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

Journal Article · Fri Jan 01 04:00:00 EST 1988 · Environ. Sci. Technol.; (United States)

DOI:https://doi.org/10.1021/es00166a010· OSTI ID:7190834

Betterton, E A; Erel, Y; Hoffmann, M R

Stability constants (K/sub 1/) for the reaction of acetaldehyde and hydroxyacetaldehyde with NaHSO/sub 3/, determined spectrophotometrically in aqueous solution, were found to be (6.90 +/- 0.54) x 10/sup 5/ M/sup -1/ and (2.0 +/- 0.5) x 10/sup 6/ M/sup -1/, respectively, where K/sub 1/ (corrected for aldehyde hydration) = (RCH(OH)SO/sub 3//sup -/)/(RCHO)(HSO/sub 3//sup -/) (..mu.. = 0.2 M; 25 /sup 0/C). Acid dissociation constants (pK/sub a3/) of a series of ..cap alpha..-hydroxyalkanesulfonate salts, RCH(OH)SO/sub 3//sup -/, were found to be 11.46 (CH/sub 3/-), 11.28 (H-), 10.30 (HOCH/sub 2/-), 10.33 (C/sub 6/..sqrt..H/sub 5/-), 10.31 (CH/sub 3/CO-), and 7.21 (Cl/sub 3/C-) (..mu.. = 0 M; 25/sup 0/C). Simple straight-line relationships were found to exist between Taft's sigma* parameter and a number to thermodynamic and kinetic properties of some aldehydes. K/sub 1/, K/sub a3/, and the rate constant for nucleophilic addition of SO/sub 3//sup 2 -/ all increase linearly with sigma*. Carbonyl species such as halogenated derivatives of acetaldehyde, certain ..beta..- and ..gamma..-dicarbonyl aldehydes, and perhaps also some highly (halogen) substituted ketones, i.e., all those species with Gamma sigma* greater than or equal to approx. 1.5 (aldehydes) or Gamma sigma* greater than or equal to approx. 2.5(ketones), could be important S(IV) reservoirs.

• Research Organization: California Institute of Technology, Pasadena (USA)
• OSTI ID: 7190834
• Journal Information: Environ. Sci. Technol.; (United States), Journal Name: Environ. Sci. Technol.; (United States) Vol. 22:1; ISSN ESTHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACETALDEHYDE
ADDUCTS
ALDEHYDES
AQUEOUS SOLUTIONS
CHEMICAL PROPERTIES
CHEMICAL REACTION KINETICS
DISPERSIONS
KINETICS
MIXTURES
ORGANIC COMPOUNDS
PHYSICAL PROPERTIES
REACTION KINETICS
SOLUTIONS
THERMODYNAMICS