Boron trifluoride 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
In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwe ...
. This pungent, colourless, and
toxic
Toxicity is the degree to which a chemical substance or a particular mixture of substances can damage an organism. Toxicity can refer to the effect on a whole organism, such as an animal, bacterium, or plant, as well as the effect on a subst ...
gas forms white fumes in moist air. It is a useful
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 ...
and a versatile building block for other
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 ...
compounds.
Structure and bonding
The geometry of a
molecule
A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
of is
trigonal planar. Its D
3h symmetry
Symmetry () in everyday life refers to a sense of harmonious and beautiful proportion and balance. In mathematics, the term has a more precise definition and is usually used to refer to an object that is Invariant (mathematics), invariant und ...
conforms with the prediction of
VSEPR theory
Valence shell electron pair repulsion (VSEPR) theory ( , ) is a conceptual model, model used in chemistry to predict the geometry of individual molecules from the number of electron pairs surrounding their central atoms. It is also named the Gill ...
. The molecule has no dipole moment by virtue of its high symmetry. The molecule is
isoelectronic
Isoelectronicity is a phenomenon observed when two or more molecules have the same structure (positions and connectivities among atoms) and the same electronic configurations, but differ by what specific elements are at certain locations in th ...
with the carbonate anion, .
is commonly referred to as "
electron deficient," a description that is reinforced by its
exothermic
In thermodynamics, an exothermic process () is a thermodynamic process or reaction that releases energy from the system to its surroundings, usually in the form of heat, but also in a form of light (e.g. a spark, flame, or flash), electricity (e ...
reactivity toward
Lewis bases.
In the
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 ...
trihalides, , the length of the B–X bonds (1.30 Å) is shorter than would be expected for single bonds,
and this shortness may indicate stronger B–X
π-bonding in the fluoride. A facile explanation invokes the symmetry-allowed overlap of a p orbital on the boron atom with the in-phase combination of the three similarly oriented p orbitals on fluorine atoms.
[ Others point to the ionic nature of the bonds in .
]
Synthesis and handling
is manufactured by the reaction of boron oxides with hydrogen fluoride
Hydrogen fluoride (fluorane) is an Inorganic chemistry, inorganic compound with chemical formula . It is a very poisonous, colorless gas or liquid that dissolves in water to yield hydrofluoric acid. It is the principal industrial source of fluori ...
:
:
Typically the HF is produced ''in situ
is a Latin phrase meaning 'in place' or 'on site', derived from ' ('in') and ' ( ablative of ''situs'', ). The term typically refers to the examination or occurrence of a process within its original context, without relocation. The term is use ...
'' from sulfuric acid and fluorite
Fluorite (also called fluorspar) is the mineral form of calcium fluoride, CaF2. It belongs to the halide minerals. It crystallizes in isometric cubic habit, although octahedral and more complex isometric forms are not uncommon.
The Mohs scal ...
(). Approximately 2300-4500 tonnes of boron trifluoride are produced every year.
Laboratory scale
For laboratory scale reactions, is usually produced in situ using boron trifluoride etherate, which is a commercially available liquid.
Laboratory routes to the solvent-free materials are numerous. A well documented route involves the thermal decomposition of diazonium salt
Diazonium compounds or diazonium salts are a group of organic compounds sharing a common functional group where R can be any organic group, such as an alkyl or an aryl, and X is an inorganic or organic anion, such as a halide. The parent, comp ...
s of :
:
It forms by treatment of a mixture boron trioxide
Boron trioxide or diboron trioxide is the oxide of boron with the formula . It is a colorless transparent solid, almost always glassy (amorphous), which can be crystallized only with great difficulty. It is also called boric oxide or boria. It h ...
and sodium tetrafluoroborate with sulfuric acid:
:
Alternatively, boron tribromide converts various organofluorine compounds to organobromines, evolving the trifluoride gas:
:3 R–F + BBr3 → 3 R–Br + BF3
Properties
Anhydrous boron trifluoride has a boiling point
The boiling point of a substance is the temperature at which the vapor pressure of a liquid equals the pressure surrounding the liquid and the liquid changes into a vapor.
The boiling point of a liquid varies depending upon the surrounding envi ...
of −100.3 °C and a critical temperature
Critical or Critically may refer to:
*Critical, or critical but stable, medical states
**Critical, or intensive care medicine
*Critical juncture, a discontinuous change studied in the social sciences.
*Critical Software, a company specializing in ...
of −12.3 °C, so that it can be stored as a refrigerated liquid only between those temperatures. Storage or transport vessels should be designed to withstand internal pressure, since a refrigeration system failure could cause pressures to rise to the critical pressure
In thermodynamics, a critical point (or critical state) is the end point of a phase equilibrium curve. One example is the liquid–vapor critical point, the end point of the pressure–temperature curve that designates conditions under which a l ...
of 49.85 bar (4.985 MPa).
