Free-radical-induced oxidation of hydroxymethanesulfonate in aqueous solution .1. A pulse radiolysis study of the reactions of (OH)-O-center dot and SO4 center dot-

被引:10
作者
Barlow, S [1 ]
Buxton, GV [1 ]
Murray, SA [1 ]
Salmon, GA [1 ]
机构
[1] UNIV LEEDS,COOKRIDGE HOSP,COOKRIDGE RADIAT RES CTR,LEEDS LS16 6QB,W YORKSHIRE,ENGLAND
来源
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS | 1997年 / 93卷 / 20期
关键词
D O I
10.1039/a703267f
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The rate constants for the reaction of . OH and SO4.- with hydroxymethanesulfonate (HMS) have been determined. The hydroxyl radical was found to react with HMS by hydrogen abstraction to form (CH)-C-.(OH)SO3-, reaction (5), with a rate constant of (3.0 +/- 0.3) x 10(8) dm(3) mol(-1) s(-1). The spectrum of the product is dependent on pH due to equilibrium (6). This equilibrium has been investigated and has a pK(a) of 6.35 +/- 0.1. The forward and reverse rate constants for the dissociation, k(6) and k(-6), are (5.9 +/- 0.5) x 10(4) s(-1) and (4.4 +/- 1.0) x 10(10) dm(3) mol(-1) s(-1), respectively. The dissociation is subject to acid-base catalysis by phosphate buffer, reaction (7), with k(7) = (9.5 +/- 0.1) x 10(8) dm(3) mol(-1) s(-1) and k(-7) = (1.32 +/- 0.02) x 10(8) dm(3) mol(-1) s(-1) (OH)-O-. + CH2(OH)SO3- --> H2O + (CH)-C-.(OH)SO3- (5) (CH)-C-.(OH)SO3- reversible arrow CH(O-)SO3- + H+ (6) (CH)-C-.(OH)SO3- + HPO42- reversible arrow (CH)-C-.(O-)SO3- + H2PO42- (7) The sulfate radical reacts with HMS with a rate constant of (1.3 +/- 0.2) x 10(6) dm(3) mol(-1) s(-1). The product of this reaction has not been identified.
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页码:3637 / 3640
页数:4
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