CAJ | 학술논문

在量子化学对SiH与HF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200～2000K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,且服从Anhenius定律.
재양자화학대SiH여HF반응계산적기출상,운용통계열역학화Wigner교정적Eyring과도태이론계산료해반응재200～2000K온도범위내적열역학함수、평형상수、빈솔인자A화속솔상수수온도적변화.계산결과표명해반응재저온하구유열역학우세,이재고온하구유동역학우세.해반응재연구적온도범위내시일방열、적감소적반응,반응적속솔상수수온도적승고이증대,차복종Anhenius정률.
On the basis of quantum chemical study of the reaction of silylidyne insertion into HF, the statistical ther- modynamics and Eyring transition state theory with Wigner correction are used to estimate the thermodynamic functions, the equilibrium constants, A factors and the rate constants of this reaction in temperature range from 200 to 200OK. The results of calculation show that the reaction of SiH insertion into HF is thermodynamically dominant at low temperature and kinetically favored at high temperature. The statistical thermodynamic calculation shows that this reaction is exothermic and of entropy decrease at 200 ～ 2000K. The kinetic calculation results indicate that this reaction obeys the Arrhenius rate law, and the rate constant of this reaction increases with increasing temperature.