Boron trifluoride is corrosive. Suitable metals for equipment handling boron trifluoride include stainless steel
Stainless steel, also known as inox, corrosion-resistant steel (CRES), or rustless steel, is an iron-based alloy that contains chromium, making it resistant to rust and corrosion. Stainless steel's resistance to corrosion comes from its chromi ...
, monel, and hastelloy. In presence of moisture it corrodes steel, including stainless steel. It reacts with polyamide
A polyamide is a polymer with repeating units linked by amide bonds.
Polyamides occur both naturally and artificially. Examples of naturally occurring polyamides are proteins, such as wool and silk. Artificially made polyamides can be made throug ...
s. Polytetrafluoroethylene
Polytetrafluoroethylene (PTFE) is a synthetic fluoropolymer of tetrafluoroethylene, and has numerous applications because it is chemically inert. The commonly known brand name of PTFE-based composition is Teflon by Chemours, a corporate spin-of ...
, polychlorotrifluoroethylene, polyvinylidene fluoride
Polyvinylidene fluoride or polyvinylidene difluoride (PVDF) is a highly non-reactive thermoplastic fluoropolymer produced by the polymerization of vinylidene difluoride. Its chemical formula is (C2H2F2)''n''.
PVDF is a specialty plastic use ...
, and polypropylene
Polypropylene (PP), also known as polypropene, is a thermoplastic polymer used in a wide variety of applications. It is produced via chain-growth polymerization from the monomer Propene, propylene.
Polypropylene belongs to the group of polyolefin ...
show satisfactory resistance. The grease used in the equipment should be fluorocarbon
Fluorocarbons are chemical compounds with carbon-fluorine bonds. Compounds that contain many C-F bonds often have distinctive properties, e.g., enhanced stability, volatility, and hydrophobicity. Several fluorocarbons and their derivatives are ...
based, as boron trifluoride reacts with the hydrocarbon-based ones.
Reactions
Unlike the aluminium and gallium trihalides, the boron trihalides are all monomer
A monomer ( ; ''mono-'', "one" + '' -mer'', "part") is a molecule that can react together with other monomer molecules to form a larger polymer chain or two- or three-dimensional network in a process called polymerization.
Classification
Chemis ...
ic. They undergo rapid halide exchange reactions:
:
Because of the facility of this exchange process, the mixed halides cannot be obtained in pure form.
Boron trifluoride is a versatile 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 ...
that 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 such Lewis bases as fluoride
Fluoride (). According to this source, is a possible pronunciation in British English. is an Inorganic chemistry, inorganic, Monatomic ion, monatomic Ion#Anions and cations, anion of fluorine, with the chemical formula (also written ), whose ...
and 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:
:
:
Tetrafluoroborate salts are commonly employed as non-coordinating anion
Anions that interact weakly with cations are termed non-coordinating anions, although a more accurate term is weakly coordinating anion. Non-coordinating anions are useful in studying the reactivity of electrophilic cations. They are commonly foun ...
s. The adduct with diethyl ether
Diethyl ether, or simply ether, is an organic compound with the chemical formula , sometimes abbreviated as . It is a colourless, highly Volatility (chemistry), volatile, sweet-smelling ("ethereal odour"), extremely flammable liquid. It belongs ...
, boron trifluoride diethyl etherate, or just boron trifluoride etherate, () is a conveniently handled liquid
Liquid is a state of matter with a definite volume but no fixed shape. Liquids adapt to the shape of their container and are nearly incompressible, maintaining their volume even under pressure. The density of a liquid is usually close to th ...
and consequently is widely encountered as a laboratory source of . Another common adduct is the adduct with 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 ...
(), which can be handled as a neat liquid.
Comparative Lewis acidity
All three lighter boron trihalides, (X = F, Cl, Br) form stable adducts with common Lewis bases. Their relative Lewis acidities can be evaluated in terms of the relative exothermicities of the adduct-forming reaction. Such measurements have revealed the following sequence for the Lewis acidity:
: < < < (strongest Lewis acid)
This trend is commonly attributed to the degree of π-bonding in the planar boron trihalide that would be lost upon pyramidalization of the molecule. which follows this trend:
: > > < (most easily pyramidalized)
The criteria for evaluating the relative strength of π-bonding are not clear, however.[ One suggestion is that the F atom is small compared to the larger Cl and Br atoms. As a consequence, the bond length between boron and the halogen increases while going from fluorine to iodine hence spatial overlap between the orbitals becomes more difficult. The lone pair electron in p''z'' of F is readily and easily donated and overlapped to empty pz orbital of boron. As a result, the pi donation of F is greater than that of Cl or Br.
In an alternative explanation, the low Lewis acidity for is attributed to the relative weakness of the bond in the adducts .
Yet another explanation might be found in the fact that the p''z'' orbitals in each higher period have an extra nodal plane and opposite signs of the wave function on each side of that plane. This results in bonding and antibonding regions within the same bond, diminishing the effective overlap and so lowering the π-donating blockage of the acidity.
