Molecular thermodynamic model for equilibria in solution: IV. Macroscopic partition functions

• Published in: Thermochimica acta Vol. 320; no. 1; pp. 277 - 283
• Main Authors: Braibanti, A., Fisicaro, E., Compari, C.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 02.11.1998; Elsevier Science
• Subjects: Chemical equilibria; Chemical thermodynamics; Chemistry; Exact sciences and technology; General and physical chemistry; General. Theory; Statistical mechanics; Theory; Statistical mechanics; Theory; Chemical equilibria; Theoretical study; Chemical equilibrium; Chemical potential; Statistical thermodynamics; Partition function
• ISSN: 0040-6031; 1872-762X
• DOI: 10.1016/S0040-6031(98)00476-6

The molecular ensembles statistically distributed according to internal specific characteristics and distinguished for the different exchanges with the surroundings are represented on the macroscopic scale by appropriate partition functions. The partition function for osmotic non-reacting ensemble is a function of concentration or activity of the ligand and is suited to the definition of thermodynamic potential μ. The partition function for thermal non-reacting ensemble shows the dependence upon the temperature and that for thermo-osmotic non-reacting ensemble shows the dependence upon both concentration and temperature. The reaction partition function is suited to show the distribution of the different species over the different enthalpy levels of the reacting ensemble. The dispersion of the distributions are represented by second derivatives of the partition function. The information contained in the entropy axis of the thermodynamic space for reacting ensembles concerning the induced dilution of the bound ligand and final dilution of the free ligand can be spanned to a formation function diagram where free energy of reaction can be graphically represented.