Chlorosulfuric acid

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Chlorosulfuric acid (IUPAC name: sulfurochloridic acid) is the inorganic compound with the formula HSO3Cl. It is also known as chlorosulfonic acid, being the sulfonic acid of chlorine. It is a distillable, colorless liquid that should be handled with care. It is hygroscopic and a powerful lachrymator.[1]

Contents
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1 Structure and properties 2 Synthesis 3 Applications 4 Safety 5 Related halosulfuric acids 6 References 7 See also

[edit] Structure and properties

Chlorosulfuric acid is a tetrahedral molecule. The formula is more descriptively written SO2(OH)Cl, but HSO3Cl is traditional. It is an intermediate, chemically and conceptually, between sulfuryl chloride (SO2Cl2) and sulfuric acid (H2SO4).[2] The compound is rarely obtained pure. Upon standing with excess sulfur trioxide, it decomposes to pyrosulfuryl chlorides:[3] 2 ClSO3H + SO3 H2SO4 + S2O5Cl2

[edit] Synthesis
The industrial synthesis entails the reaction of hydrogen chloride with a solution of sulfur trioxide in sulfuric acid:[3] HCl + SO3 ClSO3H It can also be prepared by chlorination of sulfuric acid, written here for pedagogical purposes as SO2(OH)2, vs. the usual format H2SO4: PCl5 + SO2(OH)2 ClSO3H + POCl3 + HCl The latter method is more suited for laboratory-scale operations.

[edit] Applications
ClSO2OH is used to prepare sulfonic acids, which are useful in detergents and as chemical intermediates: ROH + ClSO3H ROSO3H + HCl An early synthesis of saccharin begins with the reaction of toluene with ClSO2OH to give the ortho- and para-toluene sulfonyl chloride derivatives: CH3C6H5 + 2ClSO2OH CH3C6H4SO2Cl + H2SO4 Oxidation of the ortho isomer gives the benzoic acid derivative that then is cyclized with ammonia and neutralized with base to afford saccharin. Chlorosulphonic acid has been used as an anti-contrail agent in Ryan Model 147 reconnaissance drones, and to produce smoke screens.[4]

[edit] Safety
ClSO3H reacts violently with water to yield sulfuric acid and HCl, commonly seen as vapors fuming from the liquid. Precautions, such as proper ventilation, associated with HCl should be observed.

[edit] Related halosulfuric acids

FSO2OH is a related strong acid with a diminished tendency to evolve HF. Bromosulfonic acid, BrSO2OH, is unstable, decomposing at its melting point of 8C to give Br2, SO2, and H2SO4. Iodosulfonic acid is unknown.

[edit] References
1. ^ R.J. Cremlyn, "Chlorosulfonic Acid" Springer-Verlag New York, Inc. (Royal Society of Chemistry, 2002, 300 pp. ISBN 978-0-85404-498-6 2. ^ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001, pages 549-550 (discussion of XSO2OH for X = F, Cl, Br, I) 3. ^ a b Joachim Maas, Fritz Baunack "Chlorosulfuric Acid" in Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH, Weinheim.doi:10.1002/14356007.a07_017 4. ^ The Royal Navy at War (DVD). London: Imperial War Museum. 2005