Ab initio method, under the effective core potential(ECP) approximation at HF/LANL2DZ level, has been employed to study the reaction mechanism of the carbonyl insertion of olefin hydroformylation catalyzed by a carbo...Ab initio method, under the effective core potential(ECP) approximation at HF/LANL2DZ level, has been employed to study the reaction mechanism of the carbonyl insertion of olefin hydroformylation catalyzed by a carbonyl cobalt HCo(CO)_3. The two reaction paths have been discussed. The calculated potential energy barriers for the carbonyl migration and the ethyl group migration are 105. 0 kJ/mol and 39. 17 kJ/mol, respectively. The results indicate that the reaction path via ethyl migration is more energetically favorable than that via carbonyl insertion.展开更多
用微量热天平研究了氧化锌脱除 COS 过程中的催化加氢效应。在240～400℃的实验温区,这一过程按直接吸收及催化加氢吸收两种机理进行。吸收动力学行为可用类似未反应收缩核模型描述,并对 COS 具有一级反应特征。催化加氢使 COS 转化为 H...用微量热天平研究了氧化锌脱除 COS 过程中的催化加氢效应。在240～400℃的实验温区,这一过程按直接吸收及催化加氢吸收两种机理进行。吸收动力学行为可用类似未反应收缩核模型描述,并对 COS 具有一级反应特征。催化加氢使 COS 转化为 H_2S 再被吸收从而降低了反应能垒,成倍地加速了吸收过程的进行。吸收本身对 H_2为一级反应。分别给出了各反应速率常数的表征式及对应的活化能值。展开更多
文摘Ab initio method, under the effective core potential(ECP) approximation at HF/LANL2DZ level, has been employed to study the reaction mechanism of the carbonyl insertion of olefin hydroformylation catalyzed by a carbonyl cobalt HCo(CO)_3. The two reaction paths have been discussed. The calculated potential energy barriers for the carbonyl migration and the ethyl group migration are 105. 0 kJ/mol and 39. 17 kJ/mol, respectively. The results indicate that the reaction path via ethyl migration is more energetically favorable than that via carbonyl insertion.
文摘用微量热天平研究了氧化锌脱除 COS 过程中的催化加氢效应。在240～400℃的实验温区,这一过程按直接吸收及催化加氢吸收两种机理进行。吸收动力学行为可用类似未反应收缩核模型描述,并对 COS 具有一级反应特征。催化加氢使 COS 转化为 H_2S 再被吸收从而降低了反应能垒,成倍地加速了吸收过程的进行。吸收本身对 H_2为一级反应。分别给出了各反应速率常数的表征式及对应的活化能值。
