  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.
