【摘 要】
：
基于G3(MP2)//B3PW91/6-31G(d)水平下的电子结构信息[1],利用变分过渡态理论(CVT)计算了CH4+BCl3+H2热解反应最佳反应通道中各基元反应在200-2000 K的速率常数kCVT,获得了经小曲率隧道效应模型(SCT)校正后的速率常数kCVT-SCT,拟合了各基元反应的三参数Arrhenius速率常数表达式；用COMSOL程序,在特定实验条件下获得了1200-1600
【机 构】
：
陕西师范大学化学化工学院,陕西,西安,710062;西北工业大学理学院,陕西,西安,710072
论文部分内容阅读
基于G3(MP2)//B3PW91/6-31G(d)水平下的电子结构信息[1],利用变分过渡态理论(CVT)计算了CH4+BCl3+H2热解反应最佳反应通道中各基元反应在200-2000 K的速率常数kCVT,获得了经小曲率隧道效应模型(SCT)校正后的速率常数kCVT-SCT,拟合了各基元反应的三参数Arrhenius速率常数表达式；用COMSOL程序,在特定实验条件下获得了1200-1600 K温度下各反应物和产物浓度随时间的变化关系,求解了反应的表观活化能.结果表明,完全解离产物BC和B的浓度随着温度的升高而增大,生成B的浓度总是高于BC,且较高温度下有利于富硼产物的生成和沉积；以CH4浓度变化所表示的反应速率的对数和温度的倒数有着很好的线性关系,由此得到反应的表观活化能为208.4 kJ·mol-1,与G3(MP2)方法下计算得决速步基元反应的能垒238.6 kJ·mol-1符合[1].而以BCl3反应速率的对数值和温度的倒数在两个温度区间(700-1600 K和1700-2000 K)内分别也有着很好的线性关系,对应活化能为201.7和378.3kJ·mol-1.
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