基元对峙反应正逆活化能之差与热力学量的关系

本文讨论了基元对峙反应正逆活化能之差与热力学量之间的关系．指出了现行教材和文献在此问题上的不妥之处．明确说明：对于理想气体基元对峙反应，无论是等温等容反应还是等温等压反应，当速率常数以ke表示时，其正逆活化能之差为反应的热力学能变；对于理想稀溶液基元对峙反应，当速率常数以ke表示时，等温等容条件下正逆活化能之差为反应的热力学能变，等温等压条件下则为反应的焓变．

Relationship Between the Elementary Opposite Reaction and the Thermodynamic Variable

The relationship between the differences of positive and reverse activation energy of the elementary opposite reaction and the thermodynamic variable is discussed in the paper, which indicates that there are some improper points about this subject in some textbooks and documents. It is explained definitely in this paper, whether it is isothermal- isochoric or isothermal- isobaric reaction, for the elementary opposite reaction of ideal gas, while the rate constant is shown in kc, the differences of positive and reverse activation energy is the change of the internal energy of the reaction. For the elementary opposite reaction of ideal diluted solution, while the rate constant is shown in kc, the difference of positive and reverse activation energy is the change of the internal energy to the isothermal - isochoric reaction and is the change of the enthalpy to the isothermal- isobaric reaction.