Raman spectra of solutions of sulfur dioxide in water show only signals due to the SO2 molecule and the bisulfite ion, HSO−3.[2] The intensities of the signals are consistent with the following equilibrium:
SO2 + H2O ⇌ HSO−3 + H+Ka = 1.54×10−2; pKa = 1.81.
17O NMR spectroscopy provided evidence that solutions of sulfurous acid and protonated sulfites contain a mixture of isomers, which is in equilibrium:[3]
[H−OSO2]− ⇌ [H−SO3]−
Attempts to concentrate the solutions of sulfurous acid simply reverses the equilibrium, producing sulfur dioxide and water vapor. A clathrate with the formula 4SO2·23H2O has been crystallised. It decomposes above 7 °C.
History and production
Sulfurous acid is commonly known to not exist in its free state, and due to this, it is stated in textbooks that it cannot be isolated in the water-free form.[4] However, the molecule has been detected in the gas phase in 1988 by the dissociative ionization of diethyl sulfite.[5] The conjugate bases of this elusive acid are, however, common anions, bisulfite (or hydrogen sulfite) and sulfite. Sulfurous acid is an intermediate species in the formation of acid rain from sulfur dioxide.[6]
^Perrin, D. D., ed. (1982) [1969]. Ionisation Constants of Inorganic Acids and Bases in Aqueous Solution. IUPAC Chemical Data (2nd ed.). Oxford: Pergamon (published 1984). Entry 217. ISBN0-08-029214-3. LCCN82-16524.
^Jolly, William L. (1991), Modern Inorganic Chemistry (2nd ed.), New York: McGraw-Hill, ISBN0-07-032768-8
^Catherine E. Housecroft; Alan G. Sharpe (2008). "Chapter 16: The group 16 elements". Inorganic Chemistry, 3rd Edition. Pearson. p. 520. ISBN978-0-13-175553-6.
^D. Sülzle; M. Verhoeven; J. K. Terlouw; H. Schwarz (1988). "Generation and Characterization of Sulfurous Acid (H2SO3) and of Its Radical Cation as Stable Species in the Gas Phase". Angew. Chem. Int. Ed. Engl.27 (11): 1533–4. doi:10.1002/anie.198815331.
^McQuarrie; Rock (1987). General Chemistry (2nd ed.). New York: W.H. Freeman and Company. p. 243. ISBN0-7167-1806-5.
^L. Kolditz, Anorganische Chemie, VEB Deutscher Verlag der Wissenschaften, Berlin 1983, S. 476.