Boron Trifluoride
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Boron trifluoride is the
inorganic compound In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemi ...
with the formula BF3. 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 subs ...
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 sp ...
and a versatile building block for other boron compounds.


Structure and bonding

The geometry of a
molecule A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bio ...
of BF3 is
trigonal planar In chemistry, trigonal planar is a molecular geometry model with one atom at the center and three atoms at the corners of an equilateral triangle, called peripheral atoms, all in one plane. In an ideal trigonal planar species, all three ligands ...
. Its D3h symmetry conforms with the prediction of
VSEPR theory Valence shell electron pair repulsion (VSEPR) theory ( , ), is a 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 Gillespie-Nyholm t ...
. 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, . BF3 is commonly referred to as "
electron deficient Electron deficiency (and electron-deficient) is jargon that is used in two contexts: species that violate the octet rule because they have too few valence electrons and species that happen to follow the octet rule but have electron-acceptor properti ...
," 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 ...
reactivity toward
Lewis base 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 sp ...
s. In the boron trihalides, BX3, 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 BF3.


Synthesis and handling

BF3 is manufactured by the reaction of boron oxides with hydrogen fluoride: :B2O3 + 6 HF → 2 BF3 + 3 H2O Typically the HF is produced ''in situ'' 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 sca ...
(CaF2). Approximately 2300-4500 tonnes of boron trifluoride are produced every year.


Laboratory scale

For laboratory scale reactions, BF3 is usually produced in situ using
boron trifluoride etherate Boron trifluoride etherate, strictly boron trifluoride diethyl etherate, or boron trifluoride–ether complex, is the chemical compound with the formula BF3O(C2H5)2, often abbreviated BF3OEt2. It is a colorless liquid, although older samples can a ...
, 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 salts of : :PhN2BF4PhF + BF3 + N2 Alternatively it arises from the reaction of sodium tetrafluoroborate,
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 sulfuric acid: :6 NaBF4 + B2O3 + 6 H2SO4 → 8 BF3 + 6 NaHSO4 + 3 H2O


Properties

Anhydrous boron trifluoride has a boiling point of −100.3 °C and a critical temperature 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 of 49.85 bar (4.985 MPa). Boron trifluoride is corrosive. Suitable metals for equipment handling boron trifluoride include stainless steel,
monel Monel is a group of alloys of nickel (from 52 to 67%) and copper, with small amounts of iron, manganese, carbon, and silicon. Monel is not a cupronickel alloy because it has less than 60% copper. Stronger than pure nickel, Monel alloys are res ...
, and
hastelloy Haynes International, Inc., headquartered in Kokomo, Indiana, is one of the largest producers of corrosion-resistant and high-temperature alloys. In addition to Kokomo, Haynes has manufacturing facilities in Arcadia, Louisiana, and Mountain Hom ...
. 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 that has numerous applications. It is one of the best-known and widely applied PFAS. The commonly known brand name of PTFE-based composition is Teflon by Che ...
,
polychlorotrifluoroethylene Polychlorotrifluoroethylene (PCTFE or PTFCE) is a thermoplastic chloro fluoropolymer with the molecular formula , where ''n'' is the number of monomer units in the polymer molecule. It is similar to polytetrafluoroethene (PTFE), except that it is ...
,
polyvinylidene fluoride Polyvinylidene fluoride or polyvinylidene difluoride (PVDF) is a highly non-reactive thermoplastic fluoropolymer produced by the polymerization of vinylidene difluoride. PVDF is a specialty plastic used in applications requiring the highest pur ...
, 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 propylene. Polypropylene belongs to the group of polyolefins an ...
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 has distinctive properties, e.g., enhanced stability, volatility, and hydrophobicity. Fluorocarbons and their derivatives are commerci ...
based, as boron trifluoride reacts with the hydrocarbon-based ones.


Reactions

Unlike the aluminium and gallium trihalides, the boron trihalides are all monomeric. They undergo rapid halide exchange reactions: :BF3 + BCl3 → BF2Cl + BCl2F Because of the facility of this exchange process, the mixed halides cannot be obtained in pure form. Boron trifluoride is a versatile Lewis acid that forms
adduct An adduct (from the Latin ''adductus'', "drawn toward" 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 co ...
s with such
Lewis base 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 sp ...
s as
fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an inorganic, monatomic anion of fluorine, with the chemical formula (also written ), whose salts are typically white or colorless. Fluoride salts ...
and
ether In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula , where R and R′ represent the alkyl or aryl groups. Ethers can again b ...
s: :
CsF CSF may refer to: Biology and medicine * Cerebrospinal fluid, clear colorless bodily fluid found in the brain and spine * Colony-stimulating factor, secreted glycoproteins * Cancer slope factor, estimate the risk of cancer * Classical swine fever ...
+ BF3 → CsBF4 : O(C2H5)2 + BF3 → BF3·O(C2H5)2
Tetrafluoroborate Tetrafluoroborate is the anion . This tetrahedral species is isoelectronic with tetrafluoroberyllate (), tetrafluoromethane (CF4), and tetrafluoroammonium () and is valence isoelectronic with many stable and important species including the perch ...
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 in the ether class with the formula , sometimes abbreviated as (see Pseudoelement symbols). It is a colourless, highly volatile, sweet-smelling ("ethereal odour"), extremely flammable liq ...
, boron trifluoride diethyl etherate, or just
boron trifluoride etherate Boron trifluoride etherate, strictly boron trifluoride diethyl etherate, or boron trifluoride–ether complex, is the chemical compound with the formula BF3O(C2H5)2, often abbreviated BF3OEt2. It is a colorless liquid, although older samples can a ...
, (BF3·O(Et)2) is a conveniently handled
liquid A liquid is a nearly incompressible fluid that conforms to the shape of its container but retains a (nearly) constant volume independent of pressure. As such, it is one of the four fundamental states of matter (the others being solid, gas, an ...
and consequently is widely encountered as a laboratory source of BF3. Another common adduct is the adduct with
dimethyl sulfide Dimethyl sulfide (DMS) or methylthiomethane is an organosulfur compound with the formula (CH3)2S. Dimethyl sulfide is a flammable liquid that boils at and has a characteristic disagreeable odor. It is a component of the smell produced from co ...
(BF3·S(Me)2), which can be handled as a neat liquid.


