{"title":"2,2′-联吡啶基催化铬(VI)氧化1,2 -丙二醇的动力学和机理研究","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":"{\"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}","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}
2, 2'-Bipyridyl Catalysis of the Chromium (VI) Oxidation of 1, 2-propanediol: a Kinetic and Mechanistic Study
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.