采用分光光度法研究了2,2'-联吡啶催化Cr(Ⅵ)氧化1,3-丁二醇的反应动力学.结果表明:反应对Cr(Ⅵ)是准一级,对1,3-丁二醇是一级.在保持准一级的反应条件([1,3-丁二醇].＞＞[Cr(Ⅵ)]0)下,该反应的表观速率常数kobs随[H+]和[bipy]的增加而增加,增大反应体系的离子强度,速率常数略有增大.提出了该实验的反应机理:Cr(Ⅵ)和2,2'-联吡啶先形成活化络合物,活化络合物又和一分子的1,3-丁二醇反应,该反应和Cr(Ⅵ)直接氧化1,3-丁二醇的反应构成速控步,随后经过几步快速反应生成产物.依此机理能较好地解释实验现象,并且计算了不同温度下的催化常数和热力学参数.
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