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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 被引量:13
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作者 单金缓 刘铁英 《化学学报》 SCIE CAS CSCD 北大核心 1994年第11期1140-1144,共5页
本文采用分光光度法研究了在甲醇介质中(N,N-二乙基二硫代氨基甲酸)烷基黄原酸合钴(Ⅲ)与二丙胺,二正丁胺在298.2K~313.2K(R=Me,Et,n-Pr)的反应动力学及机理.结果表明对配合物是准一级反应,对二正丁胺是分数级.反应速率随着基团R的增... 本文采用分光光度法研究了在甲醇介质中(N,N-二乙基二硫代氨基甲酸)烷基黄原酸合钴(Ⅲ)与二丙胺,二正丁胺在298.2K~313.2K(R=Me,Et,n-Pr)的反应动力学及机理.结果表明对配合物是准一级反应,对二正丁胺是分数级.反应速率随着基团R的增加而减小,随着温度的增加而增加,随着溶剂中水含量的增大而增加.提出了一种含有前期平衡的反应机理.据此导出了一个能够解释实验事实的速率方程,求得了速控步骤的速率常数,并给出了相应的活化参数. 展开更多
关键词 烷基 黄原 二丙胺 二丁胺
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烷基黄原酸合钴(Ⅲ)与二丙胺第三步反应动力学 被引量:3
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作者 单金缓 凌芹 王安周 《物理化学学报》 SCIE CAS CSCD 北大核心 1994年第8期728-732,共5页
The title reactions with R=Me, Et, n-Pr were studied in a temperature range of 298-313K by spectrophotometry. lt was fOund that the rate with respect to [complex] is unity and that to [amine] is fractional. A linear r... The title reactions with R=Me, Et, n-Pr were studied in a temperature range of 298-313K by spectrophotometry. lt was fOund that the rate with respect to [complex] is unity and that to [amine] is fractional. A linear relationship between [amine]/kobs and [amine] was observed, where kobs stands for pseudo-first-order rate constant. The rate increases with the increase in water content of the solvent. A mechanism involying a preequllibrium of an adduct formation between the complex and aAnne was proposed. The equation derived from the mechanism explained all the experimental results and the preequllibrium constants, rate constants of the rate-determing step along with the activation parameters were evaluated. 展开更多
关键词 烷基 黄原 二丙胺
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