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Hydrofluoric Acid

HF acid

Properties

StateLiquid (aqueous solution) at room temperature
ColorColorless
SolubilityMiscible with water
Melting Point-35°C (40% solution)
Boiling Point106°C (40% solution)

About Hydrofluoric Acid

Hydrofluoric acid (HF in water, 20.006 g/mol) is one of those compounds where the textbook answer ('weak acid, pKa 3.17') and the lab reality ('arguably the most dangerous acid you'll ever handle') diverge completely. It's a weak acid in the formal sense — the H-F bond energy is so high (570 kJ/mol, the strongest of the H-X bonds) that dissociation in water is incomplete. But the chemistry of fluoride ion is what kills people. F- is small, penetrates intact skin without immediate pain, then chelates Ca(2+) and Mg(2+) ions in tissue and serum. A spill of 50% HF on as little as 2.5% of body surface area can cause fatal hypocalcemia within hours, even after the initial burn appears minor. The treatment is calcium gluconate gel rubbed into the contact site, calcium gluconate IV for systemic exposure, and sometimes intra-arterial calcium for digital exposures — every HF user should have a tube of 2.5% Ca-gluconate gel within reach before opening the bottle. Despite this, HF is irreplaceable for several jobs. It's the only common acid that dissolves SiO2 (glass): SiO2 + 6 HF → H2SiF6 + 2 H2O. That's the basis of glass etching, semiconductor wafer cleaning (the standard 'BOE' buffered oxide etch is HF/NH4F mixture), and silicon device fabrication. It's the feedstock for fluoropolymers (PTFE, PVDF) and fluorocarbon refrigerants. In petroleum refining, HF catalyzes alkylation of isobutane with light olefins to make high-octane gasoline blendstock — though most new alkylation units use H2SO4 to avoid HF's hazards.

Where you'll encounter it

If you've ever frosted glass, used a smartphone (whose silicon chip was etched with BOE solutions), driven a car burning alkylate gasoline, or even cooked on a Teflon pan — the chemistry started with HF. Every silicon wafer fabricated at TSMC, Intel, or Samsung passes through dozens of buffered oxide etch steps where HF/NH4F mixtures selectively strip SiO2 layers off the wafer surface — without HF, there is no integrated circuit. Stained-glass restoration shops use dilute HF to frost or shape the borders of replacement pieces because no other acid touches glass. In refining, HF alkylation units at older Phillips 66 and Marathon refineries combine isobutane with light olefins to produce the high-octane blendstock that boosts pump-grade gasoline above 91 octane. The PTFE coating on every nonstick pan in your kitchen traces back to TFE monomer made from HF + chloroform.

Common Uses

  • Buffered oxide etch (BOE) for SiO2 in semiconductor fabrication
  • Glass etching, frosting, and chemical strengthening of optical components
  • Feedstock for HF-based fluoropolymers including PTFE, PVDF, and FKM
  • Production of fluorocarbon refrigerants (HFCs, HFOs replacing CFCs)
  • Alkylation catalyst in petroleum refining for high-octane gasoline blendstock
  • Conversion of UO2 to UF4 then UF6 for nuclear fuel enrichment
  • Stainless steel pickling at low concentration mixed with HNO3

Safety Information

EXTREMELY HAZARDOUS — fundamentally different risk profile from other acids. Penetrates intact skin without immediate sensation, then F- chelates serum and tissue Ca(2+)/Mg(2+) causing local necrosis and systemic hypocalcemia. Even dilute HF (under 7%) can be lethal if exposure covers more than ~25 in2 of skin. OSHA PEL is 3 ppm (8-hr TWA, as F); ACGIH TLV is 0.5 ppm. GHS: H300+H310+H330 (fatal by all routes), H314 (severe burns), H410 (toxic to aquatic life). Mandatory protocol: dedicated training, calcium gluconate 2.5% gel within arm's reach, double nitrile or butyl-rubber gloves, full face shield, splash apron, fume hood with sash down, never alone, posted emergency response plan with hospital contact for IV calcium gluconate. Many academic labs simply prohibit HF and substitute NH4F or buffered alternatives wherever possible.

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 hydrofluoric acid?
HF is 20.006 g/mol — H (1.008) + F (18.998). Concentrated 49% HF stock is roughly 28.9 M with density 1.16 g/mL. The deceptively low molar mass means a small spill of concentrated HF contains a lot of fluoride: 1 mL of 49% HF carries about 549 mg of F-, more than enough to chelate the entire serum calcium pool of an adult.
Why is HF technically a weak acid but still so dangerous?
Pure thermodynamic answer: the H-F bond energy is 570 kJ/mol — the strongest of any H-X bond — and water can't pull H+ off F- as easily as it can off Cl-, Br-, or I-. So Ka is only 6.3 × 10^-4 (pKa 3.17), and at typical concentrations HF is mostly molecular. The danger has nothing to do with H+ activity. It's the F- ion: small enough to diffuse through skin and lipid membranes, with such a high affinity for Ca(2+) and Mg(2+) that it disrupts every Ca-dependent process in tissue once it gets in. Death from cardiac arrhythmia due to plummeting serum Ca is the typical mode of fatal exposure.
Why can hydrofluoric acid dissolve glass?
F- is the only halide ion small enough and electronegative enough to displace oxygen from silicon. The reaction proceeds as SiO2 + 6 HF → H2SiF6 + 2 H2O, going through SiF4 and a hexafluorosilicate intermediate. No other common acid does this — H2SO4, HCl, and HNO3 all leave silica unattacked, which is why they ship in glass bottles and HF doesn't (HF ships in PE or PTFE). The same chemistry is the basis of buffered oxide etch for selectively removing SiO2 layers from silicon wafers in chip fabrication, with NH4F added to keep the etch rate steady.