]
Hydrolysis
Boron trifluoride reacts with water to give 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 ...
and fluoroboric acid. The reaction commences with the formation of the aquo adduct, , which then loses HF that gives fluoroboric acid with boron trifluoride.
:
The heavier trihalides also hydrolyze, but to boric and hydrohalic acids, possibly due to the lower stability of the tetrahedral ions and . Because of the high acidity of fluoroboric acid, the fluoroborate ion can be used to isolate particularly electrophilic cations, such as diazonium ions, that are otherwise difficult to isolate as solids.
Uses
Organic chemistry
Boron trifluoride is most importantly used as 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 ...
, typically as a 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 ...
.[ Examples include:
* initiates ]polymerisation
In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many form ...
reactions of unsaturated compounds, such as polyether
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
* as a catalyst in some isomerization
In chemistry, isomerization or isomerisation is the process in which a molecule, polyatomic ion or molecular fragment is transformed into an isomer with a different chemical structure. Enolization is an example of isomerization, as is tautomer ...
, acylation, alkylation Alkylation is a chemical reaction that entails transfer of an alkyl group. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion, or a carbene (or their equivalents). Alkylating agents are reagents for effecting al ...
, esterification
In chemistry, an ester is a compound derived from an acid (either organic or inorganic) in which the hydrogen atom (H) of at least one acidic hydroxyl group () of that acid is replaced by an organyl group (R). These compounds contain a distin ...
, dehydration
In physiology, dehydration is a lack of total body water that disrupts metabolic processes. It occurs when free water loss exceeds intake, often resulting from excessive sweating, health conditions, or inadequate consumption of water. Mild deh ...
, condensation
Condensation is the change of the state of matter from the gas phase into the liquid phase, and is the reverse of vaporization. The word most often refers to the water cycle. It can also be defined as the change in the state of water vapor ...
, Mukaiyama aldol addition, and other reactions
Niche uses
Other, less common uses for boron trifluoride include:
* applied as dopant
A dopant (also called a doping agent) is a small amount of a substance added to a material to alter its physical properties, such as electrical or optics, optical properties. The amount of dopant is typically very low compared to the material b ...
in ion implantation
Ion implantation is a low-temperature process by which ions of one element are accelerated into a solid target, thereby changing the target's physical, chemical, or electrical properties. Ion implantation is used in semiconductor device fabrica ...
* p-type dopant for epitaxial
Epitaxy (prefix ''epi-'' means "on top of”) is a type of crystal growth or material deposition in which new crystalline layers are formed with one or more well-defined orientations with respect to the crystalline seed layer. The deposited cry ...
ly grown silicon
Silicon is a chemical element; it has symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic lustre, and is a tetravalent metalloid (sometimes considered a non-metal) and semiconductor. It is a membe ...
* used in sensitive neutron detectors in ionization chamber
The ionization chamber is the simplest type of gaseous ionisation detector, and is widely used for the detection and measurement of many types of ionizing radiation, including X-rays, gamma rays, alpha particles and beta particles. Conventionall ...
s and devices to monitor radiation levels in the Earth's atmosphere
The atmosphere of Earth is composed of a layer of gas mixture that surrounds the Earth's planetary surface (both lands and oceans), known collectively as air, with variable quantities of suspended aerosols and particulates (which create weathe ...
* in fumigation
* as a flux
Flux describes any effect that appears to pass or travel (whether it actually moves or not) through a surface or substance. Flux is a concept in applied mathematics and vector calculus which has many applications in physics. For transport phe ...
for soldering
Soldering (; ) is a process of joining two metal surfaces together using a filler metal called solder. The soldering process involves heating the surfaces to be joined and melting the solder, which is then allowed to cool and solidify, creatin ...
magnesium
* to prepare diborane
Discovery
Boron trifluoride was discovered in 1808 by Joseph Louis Gay-Lussac
Joseph Louis Gay-Lussac ( , ; ; 6 December 1778 – 9 May 1850) was a French chemist and physicist. He is known mostly for his discovery that water is made of two parts hydrogen and one part oxygen by volume (with Alexander von Humboldt), f ...
and Louis Jacques Thénard, who were trying to isolate "fluoric acid" (i.e., hydrofluoric acid
Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colorless, acidic and highly corrosive. A common concentration is 49% (48–52%) but there are also stronger solutions (e.g. 70%) and pure HF has a boiling p ...
) by combining calcium fluoride with vitrified 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 ...
. The resulting vapours failed to etch glass, so they named it ''fluoboric gas''.
See also
*List of highly toxic gases
Many gases have toxic properties, which are often assessed using the LC50 (median lethal concentration) measure. In the United States, many of these gases have been assigned an NFPA 704 health rating of 4 (may be fatal) or 3 (may cause serious ...
References
External links
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Fluorides
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Acid catalysts