, for example, the following drawing: 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 the lake, where there is a boat that should take him to the palace on the opposite bank. Symbolically, this drawing depicted a method of purifying gold (tsar) from impurities of silver and copper with the help of stibnite (wolf) - a natural sulfide of antimony, and gold formed a compound with antimony, which then, with a stream of air - the antimony evaporated in the form of three oxides, and pure gold was obtained. This method existed before XVIII century.
The antimony content in the earth's crust is 4*10 -5 wt%. World antimony reserves, estimated at 6 million tons, are concentrated mainly in China (52% of world reserves). The most common mineral is antimony luster, or stibine (stibine) Sb 2 S 3 , lead-gray color with a metallic luster, which crystallizes in the rhombic system with a density of 4.52-4.62 g / cm 3 and hardness 2. In the main mass, antimony luster 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 ore bodies, near the surface of the earth, the antimony luster undergoes oxidation, forming a number of minerals, namely senarmontite and valentite Sb 2 O 3 ; sideboard Sb2O4 ; stibiocanite Sb 2 O 4 H 2 O ; kermisite 3Sb 2 S 3 Sb 2 O . In addition to its own antimony ores, there are also ores in which antimony is found in the form of complex compounds with copper and lead
mercury and zinc (fahl ores).
Significant deposits of antimony minerals are located in China, the Czech Republic, Slovakia, Bolivia, Mexico, Japan, the USA, and 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 almost a thousand tons of antimony from abroad). 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 there was no time for antimony. Geological searches, continued by the scientist almost two decades later, were crowned with success, and already in 1934 antimony trisulfide began to be obtained from Kadamdzhay ores, and a year later the first domestic metallic antimony was smelted at a pilot plant. By 1936, there was no longer any need to buy it abroad.
PHYSICAL AND CHEMICAL
PROPERTIES.
Antimony has one crystalline form and several amorphous forms (the so-called yellow, black and explosive antimony). Under ordinary conditions, only crystalline antimony is stable; it is silvery-white in color with a bluish tint. Pure metal, when cooled slowly under a layer of slag, forms needle-shaped crystals on the surface, reminiscent of the shape of stars. The structure of the crystals is rhombohedral, a = 4.5064 A, a = 57.1 0.
Density of crystalline antimony 6.69, liquid 6.55 g / cm 3. Melting point 630.5 0 C, boiling point 1635-1645 0 C, heat of fusion 9.5 kcal / g-atom, heat of vaporization 49.6 kcal / g-atom. Specific heat capacity (cal / g deg):0.04987(20 0); 0.0537(350 0); 0.0656(650-950 0). Thermal conductivity (cal / em.sec.deg):
0.045,(0 0); 0.038(200 0); 0.043(400 0); 0.062(650 0). Antimony is fragile and easily abraded into powder; viscosity (poise); 0.015(630.5 0); 0.082(1100 0). Brinell hardness for cast antimony 32.5-34 kg / mm 2, for high purity antimony (after zone melting) 26 kg / mm 2. Modulus of elasticity 7600kg / mm 2, tensile strength 8.6 kg / mm 2, compressibility 2.43 10 -6 cm 2 / kg.
Yellow antimony is obtained by passing oxygen or air into antimonous hydrogen liquefied at -90 0; already at –50 0 it turns into ordinary (crystalline) antimony.
Black antimony is formed by rapid cooling of antimony vapor, and at approximately 400 0 it turns into ordinary antimony. The density of black antimony is 5.3. Explosive antimony is a silvery shiny metal with a density of 5.64-5.97, formed during the electrical production of antimony from a hydrochloric acid solution of antimony chloride (17-53% SbCl2 in hydrochloric acid d 1.12), with a current density ranging from 0.043 to 0.2 A / dm 2. The resulting antimony transforms into ordinary antimony with an explosion caused by friction, scratching or touching the heated metal; the explosion is caused by the exothermic process of transition from one form to another.
