Boron Trichloride
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Boron trichloride is the
inorganic compound An inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds⁠that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as ''inorganic chemistry''. Inorgan ...
with the formula BCl3. This colorless gas is a reagent in
organic synthesis Organic synthesis is a branch of chemical synthesis concerned with the construction of organic compounds. Organic compounds are molecules consisting of combinations of covalently-linked hydrogen, carbon, oxygen, and nitrogen atoms. Within the gen ...
. It is highly reactive towards water.


Production and structure

Boron Boron is a chemical element; it has symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the boron group it has three ...
reacts with
halogens The halogens () are a group (periodic table), group in the periodic table consisting of six chemically related chemical element, elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the radioactive elements astatine (At) and ten ...
to give the corresponding trihalides. Boron trichloride is, however, produced industrially by chlorination of boron oxide and
carbon Carbon () is a chemical element; it has chemical symbol, symbol C and atomic number 6. It is nonmetallic and tetravalence, tetravalent—meaning that its atoms are able to form up to four covalent bonds due to its valence shell exhibiting 4 ...
at 501 °C. :B2O3 + 3 C + 3 Cl2 → 2 BCl3 + 3 CO The carbothermic reaction is analogous to the
Kroll process The Kroll process is a pyrometallurgical industrial process used to produce metallic titanium from titanium tetrachloride. As of 2001 William Justin Kroll's process replaced the Hunter process for almost all commercial production. Process In the ...
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 Phosgene is an organic chemical compound with the formula . It is a toxic, colorless gas; in low concentrations, its musty odor resembles that of freshly cut hay or grass. It can be thought of chemically as the double acyl chloride analog of ...
. In the laboratory BCl3 can be prepared by treating with AlCl3 with BF3, a halide exchange reaction. 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. 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.


Reactions

BCl3 hydrolyzes readily to give hydrochloric acid and
boric acid Boric acid, more specifically orthoboric acid, is a compound of boron, oxygen, and hydrogen with formula . It may also be called hydrogen orthoborate, trihydroxidoboron or boracic acid. It is usually encountered as colorless crystals or a white ...
: :BCl3 + 3 H2O → B(OH)3 + 3 HCl Alcohols behave analogously giving the borate esters, e.g.
trimethyl borate Trimethyl borate is the organoboron compound with the formula B(OCH3)3. It is a colourless liquid that burns with a green flame. It is an intermediate in the preparation of sodium borohydride and is a popular reagent in organic chemistry. It i ...
. As a strong
Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any ...
, BCl3 forms
adduct In chemistry, an adduct (; alternatively, a contraction of "addition product") is a product of a direct addition of two or more distinct molecules, resulting in a single reaction product containing all atoms of all components. The resultant is ...
s with tertiary
amine In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...
s, phosphines, ethers,
thioether In organic chemistry, a sulfide (British English sulphide) or thioether is an organosulfur functional group with the connectivity as shown on right. Like many other sulfur-containing compounds, Volatile organic compound, volatile sulfides have ...
s, and halide ions. 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 In organic chemistry, an aryl is any functional group or substituent derived from an aromatic ring, usually an aromatic hydrocarbon, such as phenyl and naphthyl. "Aryl" is used for the sake of abbreviation or generalization, and "Ar" is used ...
and
alkyl In organic chemistry, an alkyl group is an alkane missing one hydrogen. The term ''alkyl'' is intentionally unspecific to include many possible substitutions. An acyclic alkyl has the general formula of . A cycloalkyl group is derived from a cy ...
boron chlorides are also of known.
Phenyl In organic chemistry, the phenyl group, or phenyl ring, is a cyclic group of atoms with the formula , and is often represented by the symbol Ph (archaically φ) or Ø. The phenyl group is closely related to benzene and can be viewed as a benzene ...
boron 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: :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 Dinitrogen tetroxide, commonly referred to as nitrogen tetroxide (NTO), and occasionally (usually among ex-USSR/Russian rocket engineers) as amyl, is the chemical compound N2O4. It is a useful reagent in chemical synthesis. It forms an equilibrium ...
, but in the gas phase the structure is staggered. 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 → B_Cl_ + ''n'' BCl3 The compounds with formulas B8Cl8 and B9Cl9 are known to contain closed cages of boron atoms.


