【摘要】 通过对理想气体等温、等容反应系统等温方程与平衡常数的探讨,得出了-RTlnKθc=ΔrAθm(cθ)的结论。将-RTlnKθc=ΔrAθm(cθ)的结论用于过渡态理论,得到了选用不同标准态时对应的速率常数公式,也得到了不同活化能与活化热力学能、活化焓之间的关系式。通过对速率常数公式间的对比,给出了活化熵、活化热力学能、活化焓、活化亥姆霍兹函数和活化吉布斯函数在选用不同标准态时的区别。由上述结论及所得关系式,解释了由-RTlnKθc=ΔrGθm(cθ)产生的矛盾,还分析了-RTlnKθc=ΔrGθm(cθ)存在的原因及可用条件。更多还原

【Abstract】 Van’t Hoff isotherm and chemical equilibrium constants for the chemical reactions in perfect gases at constant temperature and volume are discussed.As a result,the equation of-RTlnKθc=ΔrAθm(cθ) is drawn.Based on the application of-RTlnKθc=ΔrAθm(cθ) in the transition state theory,the equations of rate constants at different standard states,the relationships between activation energy and activation thermodynamic energy,as well as between activation energy and activation enthalpy are proposed.By comparison of these different equations of rate constants,the selections of thermodynamic energy,enthalpy,entropy,Helmholtz function and Gibbs function at different standard states are given.In addition,we explain the preposterous result that-RTlnKθc=ΔrGθm(cθ) is misused and give the applied conditions of-RTlnKθc=ΔrGθm(cθ).更多还原