In air under normal conditions, antimony ( Sb ) does not change, it is insoluble either in water or in organic solvents, but it easily forms alloys with many metals. In the voltage series, antimony is located between hydrogen and copper. Antimony does not displace hydrogen from acids even in dilute HCl And H2SO4 does not dissolve. However, strong sulfuric acid, when heated, converts antimony into E 2 sulfates (SO 4) 3 . Strong nitric acid oxidizes antimony to acids H 3 EO 4. Alkali solutions by themselves do not affect antimony, but in the presence of oxygen they slowly destroy it.
When heated in air, antimony burns to form oxides; it also easily combines with gas
ANTIMONY, Sb (from Turkish sрme, Latin Stibium * a. antimony; n. Antimon; f. antimoine; i. antimonio), is a chemical element of group V of the periodic system of Mendeleev, 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 product. 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 silver-white substance with a bluish tint and a metallic sheen; crystalline and 3 amorphous forms of antimony are known (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, grinds 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/m3) explodes on contact; is formed during the electrolysis of a SbCl 3 solution. Black antimony (density 5300 kg/m3) is obtained by rapidly cooling its vapors with carbon; yellow modification - when oxygen is passed through liquid hydride SbH 3. The yellow and black modifications are metastable formations and over time pass into the crystalline phase.
Antimony in compounds exhibits a valence of +5, +3, -3; chemically inactive, does not oxidize in air up to the melting point. Antimony reacts with oxygen only in a molten state, forming Sb2O 3 ; does not react with hydrogen and nitrogen under normal conditions. Actively interacts with halogens (with the exception of F2). Antimony dissolves slowly 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/m3.
The average content of antimony in the earth's crust (clarke) is 5.10 -5%, in ultrabasic rocks 1.10 -5%, basic rocks 1.10 -4%, acidic rocks 2.6.10 -5%. Antimony is concentrated in hydrothermal deposits. Antimony itself, as well as antimony-mercury, antimony-lead, gold-antimony, antimony-tungsten deposits are known. Out of 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) - a shiny silvery-white metal with a coarse-plate crystalline fractured or granular, depending on the speed of solidification from the molten state. Antimony crystallizes in obtuse rhombohedrons, very close to a cube, like bismuth (see), and has a beat. weight 6.71-6.86. Native antimony occurs in the form of scaly masses, usually containing silver, iron and arsenic; beat its weight is 6.5-7.0. This is the most fragile of metals, easily reduced to powder in an ordinary porcelain mortar. S. melts at 629.5° [According to the latest definitions (Heycock and Neville. 1895).] and is distilled at white heat; Even its vapor density was determined, which at 1640° turned out to be slightly greater than what is required to accept two atoms in a particle - Sb 2 [It was W. Meyer and G. Biltz who found in 1889 the following for the density of S. vapor in relation to air 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 densities found 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 studied the vapor densities of bismuth, arsenic and phosphorus. Only bismuth alone was capable of producing 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 Р 4 (at 515° - 1040°) and arsenic As 4 (at 860°) are difficult to dissociate from heating, especially Р 4: at 1700° from 3Р 4 only one particle - one might think - turns into 2Р 2, and As4 at the same time, it undergoes an almost complete transformation into As2. Thus, the most metallic of these elements, constituting one of the subgroups of the periodic table, is bismuth, judging by the vapor density; the properties of a non-metal belong to the greatest extent to phosphorus, while at the same time characterizing arsenic and, to a lesser extent, S.]].
