Kinetics, mechanism and thermodynamics of bisulfite-aldehyde adduct formation
Abstract
The kinetics and mechanism of bisulfite addition to benzaldehyde were studied at low pH in order to assess the importance of this reaction in stabilizing S(IV) in fog-, cloud-, and rainwater. Previously, the authors established that appreciable concentrations of the formaldehyde-bisulfite adduct (HMSA) are often present in fogwater. Measured HMSA concentrations in fogwater often do not fully account for observed excess S(IV) concentrations, however, so that other S(IV)-aldehyde adducts may be present. Reaction rates were determined by monitoring the disappearance of benzaldehyde by U.V. spectrophotometry under pseudo-first order conditions, (S(IV))/sub T/ >>(phi-CHO)/sub T/, in the pH range 0 - 4.4 at 25/sup 0/C. The equilibrium constant was determined by dissolving the sodium salt of the addition compound in a solution adjusted to pH 3.9, and measuring the absorbance of the equilibrated solution at 250 nm. A literature value of the extinction coefficient for benzaldehyde was used to calculate the concentration of free benzaldehyde. All solutions were prepared under an N/sub 2/ atmosphere using deoxygenated, deionized water and ionic strength was maintained at 1.0 M with sodium chloride.
- Authors:
- Publication Date:
- Research Org.:
- California Institute of Technology, W.M. Keck Labs., 138-78, Pasadena, CA 91125
- OSTI Identifier:
- 5432304
- Report Number(s):
- CONF-860425-
Journal ID: CODEN: ACPCA
- Resource Type:
- Conference
- Journal Name:
- Am. Chem. Soc., Div. Pet. Chem., Prepr.; (United States)
- Additional Journal Information:
- Journal Volume: 31:2; Conference: 191. American Chemical Society national meeting, New York, NY, USA, 13 Apr 1986
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 54 ENVIRONMENTAL SCIENCES; ACID RAIN; ATMOSPHERIC CHEMISTRY; BENZALDEHYDE; RAIN WATER; SULFITES; ADDITIVES; CHEMICAL REACTION KINETICS; CHEMICAL REACTION YIELD; CLOUDS; DERIVATIZATION; FOG; PH VALUE; SPECTROPHOTOMETRY; SULFUR COMPLEXES; THERMODYNAMICS; ALDEHYDES; ATMOSPHERIC PRECIPITATIONS; CHEMICAL REACTIONS; CHEMISTRY; COMPLEXES; HYDROGEN COMPOUNDS; KINETICS; ORGANIC COMPOUNDS; OXYGEN COMPOUNDS; RAIN; REACTION KINETICS; SULFUR COMPOUNDS; WATER; YIELDS; 500200* - Environment, Atmospheric- Chemicals Monitoring & Transport- (-1989)
Citation Formats
Olson, T M, Boyce, S D, and Hoffmann, M R. Kinetics, mechanism and thermodynamics of bisulfite-aldehyde adduct formation. United States: N. p., 1986.
Web.
Olson, T M, Boyce, S D, & Hoffmann, M R. Kinetics, mechanism and thermodynamics of bisulfite-aldehyde adduct formation. United States.
Olson, T M, Boyce, S D, and Hoffmann, M R. 1986.
"Kinetics, mechanism and thermodynamics of bisulfite-aldehyde adduct formation". United States.
@article{osti_5432304,
title = {Kinetics, mechanism and thermodynamics of bisulfite-aldehyde adduct formation},
author = {Olson, T M and Boyce, S D and Hoffmann, M R},
abstractNote = {The kinetics and mechanism of bisulfite addition to benzaldehyde were studied at low pH in order to assess the importance of this reaction in stabilizing S(IV) in fog-, cloud-, and rainwater. Previously, the authors established that appreciable concentrations of the formaldehyde-bisulfite adduct (HMSA) are often present in fogwater. Measured HMSA concentrations in fogwater often do not fully account for observed excess S(IV) concentrations, however, so that other S(IV)-aldehyde adducts may be present. Reaction rates were determined by monitoring the disappearance of benzaldehyde by U.V. spectrophotometry under pseudo-first order conditions, (S(IV))/sub T/ >>(phi-CHO)/sub T/, in the pH range 0 - 4.4 at 25/sup 0/C. The equilibrium constant was determined by dissolving the sodium salt of the addition compound in a solution adjusted to pH 3.9, and measuring the absorbance of the equilibrated solution at 250 nm. A literature value of the extinction coefficient for benzaldehyde was used to calculate the concentration of free benzaldehyde. All solutions were prepared under an N/sub 2/ atmosphere using deoxygenated, deionized water and ionic strength was maintained at 1.0 M with sodium chloride.},
doi = {},
url = {https://www.osti.gov/biblio/5432304},
journal = {Am. Chem. Soc., Div. Pet. Chem., Prepr.; (United States)},
number = ,
volume = 31:2,
place = {United States},
year = {Tue Apr 01 00:00:00 EST 1986},
month = {Tue Apr 01 00:00:00 EST 1986}
}