化学反应的平衡常数 K 与正、逆反应速度常数 k_f、k(?)的关系:(1)式(1)常见于无机化学、物理化学、化学动力学等教科书、专著及文献中。被人们称为定理(theo-rem)、速度商定律(the rate quotient law)、动力学和热力学的一致性(complet...化学反应的平衡常数 K 与正、逆反应速度常数 k_f、k(?)的关系:(1)式(1)常见于无机化学、物理化学、化学动力学等教科书、专著及文献中。被人们称为定理(theo-rem)、速度商定律(the rate quotient law)、动力学和热力学的一致性(complete consistency of ther-modynamics and kinetics)等。事实上,式(1)的应用有严格的条件,它仅适用于基元反应及决速步的计算数为1的总包反应。展开更多
The conventional symmetry numbers σ<sub>≠</sub><sup>’</sup> of activated complexes may lead to error in the rate constant expression of transition state theory, whereas the statistical fact...The conventional symmetry numbers σ<sub>≠</sub><sup>’</sup> of activated complexes may lead to error in the rate constant expression of transition state theory, whereas the statistical factor ι<sup>≠</sup> or ι may violate the principle of detailed balance. A mathematically precise definition of the symmetry number σ<sub>≠</sub> of activated complex is given, i.e. σ<sub>≠</sub>=<sub>i</sub>N<sub>4</sub>（?）/m, m is the number of physically distinct configurations of labelled transition state and N<sub>i</sub> is the identical atoms in the activated complex. The identical atoms must belong to the same molecule of reactants and products. The present symmetry numbers σ<sub>≠</sub> of activated complexes assure not only obtaining correct rate constant expressions but also obeying the principle of detailed balance. It can be used with the statistical factor ι to construct the structures of transition states for unimolecular and bimolecular exchange reactions.展开更多
文摘化学反应的平衡常数 K 与正、逆反应速度常数 k_f、k(?)的关系:(1)式(1)常见于无机化学、物理化学、化学动力学等教科书、专著及文献中。被人们称为定理(theo-rem)、速度商定律(the rate quotient law)、动力学和热力学的一致性(complete consistency of ther-modynamics and kinetics)等。事实上,式(1)的应用有严格的条件,它仅适用于基元反应及决速步的计算数为1的总包反应。
文摘The conventional symmetry numbers σ<sub>≠</sub><sup>’</sup> of activated complexes may lead to error in the rate constant expression of transition state theory, whereas the statistical factor ι<sup>≠</sup> or ι may violate the principle of detailed balance. A mathematically precise definition of the symmetry number σ<sub>≠</sub> of activated complex is given, i.e. σ<sub>≠</sub>=<sub>i</sub>N<sub>4</sub>（?）/m, m is the number of physically distinct configurations of labelled transition state and N<sub>i</sub> is the identical atoms in the activated complex. The identical atoms must belong to the same molecule of reactants and products. The present symmetry numbers σ<sub>≠</sub> of activated complexes assure not only obtaining correct rate constant expressions but also obeying the principle of detailed balance. It can be used with the statistical factor ι to construct the structures of transition states for unimolecular and bimolecular exchange reactions.