S. can be distilled in a stream of dry gas, for example. hydrogen, since it easily oxidizes not only in air, but also in water vapor at high temperatures, turning into oxide, or, what is the same, into antimonous anhydride:
if you melt a piece of S. on 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 temperature, C does not change in air. In terms of the forms of compounds and all chemical relationships, S. belongs to group V 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. There are two most important types of S. compounds - SbX 3 and SbX 5, where it is trivalent and pentavalent; it is very likely that these types are at the same time the only ones. S.'s halide compounds especially clearly confirm what has just been said about the forms of compounds. Trichloride
Sb2 S3 + 3HgCl2 = 2SbCl3 + 3HgS
whereby the volatile mercury sulphide remains 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). Before 1648, the volatile product was believed to contain mercury; this year Glauber showed that assumption was wrong. When the residue is heated strongly in a retort, it also volatilizes and gives a crystalline distillation of cinnabar (Cinnabaris Antimonii) HgS. The easiest way to prepare SbCl 3 from metallic carbon is by applying a slow current of chlorine to it while heating Sb + 1 ½ Cl2 = SbCl3, and after the metal disappears, a liquid product is obtained containing a certain amount of pentachloride, which is very easy to get rid of by adding powdered carbon. .:
3SbCl5 + 2Sb = 5SbCl3 ;
Finally, SbCl 3 is distilled. By heating sulfur dioxide with strong hydrochloric acid in excess, a solution of SbCl 3 is obtained, and hydrogen sulfide develops:
Sb2 S3 + 6HCl = 2SbCl3 + 3H2 S.
The same solution is obtained by dissolving S. oxide in hydrochloric acid. When distilling 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 colorless vapor, the density of which fully corresponds to the formula SbCl 3, namely equal to 7.8 relative to air. It attracts moisture from the air, dissolving 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, true salts of hydrochloric acid, but large quantities of water decompose SbCl 3, turning it into one or another oxychloride, according to the equation:
SbCl3 + 2H 2 O = (HO)2 SbCl + 2HCl = OSbCl + H 2 O + 2HCl
and 4SbCl 3 + 5H 2 O = O5 Sb4 Cl2 + 10HCl
which represent the extreme limits of the incomplete action of water (there are chloroxides of intermediate composition); a large excess of water leads to the complete removal of chlorine from the antimony compound. Water precipitates white powder of similar S. chloroxides, but part of the SbCl 3 can remain in solution and precipitate with more water. By adding hydrochloric acid, you can dissolve the precipitate again and turn it into a solution of SbCl 3 . Obviously, S. oxide (see below) is a weak base, like bismuth oxide, and therefore water - in excess - is able to take away the acid from it, turning the average salts of S. into basic salts, or, in this case, into oxychloride; adding hydrochloric acid is similar to reducing the amount of reacting water, which is why chloroxides are converted into SbCl 3. The white precipitate resulting from the action of water on SbCl 3 is called Algorot powder named after the Verona doctor who used it (at the end of the 16th century) for medical purposes.
If you saturate molten trichloride with chlorine, you get pentachloride:
SbCl3 + Cl2 = SbCl5
discovered by G. Rose (1835). It can also be obtained from metal chlorine, 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 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 during distillation it partly decomposes:
SbCl5 = SbCl3 + Cl2;
under a pressure of 22 mm, it boils at 79° - without decomposition (under these conditions, the boiling point of SbCl 3 = 113.5°). The vapor density at 218° and under a pressure of 58 mm is equal to 10.0 relative to air, which corresponds to the given partial formula (for SbCl 5 the calculated vapor density is 10.3). With the calculated amount of water at 0°, SbCl 5 gives crystalline hydrate SbCl 5 + H 2 O, soluble in chloroform and melting at 90°; with a large amount of water a clear solution is obtained, which, when evaporated over sulfuric acid, gives another crystalline hydrate SbCl 5 + 4H 2 O, no longer soluble in chloroform (Anschutz and Evans, Weber). SbCl 5 treats hot water as an acid chloride, giving in excess its acidic hydrate (see below). S. pentachloride easily transforms into trichloride if substances capable of adding chlorine are present, 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 some metal chlorides; Antimony pentachloride with various compounds and oxides also produces similar compounds. Antimony compounds are also known with other halogens, namely SbF 3 and SbF 5, SbBr3, SbJ3 and SbJ 5.
