An energy interconversion principle applied in reaction dynamics for the determination of equilibrium standard states

Chemical and other species reaction theories involving thermodynamical equilibrium states characterized by a temperature parameter 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 ⇋ A2, 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. One prediction of the principles developed here is that the equilibrium standard reaction free energy is ∗Correspondence: Christopher G. Jesudason, M019,Chemical Physics Group, Department of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia; Fax:03-79674193; Tel: 03-79674270 E-mail: [email protected]