Thermochimica Acta, Vol.320, No.1-2, 253-263, 1998
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 specific characteristics. The ensembles are classified 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 fluctuations 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.
Keywords:MACROMOLECULE LIGAND EQUILIBRIA;SITE AFFINITY CONSTANTS;STATISTICAL-MODEL;PARTITION-FUNCTION;DISPERSION SPACE;COOPERATIVITY COEFFICIENTS;BINDING CONSTANTS;METAL-LIGAND;PROBABILITY;PROTONS