, or antimonous anhydride, belongs to the type of trichloride S. and therefore can be represented by the formula Sb 2 O3, but determination of the vapor density (at 1560 °, W. Meyer, 1879), which was found equal to 19.9 relative to air, showed that this oxide should be given double formula Sb 4 O6, similarly with arsenic and phosphorous anhydrides. S. oxide occurs in nature in the form of valentinite, forming white, shiny prisms of the rhombic system, sp. weight 5.57, and less often - senarmontite - colorless or gray octahedra, with sp. 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 burning sulfur dioxide and appears as the final product of the action of water on SbCl 3 in crystalline form and in amorphous form - when treatment of metallic or sulfur dioxide with diluted nitric acid when heated. S. oxide is white in color, turns yellow when heated, melts at a higher temperature and finally evaporates at white heat. When the molten oxide is cooled, it becomes crystalline. If S. oxide is heated in the presence of air, it absorbs oxygen, turning into the non-volatile oxide SbO 2, or, more likely, into Sb 2 O4 (see below). The basic properties of S. oxide are very weak, as already indicated above; its salts are most often basic. Of the mineral oxygen acids, almost only sulfuric acid is capable of producing S. 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 slightly diluted sulfuric acid in long, silky-shiny needles; water decomposes it into soluble acidic and insoluble basic salts. There are salts with organic acids, e.g. basic antimony-potassium salt of tartaric acid, or tartar emetic 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 you add a solution of caustic potassium or soda to a solution of SbCl 3: the resulting white precipitate dissolves in an excess of the reagent, just as is the case for solutions of aluminum salts. Mostly for potassium and sodium, salts of antimonous acid are known, for example, Sb 2 O3 crystallizes from a boiling solution of sodium hydroxide 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 a basic double salt, potassium-antimony, orthoantimonous acid -
]. The corresponding acid, i.e., meta-acid (by analogy with 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 fine 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 trisulfur S. is exposed to copper sulfate in such an amount that the filtrate ceases to give an orange precipitate with acetic acid - the precipitate then turns out white and has the indicated composition.
A higher oxide such as S. pentachloride is antimony anhydride Sb2 O5. It is obtained by the action of vigorously boiling nitric acid on S. powder or its oxide; the resulting powder is then gently heated; it usually contains an admixture of lower oxide. In its pure form, the anhydride can be obtained from solutions of antimony acid salts, 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 color blue litmus paper red. The anhydride is completely insoluble in nitric acid, but it dissolves completely in hydrochloric (strong) acid, although slowly; when heated with ammonia it can volatilize. Three hydrates of antimony anhydride are known, with a composition corresponding to phosphorus anhydride hydrates. Orthoantimonic acid H3 SbO4 is obtained from potassium metaantimony by treating it with dilute nitric acid and has the proper composition after washing and drying at 100°; at 175° it turns into meta-acid HSbO3; both hydrates are white powders, soluble in solutions of caustic potash and difficult in water; with stronger heating they turn into anhydride. Pyrosantimonic acid(Fremy called it metaacid) is obtained by the action of hot water on S. pentachloride in the form of a white precipitate, which, when dried in air, has the composition H 4 Sb2 O7 + 2H 2 O, and at 100° it turns into an anhydrous acid, which at 200° ( and even just standing under water - over time) turns into meta-acid. Pyroacid is more soluble in water than orthoacid; it is also capable of dissolving in cold ammonia, which ortho acid is not capable of. Salts are known only for meta- and pyroacids, which probably gives the right to give the orthoacid the formula HSbO 3 + H2O and consider it a metaacid hydrate. Sodium and potassium metasalts are obtained by fusing metal saltpeter (or sulfur dioxide powder) with the corresponding saltpeter. With KNO 3, after washing with water, a white powder is obtained, soluble in a noticeable amount in water and capable of crystallizing; salt isolated from 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 you pass CO 2 through a solution of potassium salt, you get a sparingly soluble precipitate of such an acid salt 2K 2 O∙3Sb2 O5 + 7H2 O (this is after drying at 100°, after drying at 350° there is still 2H 2 O). If a meta-acid is dissolved in a hot ammonia solution, then upon cooling the ammonium salt (NH 4 )SbO3 crystallizes, which is difficult to dissolve in the cold. By oxidizing S. oxide, dissolved in caustic potassium (antimony acid potassium), with a chameleon and then evaporating the filtrate, one obtains acid pyroantimony acid potassium K 2 H2 Sb2 O7 + 4H 2 O; this salt is quite soluble in water (at 20° - 2.81 parts of anhydrous salt in 160 parts of water) and serves as a reagent for qualitative analysis of sodium salts (in an average solution), since the corresponding crystalline salt is Na 2 H2 Sb2 O7 + 6H2O is very poorly soluble in water. This can be said to be the most difficult to dissolve sodium salt, especially in the presence of some alcohol; when there is only 0.1% sodium salt in the solution, then in this case a crystalline precipitate of pyrosalt appears. Since 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 sparingly 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, and strong acids completely displace antimony acid. Almost all antimoniates are soluble in hydrochloric acid.
