山东工程学院学报
山東工程學院學報
산동공정학원학보
JOURNAL OF SHANDONG INSTITUTE OF TECHNOLOGY
2002年
2期
20-24
,共5页
次甲基硅插入反应%热力学及动力学性质%量子化学
次甲基硅插入反應%熱力學及動力學性質%量子化學
차갑기규삽입반응%열역학급동역학성질%양자화학
silylidyne insertion reaction%thermodynamic and kinetic studies%quantum chemistry
在量子化学对SiH与HCl反应计算的基础上,运用统计热力学和Wigner校正的Eyring过渡态理论计算了该反应在73.15～1873.15K温度范围内的热力学函数、平衡常数、频率因子A和速率常数随温度的变化.计算结果表明该反应在低温下具有热力学优势,而在高温下具有动力学优势.该反应在研究的温度范围内是一放热、熵减少的反应,反应的速率常数随温度的升高而增大,而且服从Arrhenius定律.
在量子化學對SiH與HCl反應計算的基礎上,運用統計熱力學和Wigner校正的Eyring過渡態理論計算瞭該反應在73.15～1873.15K溫度範圍內的熱力學函數、平衡常數、頻率因子A和速率常數隨溫度的變化.計算結果錶明該反應在低溫下具有熱力學優勢,而在高溫下具有動力學優勢.該反應在研究的溫度範圍內是一放熱、熵減少的反應,反應的速率常數隨溫度的升高而增大,而且服從Arrhenius定律.
재양자화학대SiH여HCl반응계산적기출상,운용통계열역학화Wigner교정적Eyring과도태이론계산료해반응재73.15～1873.15K온도범위내적열역학함수、평형상수、빈솔인자A화속솔상수수온도적변화.계산결과표명해반응재저온하구유열역학우세,이재고온하구유동역학우세.해반응재연구적온도범위내시일방열、적감소적반응,반응적속솔상수수온도적승고이증대,이차복종Arrhenius정률.
On the basis of quantum chemical study of the silylidyne insertion reaction with HCl, the statistical thermodynamics and Eyring transition state theory with Wigner correction are used to compute the thermodynamic functions, the equilibrium constants. A factor and the rate constants of this reaction in the temperature range 200～2000K. The calculation results show that the SiH insertion reaction into HCl is thermodynamically dominant at low temperature and kinetically favored at higher temperature. The statistical thermodynamic calculation shows that this reaction is exothermic and of entropy decrease at 73.15 ～ 1873.15K. The kinetic calculation results indicate that this reaction obeys the Arrhenius rate law, and the rate constant of this reaction increases with increasing temperature.
