An energy interconversion principle applied in reaction dynamics for the determination of equlibrium standard states (Q2503725)

The paper concerns a description of the equilibrium states of chemical reactions in terms of statistical molecular dynamics. It is shown that most molecular bonds can be modeled as a rotation heat engine. Expressions are derived for the standard Gibbs free energy, enthalpy and entropy. The empirically determined Gibbs free energy of a dimer reaction \(2A\rightarrow A_2\) compares well with the obtained theoretical estimate. The equilibrium constant and other kinetic parameters are related to the rate constant of the reaction. It explains the commonly observed linear relationship between the logarithms of the rate constant and equilibrium constant. These relationships could include analogues of the Hammett correlations used extensively in physical organic chemistry, as well as others which are temperature dependent. It is demonstrated that the equilibrium standard reaction free energy is more dependent on the height of the intermolecular potential than its depth. As a result the sign of the standard reaction free energy can change for varying barrier height with fixed well depth.