When each of the described oxides of S is strongly heated in air, another oxide is obtained, namely Sb 2 O4:
Sb2 O5 = Sb2 O4 + ½O2 and Sb 2 O3 + ½O2 = Sb2 O4.
This oxide can be considered to contain trivalent and pentavalent S., i.e. in this case it would be the middle salt of orthoantimony acid Sb "" SbO4 or the main salt of meta-acids OSb-SbO 3. This oxide is the most stable at high temperatures and is analogous to 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 difficult to dissolve in acids and obtained together with Sb 2 O3 when burning natural sulfur dioxide. - 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, a double antimony-potassium salt of orthoantimony acid (OSb)K 2 SbO4. Hydrochloric acid precipitates from a solution of such a salt the acid salt K 2 Sb4 O9, which can be considered a double salt of pyroantimony acid, namely (OSb) 2 K2 Sb2 O7. In nature, similar double (?) salts for calcium and copper are found: romeite (OSb)CaSbO4 and ammyolite (OSb)CuSbO4. Sb can be weighed in the form of Sb 2 O4 during quantitative analysis; it is only necessary to calcinate the washed oxygen compound of the metal with good air access (in an open crucible) and carefully take care that flammable gases from the flame do not enter the crucible.
According to the method of formation of sulfur compounds, sulfur, like arsenic, can be considered a true metal with more right than, for example, chromium. All trivalent S. compounds in acidic solutions (preferably in the presence of hydrochloric acid) under the action of hydrogen sulfide are converted into an orange-red precipitate of trisulfur 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 pentasulfur S. Sb 2 S5, which usually also contains an admixture of Sb 2 S3 and free sulfur; pure Sb 2 S5 is obtained when excess hydrogen sulfide water is added to an acidified solution of antimony salt (Bunsen) at ordinary temperature; 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 is 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 similar to the oxygen salts of elements of the phosphorus group; they contain divalent sulfur instead of oxygen and are usually called sulfonic acids, which leads to confusion of concepts, reminiscent of salts of organic sulfonic acids, which would be best always called sulfonic acids [Similarly, the names of sulfoanhydrides (SnS 2, As2 S5, etc.) and sulfo bases (N 2 S, BaS, etc.) should be replaced with thio anhydrides and thio bases.]. Trisulfur S. Sb 2 S3 under the name antimony shine 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 luster; beat weight 4.62; fusible and easily crushed into powder, which stains fingers like graphite and has long been used as a cosmetic for eyeliner; under the name “antimony” it was and is probably still used for this purpose in our country. Black sulphurous S. in trade (Antimonium crudum) is smelted ore; This material, when fractured, presents a gray color, metallic luster and crystalline structure. In nature, in addition, there are numerous salt-like compounds of Sb 2 S3 with various sulfur metals (thiobases), 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, sulfide zinc, copper, iron and arsenic, are the so-called. faded ores. If molten trisulfur S. is subjected to rapid cooling until solidification (poured into water), then it is obtained in an amorphous form and then has a lower beat. weight, exactly 4.15, has a lead-gray color, in thin layers it appears hyacinth-red and in powder form has a red-brown color; it does not conduct electricity, which is characteristic of a crystalline modification. From the so-called antimony liver(hepar antimontii), which is obtained by fusing crystalline Sb 2 S3 with caustic potassium or potash and contains a mixture of thioantimonite and potassium stibite [Solutions of such liver are very capable of absorbing oxygen from the air. Another type of liver, which is prepared from a powdered mixture of Sb 2 S3 and saltpeter (in equal quantities), and the reaction begins 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, also K 2 SO4, as well as a certain amount of antimony acid (K-salt).]:
