{"title":"2, 2'-Bipyridyl Catalysis of the Chromium (VI) Oxidation of 1, 2-propanediol: a Kinetic and Mechanistic Study","authors":"J. Shan, L. Fan, S. Huo, C. Han, S. Shen","doi":"10.1515/IRM.2008.6.4.281","DOIUrl":null,"url":null,"abstract":"The kinetics and mechanism of 2 , ′-bipyridyl (bpy) catalysis of the chromium(VI) oxidation of 1, 2-propanediol in aqueous acidic medium has been studied spectrophotometrically. The reaction shows pseudo-first order with respect to Cr(VI) and fractional order with respect to 1 , 2-propanediol. The observed rate constant ( kobs) increases with the increase in [H +] and [bpy]. Change in ionic strength does not influence the rate obviously and no free radicals are detected. Thus, HCrO 4 is assumed the main existing species of Cr(VI). Based on the experimental results, a probable reaction mechanism of oxidation is proposed. The rate equation derived from the mechanism can explain all the experimental phenomena. The activation parameters along with rate constants of the rate-determining step have been calculated.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"9 1","pages":"281 - 286"},"PeriodicalIF":0.0000,"publicationDate":"2008-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"BioInorganic Reaction Mechanisms","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1515/IRM.2008.6.4.281","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
Abstract
The kinetics and mechanism of 2 , ′-bipyridyl (bpy) catalysis of the chromium(VI) oxidation of 1, 2-propanediol in aqueous acidic medium has been studied spectrophotometrically. The reaction shows pseudo-first order with respect to Cr(VI) and fractional order with respect to 1 , 2-propanediol. The observed rate constant ( kobs) increases with the increase in [H +] and [bpy]. Change in ionic strength does not influence the rate obviously and no free radicals are detected. Thus, HCrO 4 is assumed the main existing species of Cr(VI). Based on the experimental results, a probable reaction mechanism of oxidation is proposed. The rate equation derived from the mechanism can explain all the experimental phenomena. The activation parameters along with rate constants of the rate-determining step have been calculated.