能量互变原理在反应动力学中用于确定平衡标准态
An energy interconversion principle applied in reaction dynamics for the determination of equilibrium standard states
摘要：
涉及化学平衡态的化学理论总是利用统计力学平衡密度分布。本文首先定义了热功变换的概念--热力学相干性，并指出大多数分子键具有上述热功变换性质，将化学键模拟为“离心式热机“。表达式推导出标准吉布斯自由能，焓和熵的键坐标不需要符合非简并玻尔兹曼状态，因为键断裂和形成的过程中，有方向，而平衡分布时，导出的哈密顿量是固定的形式，这是不是使用本地化哈密顿的化学反应的情况。由已知的二聚体反应2A--> A_2的分子动力学模拟经验确定的吉布斯自由能与理论估计相当符合。导出了反应速率与平衡常数及其它动力学参数之间的关系式，并将通常所观察到的反应速率常数与平衡常数之间的线性关系建立在更坚实的理论基础上。这些关系可以包括物理有机化学中广泛使用的Hammett相关性的类似物，以及其他依赖于温度的关系。
英文摘要：
Chemical theories involving thermodynamical equilibrium states invariably utilize statistical mechanical equilibrium density distributions. Here, a definition of heat-work transformation termed thermo mechanical coherence is first made, and it is conjectured that most molecular bonds have the above heat-work transformation property, which models a chemical bond as a "`centrifugal heat engine"' . Expressions are derived for the standard Gibbs free energy, enthalpy, and entropy where the bond coordinates need not conform to a non degenerate Boltzmann state, since bond breakdown and formation are processes that have direction, whereas equilibrium distributions are derived when the Hamiltonian is of fixed form, which is not the case for chemical reactions using localized Hamiltonians. The empirically determined Gibbs free energy from a known molecular dynamics simulation of a dimer reaction 2A--> A_2, accords rather well with the theoretical estimate. A relation connecting the rate of reaction with the equilibrium constant and other kinetic parameters is derived and could place the commonly observed linear relationship between the logarithms of the rate constant and equilibrium constant on a firmer theoretical footing. These relationships could include analogues of the Hammett correlations used extensively in physical organic chemistry, as well as others which are temperature dependent.
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