2Sb2 S3 + 4KOH = 3KSbS2 + KSbO2 + 2H2 O
in the same way, it is possible to obtain amorphous trisulfur S., for which the liver is extracted 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 highly diluted acid (tartaric acid at the end) and water and dried at 100°. The result is a light red-brown, easily soiled sulfur dioxide powder, soluble in hydrochloric acid, caustic and carbonic alkalis much more easily than crystalline Sb 2 S3. Similar preparations of sulphurous S., only not completely pure, have been known for a long time under the name of “mineral kermes” and have found use 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 S. oxide, loses (washed) water at 100°-130° and turns into a black modification at 200°; under a layer of dilute hydrochloric acid in a stream of carbon dioxide, this transformation occurs already during boiling (lecture experiment by Mitchell, 1893). If you add hydrogen sulfide water to a solution of tartar emetic, you get an orange-red (under transmitted light) solution of colloidal Sb 2 S3, which precipitates with the addition of calcium chloride and some other salts. Heating in a stream of hydrogen leads Sb 2 S3 to complete reduction of the metal, but in a nitrogen atmosphere it only sublimes. Crystalline Sb 2 S3 is used for the preparation of other compounds of S., and is also used as a flammable substance in a mixture with Berthollet salt and other oxidizing agents for pyrotechnic purposes, is included in 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 indicated above, or through the decomposition with dilute acid of the mentioned soluble thiosalts:
2K 3 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 sulfur from antimony luster by fusing it with tartar and saltpeter, by the action of acetic acid and recommended it as a laxative (panacea antimonialis seu sulfur purgans universale). This sulfur compound has to be dealt with during analysis: hydrogen sulfide precipitates metals of the 4th and 5th analytical groups from an acidified solution; S. is among the latter; it is usually precipitated 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 SbX 5 type in the precipitated solution) and then is separated by the action of ammonium polysulfide from the sulfur metals of the 4th groups that remain in the sediment; Sb 2 S3 is converted by ammonium polysulphide into Sb 2 S5 and then all S. appears in solution in the form of ammonium thiosalt of the highest type, from which, after filtration, it is precipitated by acid along with each other. sulfur metals of group 5, if any were present in the substance under study. S. pentasulfur is insoluble in water, easily soluble in aqueous solutions of caustic alkalis, their carbon dioxide salts and sulfur alkali metals, also in ammonium sulphide 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, it decomposes 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. Thiostimate ampium, or “Schlippe salt”, which crystallizes in large regular tetrahedra, colorless or yellowish, with 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 sodium hydroxide of a certain concentration or by fusing anhydrous sodium sulfate and Sb 2 S3 with coal 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. Potassium salt can be obtained in a similar way, and 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. Pentasulfide S. is used in the vulcanization of rubber (see) and gives it the famous brown-red color. Antimonous hydrogen
2SbH3 + 6S = Sb2 S 3 + 3H2 S
which results in an orange-red modification of Sb 2 S3; Hydrogen sulfide, which itself decomposes in this case, has a decomposing effect, even in the dark:
2SbH3 + 3H 2 S = Sb2 S3 + 6H 2.
