MOLECULAR THERMODYNAMIC MODEL FOR EQUILIBRIA IN SOLUTION - III - EQUILIBRIUM-CONSTANTS AND CORRELATION-FUNCTIONS IN PROBABILITY, THERMODYNAMIC, AND KINETIC-ENERGY SPACE

The partition functions of solution thermodynamics at the macroscopic level of description correspond to typical distributions of particles at the microscopic molecular level. The partition functions can be rep resented in probability space which is the domain of formation constan ts, dilution, concentrations, probability correlation function, free-e nergy probability, enthalpy probability, and entropy probability. Type s of ensembles, either reacting or non-reacting, yield characteristic probability diagrams. The first moment of the probability distribution belongs to thermodynamic space which is the domain of the extensive t hermodynamic variables. The ratios of heat, free energy, enthalpy, ent ropy to thermal energy RT, as well as logarithm of activity coefficien t, logarithm of probability correlation function, and logarithm of equ ilibrium constant can be measured in affinity thermodynamic space. The properties of the ensembles can be also represented in kinetic energy probability space which corresponds to the experimental domain of the rmal dilutions, with variable {(1/[A])(T)} and in kinetic energy therm odynamic space which is the domain of absolute free energy, enthalpy a nd entropy, of -RTln[A], and of heat and work. (C) 1998 Elsevier Scien ce B.V.