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Boron Trifluoride

BF3 inorganic

Properties

StateGas (colorless, pungent, fuming in moist air)
ColorColorless
SolubilityReacts with water (forms fluoboric acid and boric acid); very soluble in organic solvents as adducts
Melting Point-127°C
Boiling Point-100°C

About Boron Trifluoride

Boron trifluoride is the canonical Lewis acid — the molecule G. N. Lewis pointed at when he wrote down the electron-pair definition of acidity in 1923, and the molecule every undergraduate textbook still uses to introduce the concept. The geometry is trigonal planar with a vacant 2p orbital perpendicular to the BF3 plane, and that empty orbital is the entire reason BF3 is interesting: it grabs electron pairs from anything basic enough to donate, snapping into tetrahedral geometry as it does so. There's a counterintuitive twist in the boron-halide series, though. Naïvely you'd expect BF3 to be the weakest Lewis acid of BX3 because fluorine is the most electronegative halogen and should pull the most electron density off boron. In the gas phase that argument actually works, because BF3 enjoys substantial pi back-donation from the fluorine lone pairs into boron's empty p-orbital — a partial double-bond character that satisfies boron's electron deficiency without needing an external donor. But once a Lewis base attacks and forces boron to rehybridize from sp2 to sp3, that pi back-donation has to break, and the cost of breaking it is highest for BF3 because F-B pi-bonding is the strongest. The net result, in solution, is that BF3 ends up a stronger Lewis acid than BCl3 or BBr3 toward most donors. Synthetic chemists exploit this constantly: BF3-OEt2 (BF3 etherate, a fuming liquid) catalyzes Friedel-Crafts acylations, epoxide ring-openings, Mukaiyama aldols, glycosylations, polymerizations of styrene and vinyl ethers, and dozens of other transformations. The 10B isotope also has a 3837 barn neutron-capture cross-section, which is why BF3-filled proportional counters are still standard for thermal-neutron detection in reactor instrumentation.

Where you'll encounter it

If you've worked in an organic synthesis lab, you've almost certainly opened a brown-glass bottle of BF3-OEt2 — a colorless to pale yellow fuming liquid that smells aggressively of ether and HF, and that has a pyrophoric tendency if exposed to a wet stir bar. The pure gas is far worse: BF3 cylinders require Monel or stainless regulators (it eats brass), and any moisture in the line forms HF and silicate plumes that etch glass valves. In a petroleum refinery, BF3 is one of the catalysts used in alkylation units that combine isobutane with light olefins to make high-octane gasoline blendstock.

Common Uses

  • Lewis acid catalyst as BF3-OEt2 for Friedel-Crafts, Mukaiyama aldol, and glycosylation
  • Cationic polymerization initiator for vinyl ethers, styrene, and isobutene oligomers
  • Petroleum alkylation catalyst combining isobutane with C3-C5 olefins for gasoline blendstock
  • Thermal-neutron detector fill gas in BF3 proportional counters for reactor instrumentation
  • Teaching example of Lewis acid-base theory, including the BCl3 reactivity-order paradox

Safety Information

GHS: Acute Tox. 2 (inhalation), Skin Corr. 1A, Eye Dam. 1. Hydrolyzes violently with water or moist air to give HF and boric acid — meaning every leak generates HF mist, and any skin contact requires immediate calcium gluconate gel application. ACGIH TLV: 1 ppm ceiling. Cylinders need stainless or Monel regulators (corrodes brass), and the work area needs continuous local exhaust ventilation plus an HF first-aid kit on the wall. Never bring a wet glove anywhere near a BF3 line.

This safety summary is for educational reference only and may not be complete. It is not a substitute for Safety Data Sheets (SDS), medical advice, or professional chemical safety guidance. Always consult appropriate SDS and qualified professionals before handling chemicals.

Constituent Elements

Frequently Asked Questions

What is the molar mass of boron trifluoride?
BF3 calculates to 67.806 g/mol: boron at 10.81 plus three fluorines at 18.998 (totaling 56.994). At STP that gives a gas density of about 3.0 g/L, more than twice the density of air, which is why BF3 leaks pool at floor level and any ventilation strategy needs to draw from low in the room rather than from the ceiling.
Why is BF3 a Lewis acid?
Boron has only 3 valence electrons and forms 3 bonds in BF3, which leaves it 2 electrons short of an octet — a vacant 2p orbital sits perpendicular to the trigonal-planar BF3 plane, ready to accept any incoming electron pair. When a Lewis base like ether or amine approaches from above or below the molecular plane, the p-orbital accepts the donated lone pair, the boron rehybridizes from sp2 to sp3, and a tetrahedral adduct forms (F3B-OEt2 in the case of diethyl ether). That ability to accept an electron pair is the entire definition of a Lewis acid.
What is BF3 etherate?
BF3-OEt2, the diethyl ether complex of boron trifluoride. It's a fuming colorless-to-pale-yellow liquid (bp 126 °C, density 1.13 g/mL) where the ether oxygen donates its lone pair into the empty B-2p orbital, giving a stable tetrahedral adduct that's vastly easier to handle than the gas. The complex is in equilibrium with free BF3 and ether, so it works as a slow-release source of BF3 in solution — perfect for catalysis. Fischer Scientific, Aldrich, and TCI all sell it at around 48 percent BF3 by weight, and it's one of the most commonly stocked Lewis acids on the synthetic chemistry shelf.