Molecular thermodynamic model for equilibria in solution. III. Equilibrium constants and correlation functions in probability, thermodynamic, and kinetic energy space

The partition functions of soln. thermodn. at the macroscopic level of description correspond to typical distributions of particles at the microscopic mol. level. The partition functions can be represented in probability space which is the domain of formation consts., diln., concns., probability correlation function, free-energy probability, enthalpy probability, and entropy probability. Types of ensembles, either reacting or non-reacting, yield characteristic probability diagrams. The first moment of the probability distribution belongs to thermodn. space which is the domain of the extensive thermodn. variables. The ratios of heat, free energy, enthalpy, entropy to thermal energy RT, as well as logarithm of activity coeff., logarithm of probability correlation function, and logarithm of equil. const. can be measured in affinity thermodn. space. The properties of the ensembles can be also represented in kinetic energy probability space which corresponds to the exptl. domain of thermal dilns., with variable {(1/[A])T} and in kinetic energy thermodn. space which is the domain of abs. free energy, enthalpy and entropy, of -RT ln[A], and of heat and work.