If you pass SbH 3 (with H 2) into a solution of silver nitrate, you get a black precipitate, which represents antimony silver with an admixture of metallic silver:
SbH3 + 3AgNO3 = Ag3 Sb + 3HNO3 ;
This compound of S. is also found in nature - dyscrasite. Organometallic compounds
WITH . find very significant application; the presence of S in them causes an increase in the shine and hardness, and in significant quantities, the fragility of the metals alloyed with it. An alloy consisting of lead and S. (usually 4 parts and 1 part) 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 parts tin, 1 part tin and contains copper (up to 0.1%); it is used for making teapots, coffee pots, etc. dishes. “White, or anti-friction, metal” - alloys used for bearings; such alloys contain about 10% S. and up to 85% tin, which is sometimes replaced by almost half of lead (Babbit's metall), in addition, up to 5% copper, the amount of which falls in favor of S. to 1.5%, if in the alloy contains lead; 7 parts of iron with 3 parts of iron form a “Reaumur alloy” at white heat, which is very hard and produces sparks when processed with a file. Two crystalline compounds with zinc (Cooke jr.) Zn3 Sb2 and Zn 2 Sb2 are known. and a purple alloy with copper of the composition Cu 2 Sb (Regulus Veneris). Alloys with sodium or potassium, which are prepared by fusing carbon dioxide with alkali metals and coal, as well as by heating carbon dioxide with tartar, are quite constant in the solid state in air. but in the form of powders and with a significant content of alkali metal, they are capable of self-ignition in air, and with water they release hydrogen, produce caustic alkali in solution and antimony powder in the sediment. An alloy that is obtained at white heat is a close mixture of 5 parts of tartar and 4 parts of C. , contains up to 12% potassium and is used to obtain organometallic compounds of S. (see. also Alloys).
2SbCl3 + 3ZnR2 = 2SbR 3 + 3ZnCl2,
where R = CH 3 or C 2 H5, etc., as well as in the interaction of RJ, alcohol iodide radicals, with the above-mentioned alloy of S. 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 insoluble in water, have an onion-like odor, and spontaneously ignite in air. By connecting with RJ, stibines give stibonium iodide R4 Sb-J, from which - completely analogous to ammonium iodide, phosphonium and arsonium tetra-substituted hydrocarbon radicals - one can obtain basic hydrates of substituted stibonium oxides R 4 Sb-OH, which have the properties of caustic alkalis. But, in addition, stibines are very similar in their relationships to divalent metals of an electropositive nature; 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(C2H5)3 + 2ClH = (C2H5)3 Sb = Cl2 + H2.
Sulfur stibines precipitate from salt solutions sulfur 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 the sulfuric acid with caustic barite:
(C2 H5 )3 Sb = SO 4 + Ba(OH) 2 = (C 2 H5 )3 Sb = O + BaSO 4 + H 2 O.
Such oxides are also obtained by careful action of air on the stibines; They are soluble in water, neutralize acids and precipitate oxides of real metals. In composition and structure, stibine oxides are completely similar to phosphine and arsine oxides, but differ from them in strongly pronounced basic properties. Triphenylstibine 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 capable of combining with halogens, but not with sulfur or CH 3 J: the presence of negative phenyls reduces, therefore, the metallic properties of stibines; this is all the more interesting since the corresponding ratios of similar compounds of the more metallic bismuth are completely opposite: bismuthines Β iR3, containing saturated 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 must 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 encyclopedic Dictionary
- (French Chlore, German Chlor, English Chlorine) an element from the group of halogens; its sign is Cl; atomic weight 35.451 [According to Clarke's calculation of Stas data.] at O = 16; Cl 2 particle, which is well matched by its densities found by Bunsen and Regnault in relation to... ...
- (chemical; Phosphore French, Phosphor German, Phosphorus English and Lat., whence the designation P, sometimes Ph; atomic weight 31 [In modern times, the atomic weight of Ph. was found (van der Plaats) to be: 30.93 by restoration with a certain weight of 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 are adjacent to it in their chemical properties, got the name... ... 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 Ag2S]) belongs to the group the most important non-metallic elements. She… … Encyclopedic Dictionary F.A. Brockhaus and I.A. Efron
Y; and. [Persian. surma metal] 1. Chemical element (Sb), a bluish-white metal (used in various alloys in technology, in printing). Antimony smelting. A compound of antimony and 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 medicinally as an emetic. Dictionary of foreign words included in the Russian language. Chudinov A.N., 1910. ANTIMONY antimony, gray metal; beat V. 6.7;… … Dictionary of foreign words of the Russian language
