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Kinetics of the formation of hydroxyacetaldehyde-sulfur(IV) adducts at low pH

Olson, Terese M. and Torry, Lori A. and Hoffmann, Michael R. (1988) Kinetics of the formation of hydroxyacetaldehyde-sulfur(IV) adducts at low pH. Environmental Science and Technology, 22 (11). pp. 1284-1289. ISSN 0013-936X. http://resolver.caltech.edu/CaltechAUTHORS:20150814-140635044

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Abstract

The kinetics of the addition of hydroxyacetaldehyde and S(1V) was studied spectrophotometrically over the pH range of 0.7-3.3. Formation rates of the adduct 1,2-dihydroxy-1-ethanesulfonate (DHES) were consistent with the following three-term rate exmession: d[DHES]/dt = (k_0{H^+}α_1/K_(a0) + (k_1α_1 + k_2α_2) C_2H_3O_2]t[S(IV)] where [C_2H_3O_2]_t = [CH_2(OH)CHO] + CH_2(OH)CH(OH)_2] [S-(IV)] = [H_2O•SO_2] + [HSO_3^-] + [SO_3^(2-)],[S(IV)], and α_2 = [SO_3^(2-)]/ [S(IV)], and K_(a0) is the acid dissociation constant for CH_2(OH)C^+HOH. The rate constant k_0 corresponds to a proton-catalyzed pathway in which bisulfite reacts with the carbocation CH_2(OH)C^+_-HOH. A value for the constant k_0/K_(a0) was determined as 5.4 (±2.0) M^(-2), s^(-1) (25 ºC, µ = 0.2 M). The intrinsic constants k_1 and k_2 are the respective rate constants for the reactions of HSO_3^- and SO_3^(2-) with unhydrated hydroxyacetaldehyde, where it was determined that k_1 = 1.74 (±0.16) M^(-1) s^(-1) and k_2 = 5.02 (±0.12) x 10^4 M^(-1) s^(-1). Because of the high intrinsic solubility of CH_2(OH)CHO, calculated DHES formation rates in fogwater and cloudwater are faster than the addition rate of formaldehyde and S(IV). DHES is shown to satisfy the criteria of a significant S(IV) reservoir in atmospheric droplets.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/es00176a006DOIArticle
http://pubs.acs.org/doi/abs/10.1021/es00176a006PublisherArticle
ORCID:
AuthorORCID
Hoffmann, Michael R.0000-0002-0432-6564
Additional Information:© 1988 American Chemical Society. Received for review February 9, 1988. Accepted April 26, 1988. We gratefully acknowledge the Electric Power Research Institute for Organic Acids and Buses; Chapman and Hall: London, (RP1630-47), the U.S. Environmental Protection Agency 1981. (R811496-01-1), and the U.S. Public Health Service (ES04635-01) for their financial support.
Funders:
Funding AgencyGrant Number
Electric Power Research Institute (EPRI)RP 1630-47
Environmental Protection Agency (EPA)R811496-01-1
U.S. Public Health Service (USPHS)ES04635-01
Record Number:CaltechAUTHORS:20150814-140635044
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150814-140635044
Official Citation:Kinetics of the formation of hydroxyacetaldehyde-sulfur(IV) adducts at low pH Terese M. Olson, Lori A. Torry, and Michael R. Hoffmann Environmental Science & Technology 1988 22 (11), 1284-1289 DOI: 10.1021/es00176a006
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59546
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:17 Aug 2015 16:32
Last Modified:17 Aug 2015 16:32

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