Molecular thermodynamic model for equilibria in solution. I. Reacting and non-reacting ensembles

The partition functions of solution thermodynamics are mathematical representations of the properties of molecular ensembles statistically distributed according to specifc characteristics. The ensembles are classi®ed as non-reacting or reacting. The non-reacting ensembles are characterized by one mean enthalpy level with dispersion around the mean. The reacting ensembles are characterized by two or more distinctly separated enthalpy levels over which the different species are variably distributed, depending on concentration and/or temperature. The non-reacting ensembles can be distinguished into microcanonical, thermal, osmotic, thermo-osmotic ensembles, depending on the type of exchange with the surroundings which is connected to the ¯uctuations of the ensemble variables. The reacting ensembles can be distinguished into thermal, osmotic, thermo-osmotic, electrochemical, electro-osmotic, electrothermal, electro-thermo-osmotic ensembles, depending on the type of reaction and of exchange with the surroundings.