Comparative Lewis acidity

All three lighter boron trihalides, BX3 (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: :BF3 < BCl3 < BBr3 < BI3(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 BX3 molecule. which follows this trend: :BF3 > BCl3 > BBr3 < BI3 (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, and 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 BF3 is attributed to the relative weakness of the bond in the adducts F3B−L.


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 borate or boracic acid. It is usually encountered as colorless crystals or a white powder, that dissolve ...
and
fluoroboric acid Fluoroboric acid or tetrafluoroboric acid (archaically, fluoboric acid) is an inorganic compound with the chemical formula +BF4−], where H+ represents the solvated proton. The solvent can be any suitably Lewis-basic entity. For instance, in w ...
. The reaction commences with the formation of the aquo adduct, H2O−BF3, which then loses HF that gives fluoroboric acid with boron trifluoride. :4 BF3 + 3 H2O → 3 HBF4 + B(OH)3 The heavier trihalides do not undergo analogous reactions, 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 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. General properti ...
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 special branch of chemical synthesis and is concerned with the intentional construction of organic compounds. Organic molecules are often more complex than inorganic compounds, and their synthesis has developed into one o ...
, 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 sp ...
. 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 for ...
reactions of
unsaturated compound In chemistry, a saturated compound is a chemical compound (or ion) that resists the addition reactions, such as hydrogenation, oxidative addition, and binding of a Lewis base. The term is used in many contexts and for many classes of chemical ...
s, such as
polyether In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula , where R and R′ represent the alkyl or aryl groups. Ethers can again be ...
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 tautome ...
,
acylation In chemistry, acylation (or alkanoylation) is the chemical reaction in which an acyl group () is added to a compound. The compound providing the acyl group is called the acylating agent. Because they form a strong electrophile when treated wit ...
,
alkylation Alkylation is the transfer of an alkyl group from one molecule to another. 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 effectin ...
,
esterification In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glyceride ...
,
dehydration In physiology, dehydration is a lack of total body water, with an accompanying disruption of metabolic processes. It occurs when free water loss exceeds free water intake, usually due to exercise, disease, or high environmental temperature. Mi ...
,
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 The Mukaiyama aldol addition is an organic reaction and a type of aldol reaction between a silyl enol ether and an aldehyde or formate. The reaction was discovered by Teruaki Mukaiyama (1927–2018) in 1973. His choice of reactants allows fo ...
, 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 trace of impurity element that is introduced into a chemical material to alter its original electrical or optical properties. The amount of dopant necessary to cause changes is typically very low. Wh ...
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 physical, chemical, or electrical properties of the target. Ion implantation is used in semiconductor device fa ...
* p-type dopant for
epitaxial Epitaxy refers to 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 crystalline film is called an epit ...
ly grown
silicon Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic ...
* used in sensitive neutron detectors in
ionization chamber The ionization chamber is the simplest type of gas-filled radiation detector, and is widely used for the detection and measurement of certain types of ionizing radiation, including X-rays, gamma rays, and beta particles. Conventionally, the ter ...
s and devices to monitor radiation levels in the
Earth's atmosphere The atmosphere of Earth is the layer of gases, known collectively as air, retained by Earth's gravity that surrounds the planet and forms its planetary atmosphere. The atmosphere of Earth protects life on Earth by creating pressure allowing f ...
* in
fumigation Fumigation is a method of pest control or the removal of harmful micro-organisms by completely filling an area with gaseous pesticides—or fumigants—to suffocate or poison the pests within. It is used to control pests in buildings (s ...
* 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 to physics. For transport ...
for
soldering Soldering (; ) is a process in which two or more items are joined by melting and putting a filler metal ( solder) into the joint, the filler metal having a lower melting point than the adjoining metal. Unlike welding, soldering does not in ...
magnesium * to prepare
diborane Diborane(6), generally known as diborane, is the chemical compound with the formula B2H6. It is a toxic, colorless, and pyrophoric gas with a repulsively sweet odor. Diborane is a key boron compound with a variety of applications. It has attracte ...


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 (with Alexander von Humboldt), for two laws ...
and
Louis Jacques Thénard Louis Jacques Thénard (4 May 177721 June 1857) was a French chemist. Life He was born in a farm cottage near Nogent-sur-Seine in the Champagne district the son of a farm worker. In the post-Revolution French educational system , most boys rec ...
, 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 colourless, acidic and highly corrosive. It is used to make most fluorine-containing compounds; examples include the commonly used pharmaceutical antidepr ...
) by combining
calcium fluoride Calcium fluoride is the inorganic compound of the elements calcium and fluorine with the formula CaF2. It is a white insoluble solid. It occurs as the mineral fluorite (also called fluorspar), which is often deeply coloured owing to impurities. ...
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 borate or boracic acid. It is usually encountered as colorless crystals or a white powder, that dissolve ...
. 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 dose) 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 or perma ...


References


External links

* * * * * * {{DEFAULTSORT:Boron Trifluoride Fluorides Boron compounds Boron halides Industrial gases Acid catalysts