Aldehyde-bisulfite adducts: prediction of some of their thermodynamic and kinetic properties

Eric Betterton, Y. Erel, M. R. Hoffmann

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Abstract

Stability constants (K1) for the reaction of acetaldehyde and hydroxyacetaldehyde with NaHSO3, determined spectrophotometrically in aqueous solution, were found to be (6.90 ± 0.54) x 105 M-1 and (2.0 ± 0.5) x 106 M-1, respectively, where K1 (corrected for aldehyde hydration) = [RCH(OH)SO3-]/[RCHO][HSO3-] (μ = 0.2 M; 25°C). Acid dissociation constants (pK(a3)) of a series of α-hydroxyalkanesulfonate salts, RCH(OH)SO3-, were found to be 11.46 (CH3-), 11.28 (H-), 10.30 (HOCH2-), 10.33 (C6-H5-), 10.31 (CH3CO-), and 7.21 (Cl3C-) (μ = 0 M; 25°C). Simple straight-line relationships were found to exist between Taft's σ* parameter and a number of thermodynamic and kinetic properties of some aldehydes. K1, K(a3), and the rate constant for nucleophilic addition of SO32- all increase linearly with σ*. Carbonyl species such as halogenated derivatives of acetaldehyde, certain β- and γ-dicarbonyl aldehydes, and perhaps also some highly (halogen) substituted ketones, i.e., all those species with Σσ* ≥ ~1.5 (aldehydes) or Σσ* ≥ ~2.5 (ketones), could be important S(IV) reservoirs.

Original languageEnglish (US)
Pages (from-to)92-99
Number of pages8
JournalEnvironmental Science and Technology
Volume22
Issue number1
Publication statusPublished - Jan 1988
Externally publishedYes

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ASJC Scopus subject areas

  • Environmental Science(all)
  • Environmental Chemistry
  • Environmental Engineering

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