采用分光光度法研究了在25～40 ℃的酸性介质中2,2'-联吡啶(bpy)催化Cr(Ⅵ) 氧化1,2-丁二醇(1,2-butanediol)的反应动力学及其机理.结果表明:反应对Cr(Ⅵ)是准一级,对1,2-丁二醇是分数级.在保持准一级反应条件 ([1,2-butanediol]0 [Cr(Ⅵ)]0 )下,该反应的表观速率常数kobs随着[H+]的增加而增大,随着[bpy]的增加而增大,并且无盐效应.据此实验现象,笔者提出了该反应的反应机理,并且由假设的反应机理推出的速率方程能很好地解释全部实验现象,为减少Cr(Ⅵ)对环境污染提供了理论依据.
[1] 李艳廷, 李方, LI Yan-ting, LI Fang. 环境中无机铬形态分析研究进展 [J]. 化学研究与应用 2000.doi:10.3969/j.issn.1004-1656.2000.05.003
[2] 李静萍, 杜亚利. 铬对人体的作用 [J]. 甘肃科技 2003.doi:10.3969/j.issn.1000-0952.2003.12.062
[3] 史黎薇. 铬化合物对健康影响的研究进展 [J]. 卫生研究 2003.doi:10.3969/j.issn.1000-8020.2003.04.039
[4] 闫良国, 张旭桢, 王晓东, 李超, 魏琴. 催化动力学光度法测定痕量铬研究进展 [J]. 济南大学学报(自然科学版) 2003.doi:10.3969/j.issn.1671-3559.2003.02.031
[5] 张育川. 1, 2-丁二醇 [J]. 精细与专用化学品 2003.doi:10.3969/j.issn.1008-1100.2003.23.009
[6] ABID M, KHAN Z. The effect of complexing agents on the DMF-chromium (Ⅵ) reaction:A kinetic study [J]. Transactions Metal Chemistry 2003, 28.
[7] MEENAKSHISUNDARAM S, MARKKANDAN R. 1, 10-Phenanthroline catalysed HCrO4-oxidation of some substituted trans-cinnamic acids [J]. Transactions Metal Chemistry 2004, 29.
[8] Signorella S., Daier V., Sala LF., Lafarga R.. The reduction of Cr-VI to Cr-III by the alpha and beta anomers of D-glucose in dimethyl sulfoxide. A comparative kinetic and mechanistic study [J]. Carbohydrate research 2000, 2(2).
[9] KHAN Z, RAFIQUEE MD Z A, KABIR-UD-DIN. Oxidation of L-methionine with aqueous chromic acid:a kinetic study [J]. Transactions Metal Chemistry 1997, 22.
[10] KHAN Z, MASAN S, RAJU. A mechanistic study of the ethylenediaminetetraacetic acid-, 2, 2'-bipyridyl-, and manganese(Ⅱ)-assisted one-step two-and three-electron oxidation of lactic acid by chromium(Ⅵ) [J]. Transactions Metal Chemistry 2003, 28.
[11] Kabir-ud-Din, Khaled Hartani, Zaheer Khan. One-step three-electron oxidation of tartaric and glyoxylic acids by chroium(VI) in the absence and presence of manganese(II) [J]. Transition Metal Chemistry 2002, 6(6).
[12] KHAN Z, KABIR-UD-DIN. Kinetics and mechanism of ethylenediaminetetraacetic acid-, 2, 2'-bipyridyl-, and 1, 10-phenanthroline-assisted chromium(Ⅵ) oxidation of 2-propanol [J]. Transactions Metal Chemistry 2002, 27.
[13] KITA E, PIETKIEWICZ A. A kinetic study of the oxidation of 2-(2-hydroxyethyl)pyridine by chromium(Ⅵ) in strongly acidic aqueous solutions of HClO4 [J]. Transactions Metal Chemistry 2000, 25.
[14] MANSOUR M A. Kinetics and mechanism of chromium(Ⅵ) oxidation of L-methionine [J]. Transactions Metal Chemistry 2002, 27.
[15] 曾汉维, 林遵远, 毛玉麟. 2, 2'-联吡啶类催化铬酸氧化异丙醇的反应动力学研究 [J]. 有机化学 1994, 14.
[16] FEIGL F. Spot tests in organic analysis [M]. New York:Elsesvier Scientific Publishing Company 1966.
[17] KHAN Z, HASHMI A A, KABIR-UD-DIN. Reduction of chromium(Ⅵ) by phosphonic acid [J]. Transactions Metal Chemistry 1998, 23.
[18] 金家骏. 液相化学反应动力学原理 [M]. 上海:上海科学技术出版社 1984.
[19] 单金缓, 刘铁英. 二(N, N-二乙基二硫代氨基甲酸)烷基黄原酸合钴(Ⅲ)与二丙胺和二丁胺反应的动力学 [J]. 化学学报 1994, 52.
[20] 傅献彩, 沈文霞, 姚天扬. 物理化学 [M]. 北京:高等教育出版社 1990.
