{"title":"硫酸水溶液中铬(III)催化铈(IV)氧化丙-1-醇和丁-1-醇的动力学及机理","authors":"A. Das, S. Mondal, D. Kar, M. Das","doi":"10.1515/irm-1999-0211","DOIUrl":null,"url":null,"abstract":"The kinetics and mechanism of chromium(III) catalysed oxidation of propan-1-ol and butan-1-ol by cerium(IV) in aqueous sulfuric acid media have been studied at different temperatures (30-40° C) under the conditions, [substrate]T(0.025-0.70 mol dm-3) × [CeIV]T (2.5-4.5 × 10-3 mol dm-3) in the presence of [Cr]T = 0.0025-0.07 mol dm-3. At fixed [H+] and [HSO-4 ] the observed rate law conforms to: -d ln[CeIV]/df =kobs =A[S]T[Cr]T/{B + C[Cr]T(D + E[S]T)}, where, A, B, C, D and Ε are constants expressed in terms of different rate constants and equilibrium constants; [S]Tand [Cr]T denote the total substrate (i.e. propan-l-ol or butan-l-ol) and total chromium concentration respectively. The proposed mechanism involves the association of catalyst, substrate and oxidant at some pre-equilibrium steps before the electron transfer step. The overall process is found catalysed by H+ . From the [HSO-4] dependence, Ce(SO4)2 has been found kinetically active.","PeriodicalId":8996,"journal":{"name":"BioInorganic Reaction Mechanisms","volume":"73 1","pages":"169 - 176"},"PeriodicalIF":0.0000,"publicationDate":"1999-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"2","resultStr":"{\"title\":\"Kinetics and Mechanism of Chromium(III) Catalysed Oxidation of Propan-1-ol and Butan-1-ol by Cerium(IV) in Aqueous Sulfuric acid Media\",\"authors\":\"A. Das, S. Mondal, D. Kar, M. Das\",\"doi\":\"10.1515/irm-1999-0211\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The kinetics and mechanism of chromium(III) catalysed oxidation of propan-1-ol and butan-1-ol by cerium(IV) in aqueous sulfuric acid media have been studied at different temperatures (30-40° C) under the conditions, [substrate]T(0.025-0.70 mol dm-3) × [CeIV]T (2.5-4.5 × 10-3 mol dm-3) in the presence of [Cr]T = 0.0025-0.07 mol dm-3. At fixed [H+] and [HSO-4 ] the observed rate law conforms to: -d ln[CeIV]/df =kobs =A[S]T[Cr]T/{B + C[Cr]T(D + E[S]T)}, where, A, B, C, D and Ε are constants expressed in terms of different rate constants and equilibrium constants; [S]Tand [Cr]T denote the total substrate (i.e. propan-l-ol or butan-l-ol) and total chromium concentration respectively. The proposed mechanism involves the association of catalyst, substrate and oxidant at some pre-equilibrium steps before the electron transfer step. The overall process is found catalysed by H+ . From the [HSO-4] dependence, Ce(SO4)2 has been found kinetically active.\",\"PeriodicalId\":8996,\"journal\":{\"name\":\"BioInorganic Reaction Mechanisms\",\"volume\":\"73 1\",\"pages\":\"169 - 176\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1999-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"2\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"BioInorganic Reaction Mechanisms\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1515/irm-1999-0211\",\"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-1999-0211","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Kinetics and Mechanism of Chromium(III) Catalysed Oxidation of Propan-1-ol and Butan-1-ol by Cerium(IV) in Aqueous Sulfuric acid Media
The kinetics and mechanism of chromium(III) catalysed oxidation of propan-1-ol and butan-1-ol by cerium(IV) in aqueous sulfuric acid media have been studied at different temperatures (30-40° C) under the conditions, [substrate]T(0.025-0.70 mol dm-3) × [CeIV]T (2.5-4.5 × 10-3 mol dm-3) in the presence of [Cr]T = 0.0025-0.07 mol dm-3. At fixed [H+] and [HSO-4 ] the observed rate law conforms to: -d ln[CeIV]/df =kobs =A[S]T[Cr]T/{B + C[Cr]T(D + E[S]T)}, where, A, B, C, D and Ε are constants expressed in terms of different rate constants and equilibrium constants; [S]Tand [Cr]T denote the total substrate (i.e. propan-l-ol or butan-l-ol) and total chromium concentration respectively. The proposed mechanism involves the association of catalyst, substrate and oxidant at some pre-equilibrium steps before the electron transfer step. The overall process is found catalysed by H+ . From the [HSO-4] dependence, Ce(SO4)2 has been found kinetically active.