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Boron trichloride is the inorganic compound with the formula BCl3. This colorless gas is a reagent in organic synthesis. It is highly reactive towards water.
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| Names | |||
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| IUPAC name
Boron trichloride | |||
| Other names
Boron(III) chloride Trichloroborane | |||
| Identifiers | |||
3D model (JSmol) |
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| ChemSpider | |||
| ECHA InfoCard | 100.030.586 | ||
| EC Number |
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PubChem CID |
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| RTECS number |
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| UNII | |||
CompTox Dashboard (EPA) |
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| Properties | |||
| BCl3 | |||
| Molar mass | 117.17 g/mol | ||
| Appearance | Colorless gas, fumes in air | ||
| Density | 1.326 g/cm3 | ||
| Melting point | −107.3 °C (−161.1 °F; 165.8 K) | ||
| Boiling point | 12.6 °C (54.7 °F; 285.8 K)[1] | ||
| hydrolysis | |||
| Solubility | soluble in CCl4, ethanol | ||
| -59.9·10−6 cm3/mol | |||
Refractive index (nD) |
1.00139 | ||
| Structure | |||
| Trigonal planar (D3h) | |||
| zero | |||
| Thermochemistry | |||
Heat capacity (C) |
107 J/mol K | ||
Std molar entropy (S⦵298) |
206 J/mol K | ||
Std enthalpy of formation (ΔfH⦵298) |
-427 kJ/mol | ||
Gibbs free energy (ΔfG⦵) |
-387.2 kJ/mol | ||
| Hazards[2] | |||
| Occupational safety and health (OHS/OSH): | |||
Main hazards |
May be fatal if swallowed or if inhaled Causes serious burns to eyes, skin, mouth, lungs, etc. Contact with water gives HCl | ||
| GHS labelling: | |||
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| Danger | |||
| H300, H314, H330[note 1] | |||
| NFPA 704 (fire diamond) | |||
| Flash point | Non-flammable | ||
| Safety data sheet (SDS) | ICSC | ||
| Related compounds | |||
Other anions |
Boron trifluoride Boron tribromide Boron triiodide | ||
Other cations |
Aluminium trichloride Gallium trichloride | ||
Related compounds |
Boron trioxide Carbon tetrachloride | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Boron reacts with halogens to give the corresponding trihalides. Boron trichloride is, however, produced industrially by chlorination of boron oxide and carbon at 501 °C.
- B2O3 + 3 C + 3 Cl2 → 2 BCl3 + 3 CO
The carbothermic reaction is analogous to the Kroll process for the conversion of titanium dioxide to titanium tetrachloride. One consequence of this synthesis route is that samples of boron trichloride are often contaminated with phosgene.[3]
In the laboratory BCl3 can be prepared by treating with AlCl3 with BF3, a halide exchange reaction.[4]
BCl3 is a trigonal planar molecule like the other boron trihalides. The B-Cl bond length is 175 pm. A degree of π-bonding has been proposed to explain the short B− Cl distance, although there is some debate as to its extent.[4] BCl3 does not dimerize, although NMR studies of mixtures of boron trihalides shows the presence of mixed halides. The absence of dimerisation contrasts with the tendencies of AlCl3 and GaCl3, which form dimers or polymers with 4 or 6 coordinate metal centres.
BCl3 hydrolyzes readily to give hydrochloric acid and boric acid:
- BCl3 + 3 H2O → B(OH)3 + 3 HCl
Alcohols behave analogously giving the borate esters, e.g. trimethyl borate.
As a strong Lewis acid, BCl3 forms adducts with tertiary amines, phosphines, ethers, thioethers, and halide ions.[5] Adduct formation is often accompanied by an increase in B-Cl bond length. BCl3•S(CH3)2 (CAS# 5523-19-3) is often employed as a conveniently handled source of BCl3 because this solid (m.p. 88-90 °C) releases BCl3:
- (CH3)2S·BCl3 ⇌ (CH3)2S + BCl3
The mixed aryl and alkyl boron chlorides are also of known. Phenylboron dichloride is commercially available. Such species can be prepared by the redistribution reaction of BCl3 with organotin reagents:
- 2 BCl3 + R4Sn → 2 RBCl2 + R2SnCl2
Reduction
Reduction of BCl3 to elemental boron is conducted commercially in the laboratory, when boron trichloride can be converted to diboron tetrachloride by heating with copper metal:[6]
- 2 BCl3 + 2 Cu → B2Cl4 + 2 CuCl
B4Cl4 can also be prepared in this way. Colourless diboron tetrachloride (m.p. -93 °C) is a planar molecule in the solid, (similar to dinitrogen tetroxide, but in the gas phase the structure is staggered.[4] It decomposes (disproportionates) at room temperatures to give a series of monochlorides having the general formula (BCl)n, in which n may be 8, 9, 10, or 11.
- n B2Cl4 → BnCln + n BCl3
The compounds with formulas B8Cl8 and B9Cl9 are known to contain closed cages of boron atoms.
Boron trichloride is a starting material for the production of elemental boron. It is also used in the refining of aluminium, magnesium, zinc, and copper alloys to remove nitrides, carbides, and oxides from molten metal. It has been used as a soldering flux for alloys of aluminium, iron, zinc, tungsten, and monel. Aluminium castings can be improved by treating the melt with boron trichloride vapors. In the manufacture of electrical resistors, a uniform and lasting adhesive carbon film can be put over a ceramic base using BCl3. It has been used in the field of high energy fuels and rocket propellants as a source of boron to raise BTU value. BCl3 is also used in plasma etching in semiconductor manufacturing. This gas etches metal oxides by formation of a volatile BOClx and MxOyClz compounds.
BCl3 is used as a reagent in the synthesis of organic compounds. Like the corresponding bromide, it cleaves C-O bonds in ethers.[1][7]
BCl3 is an aggressive reagent that can form hydrogen chloride upon exposure to moisture or alcohols. The dimethyl sulfide adduct (BCl3SMe2), which is a solid, is much safer to use,[8] when possible, but H2O will destroy the BCl3 portion while leaving dimethyl sulfide in solution.
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