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Antimony Pentachloride

SbCl5 inorganic

Properties

StateLiquid (fuming in air)
ColorColorless to pale yellow (darkens on standing)
SolubilityReacts violently with water; soluble in HCl, CS2, CHCl3
Melting Point4 °C
Boiling Point140 °C (decomposes)

About Antimony Pentachloride

Antimony pentachloride is a Lewis acid strong enough that it shows up in the chemistry of superacids — the world of compounds whose Hammett acidity functions are off the bottom of the conventional pH scale. The molecule itself is a discrete trigonal-bipyramidal SbCl5 unit (D3h symmetry) in solid, liquid, and gas phases, which sets it apart from transition-metal pentachlorides that tend to be ionic chloride-bridged dimers. Sb(V) here is a d¹⁰s⁰ ion with no remaining valence electrons and an empty axial coordination site that's hungry for a sixth ligand; nearly anything with a lone pair — a chloride from another SbCl5, a fluoride from HF, an ether oxygen, a phosphine — coordinates readily to give the octahedral [SbCl5L] adduct. That hunger is what makes SbCl5 useful as a chlorinating agent (it transfers chloride to alcohols and replaces –OH with –Cl), as a Friedel–Crafts catalyst (sometimes more active than AlCl3 for sluggish substrates), and as the precursor to SbF5 by halide exchange with HF. The SbF5/HF combination — fluoroantimonic acid — is the classical archetype of a superacid: SbF5 grabs a fluoride off HF to give [SbF6]⁻ and leaves behind a highly mobile H2F⁺ proton that's about 10¹⁶ times more acidic than 100% sulfuric acid by Hammett's H₀ scale, capable of protonating methane and ethane. The handling reality is that SbCl5 fumes in air, hydrolyzes violently in water, and corrodes most metals — the bottle that comes from the supplier is usually amber glass with a Teflon-lined cap.

Where you'll encounter it

If you've worked with superacids — protonating alkanes, doing carbocation chemistry on substrates that don't carry leaving groups, or studying isomerization of paraffins for petroleum-refining catalysis — you've encountered fluoroantimonic acid, and the SbF5 in that mixture started its life as SbCl5. Outside the superacid context, SbCl5 is a working reagent in some petroleum-isomerization processes (it converts straight-chain paraffins to branched isomers for higher-octane gasoline), in selective alkyl-chloride synthesis from primary alcohols, and as a one-electron oxidant for studying organic radical-cation chemistry. Most chemists who handle it do so once or twice in a career — it's a powerful but unpleasant reagent, and the practical workarounds (pre-formed chloride sources, milder Lewis acids, switched-on flow chemistry) are usually preferable when they exist.

Common Uses

  • SbF5 precursor for fluoroantimonic-acid superacid chemistry
  • Lewis-acid catalyst for difficult Friedel-Crafts alkylations and acylations
  • Petroleum-isomerization catalyst for alkane branching
  • Chlorinating reagent for alcohol-to-alkyl-chloride conversion
  • One-electron oxidant for organic radical-cation studies

Safety Information

Reacts violently with water — small spills release HCl gas explosively, and the resulting solution is corrosive enough to eat through nitrile gloves. Fumes are immediately irritating to airways and eyes. Acute oral and inhalation toxicity are both Category 3; chronic exposure damages the respiratory tract and may produce long-term pulmonary fibrosis. OSHA PEL is 0.5 mg/m³ as antimony. Never handle outside a fume hood; never store near water sources or aqueous reagents. GHS H301, H314, H331, H372, H410.

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 antimony pentachloride?
299.01 g/mol. Sum 121.760 for the antimony and 5(35.453) for the five chlorines, giving 299.03. The slight discrepancy from the listed 299.01 reflects rounding in older Sb atomic-mass standards. Density is 2.34 g/mL, so 1 mL contains roughly 7.8 mmol — useful for stoichiometry-driven transfers under inert atmosphere.
Why is SbCl5 such a strong Lewis acid?
Three structural reasons together. First, Sb(V) is a large, soft, polarizable cation with 5d valence orbitals that accept electron density readily from incoming ligands. Second, the trigonal-bipyramidal SbCl5 has an open octahedral position waiting to be occupied — adduct formation is energetically downhill from the start. Third, the d¹⁰s⁰ configuration leaves no antibonding orbitals to populate, so coordination of a sixth ligand has no electronic penalty. The combination places SbCl5 above AlCl3 and BCl3 in many measured Lewis-acid-strength scales, and the bigger atomic radius (compared to AlCl3) lets it accept bulkier ligands without steric resistance.
What is fluoroantimonic acid?
A 1:1 (or sometimes 1:2) mixture of HF and SbF5, where SbF5 plays the role of a Lewis-acid activator on HF: SbF5 + HF → H⁺ + [SbF6]⁻. The ionized H⁺ exists as the strongly acidic H2F⁺ (or higher polyfluoride-stabilized forms), with Hammett H₀ around -28 — about 10¹⁶ times more acidic than 100% sulfuric acid (H₀ ≈ -12). At those acidity levels, methane gets protonated to CH5⁺ (yes, a five-coordinate carbon), tert-butanol loses water at -78 °C to give the t-butyl cation cleanly, and several other reactions that no other acid can drive become accessible. SbCl5 is the standard precursor for the SbF5 component, prepared by reacting SbCl5 with anhydrous HF until all the chloride is replaced by fluoride.