Uses

Boron trichloride is a starting material for the production of elemental boron. It is also used in the
refining Refining is the process of purification of a (1) substance or a (2) form. The term is usually used of a natural resource that is almost in a usable form, but which is more useful in its pure form. For instance, most types of natural petroleum w ...
of
aluminium Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
,
magnesium Magnesium is a chemical element; it has Symbol (chemistry), symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 ...
, zinc, and
copper Copper is a chemical element; it has symbol Cu (from Latin ) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkish-orang ...
alloys to remove
nitride In chemistry, a nitride is a chemical compound of nitrogen. Nitrides can be inorganic or organic, ionic or covalent. The nitride anion, N3−, is very elusive but compounds of nitride are numerous, although rarely naturally occurring. Some nitr ...
s,
carbide In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece. Interstitial / Metallic carbides The carbides of th ...
s, and
oxides An oxide () is a chemical compound containing at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion (anion bearing a net charge of −2) of oxygen, an O2− ion with oxygen in the oxidation state o ...
from molten metal. It has been used as a soldering flux for alloys of aluminium,
iron Iron is a chemical element; it has symbol Fe () and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, forming much of Earth's o ...
,
zinc Zinc is a chemical element; it has symbol Zn and atomic number 30. It is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic tabl ...
,
tungsten Tungsten (also called wolfram) is a chemical element; it has symbol W and atomic number 74. It is a metal found naturally on Earth almost exclusively in compounds with other elements. It was identified as a distinct element in 1781 and first ...
, 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 A ceramic is any of the various hard, brittle, heat-resistant, and corrosion-resistant materials made by shaping and then firing an inorganic, nonmetallic material, such as clay, at a high temperature. Common examples are earthenware, porcela ...
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 Plasma etching is a form of plasma processing used to fabricate integrated circuits. It involves a high-speed stream of glow discharge (Plasma (physics), plasma) of an appropriate gas mixture being shot (in pulses) at a sample. The plasma source, ...
in
semiconductor A semiconductor is a material with electrical conductivity between that of a conductor and an insulator. Its conductivity can be modified by adding impurities (" doping") to its crystal structure. When two regions with different doping level ...
manufacturing. This gas etches metal oxides by formation of a volatile BOClx and MxOyClz compounds. BCl3 is used as a
reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...
in the synthesis of organic compounds. Like the corresponding bromide, it cleaves C-O bonds in
ether In organic chemistry, ethers are a class of compounds that contain an ether group, a single oxygen atom bonded to two separate carbon atoms, each part of an organyl group (e.g., alkyl or aryl). They have the general formula , where R and R ...
s.


Safety

BCl3 is an aggressive reagent that can form
hydrogen chloride The Chemical compound, compound hydrogen chloride has the chemical formula and as such is a hydrogen halide. At room temperature, it is a colorless gas, which forms white fumes of hydrochloric acid upon contact with atmospheric water vapor. Hyd ...
upon exposure to moisture or
alcohol Alcohol may refer to: Common uses * Alcohol (chemistry), a class of compounds * Ethanol, one of several alcohols, commonly known as alcohol in everyday life ** Alcohol (drug), intoxicant found in alcoholic beverages ** Alcoholic beverage, an alco ...
s. The
dimethyl sulfide Dimethyl sulfide (DMS) or methylthiomethane is an organosulfur compound with the formula . It is the simplest thioether and has a characteristic disagreeable odor. It is a flammable liquid that boils at . It is a component of the smell produc ...
adduct (BCl3SMe2), which is a solid, is much safer to use, when possible, but H2O will destroy the BCl3 portion while leaving dimethyl sulfide in solution.


See also

* List of highly toxic gases


References


Notes


Further reading

* *


External links

* {{Authority control Boron compounds Chlorides Boron halides