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

Journal Article · Fri Jan 01 00:00:00 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), Vol. 22:1
• Country of Publication: United States
• Language: English

Related Subjects

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