EFFECT OF HYDROGEN-PEROXIDE ON THE ALKALINE-HYDROLYSIS OF CARBON-DISULFIDE

被引:22
作者
ELLIOTT, S [1 ]
机构
[1] UNIV CALIF IRVINE,DEPT CHEM,IRVINE,CA 92717
关键词
D O I
10.1021/es00072a017
中图分类号
X [环境科学、安全科学];
学科分类号
08 ; 0830 ;
摘要
The stability of carbon disulfide in aqueous alkaline solutions has been compared in the absence and presence of hydrogen peroxide, by a headspace gas chromatography technique. Reactant decay is first order in CS2 and OH− in solutions containing sodium hydroxide alone. At room temperature, the second-order rate constant 1 × 10−3 M−1 s−1 matches previous measurements for basic hydrolysis and, along with the activation energy 22 kcal mol−1, is consistent with rate control in a carbonate-like hydration step. In alkaline hydrogen peroxide solutions, loss is also first order in H2O2, suggesting reaction between CS2 and the HO2− anion with a second-order rate constant in the range 10-100 M−1 s−1. © 1990, American Chemical Society. All rights reserved.
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页码:264 / 267
页数:4
相关论文
共 25 条
[1]   KINETICS OF HYDROLYSIS AND OXIDATION OF CARBON-DISULFIDE BY HYDROGEN-PEROXIDE IN ALKALINE-MEDIUM AND APPLICATION TO CARBONYL SULFIDE [J].
ADEWUYI, YG ;
CARMICHAEL, GR .
ENVIRONMENTAL SCIENCE & TECHNOLOGY, 1987, 21 (02) :170-177
[2]  
Andreae M.O., 1986, ROLE AIR SEA EXCHANG, P331, DOI DOI 10.1007/978-94-009-4738-2_14
[3]   ENHANCED REACTIVITY OF NUCLEOPHILES - ORBITAL SYMMETRY AND SO-CALLED ALPHA-EFFECT [J].
AUBORT, JD ;
HUDSON, RF .
JOURNAL OF THE CHEMICAL SOCIETY D-CHEMICAL COMMUNICATIONS, 1970, (15) :937-&
[4]  
CHERKASSKAYA PM, 1953, J APPL CHEM-USSR, V26, P55
[5]   DETERMINATION OF DISSOLVED SULFIDE AND SEDIMENTARY SULFUR SPECIATION USING GAS-CHROMATOGRAPHY PHOTOIONIZATION DETECTION [J].
CUTTER, GA ;
OATTS, TJ .
ANALYTICAL CHEMISTRY, 1987, 59 (05) :717-721
[6]  
DYRSSEN D, UNPUB MAR CHEM
[7]   FACTORS DETERMINING NUCLEOPHILIC REACTIVITIES [J].
EDWARDS, JO ;
PEARSON, RG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1962, 84 (01) :16-&
[8]   CARBONYL SULFIDE HYDROLYSIS AS A SOURCE OF HYDROGEN-SULFIDE IN OPEN OCEAN SEAWATER [J].
ELLIOTT, S ;
LU, E ;
ROWLAND, FS .
GEOPHYSICAL RESEARCH LETTERS, 1987, 14 (02) :131-134
[9]   THE DISSOCIATION CONSTANT OF HYDROGEN PEROXIDE AND THE ELECTRON AFFINITY OF THE HO2 RADICAL [J].
EVANS, MG ;
URI, N .
TRANSACTIONS OF THE FARADAY SOCIETY, 1949, 45 (03) :224-230
[10]  
HOVENKAMP SG, 1963, J POLYM SCI C, P341