The activity coefficient within the solvation thermodynamics formalism: Fundamentals and applications to neutral solutes

Raposo, Diego; Longo, Ricardo L.

doi:10.1016/j.molliq.2019.03.025

Cited by 2 publications

(2 citation statements)

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“…Besides, from the ST, it is possible to delineate the SGE of a molecule as a function of the SGEs of all of its conformers, along with other conformational properties. 43,44 Although its use is largely applied in the calculation of SGEs from experimental data in correct concentration scales, the whole formalism can be used to the understanding of chemical reactions in solution, in the calculation of the activity coefficient, 45 and in the study of the conformational equilibrium, 46 among others. 47 The link between thermodynamic properties of rigid conformers and the properties of the flexible molecule (which includes the probabilistic distribution and individual properties of each conformer) was already addressed by Arieh Ben-Naim, who deduced an useful equation to obtain the total SGE of a molecule i in phase α, ΔG i,α * , in terms of the SGE of the conformer P, ΔG i,α * (P), considering all possible conformers: 43,…”

Section: Introductionmentioning

confidence: 99%

“…The ST is a theory that links a rigorous microscopic definition of solvation with the thermodynamic (macroscopic) properties associated with this process. , It gives a solid theoretical basis to describe the thermodynamics of solvation and other processes (such as other transference processes between fluids or chemical reactions), providing equations that can be used to make experimental predictions, and that allows a precise interpretation of previous experimental results. Besides, from the ST, it is possible to delineate the SGE of a molecule as a function of the SGEs of all of its conformers, along with other conformational properties. , Although its use is largely applied in the calculation of SGEs from experimental data in correct concentration scales, the whole formalism can be used to the understanding of chemical reactions in solution, in the calculation of the activity coefficient, and in the study of the conformational equilibrium, among others…”

Section: Introductionmentioning

confidence: 99%

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Effect of Conformational Equilibrium on Solvation Properties of 1,2-DCE in Water: A Solvation Thermodynamics and 3D-RISM Study

Raposo

2023

J. Phys. Chem. B

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The contributions of the enthalpy and entropy of solvation for the study of chemical and biological systems are important in the prediction, interpretation, and manipulation of these processes. The relation between solvation Gibbs energies, enthalpies, and entropies of solvation, and their rigorous relation with the conformational equilibrium, are derived for the first time and applied with a computational method, in accordance with the Solvation Thermodynamics previous results, to 1,2-dichloroethane solvation in water. The rigid conformer calculations in solution were performed by using PC+/3D-RISM approach, with the conformational averaged results for enthalpy and solvation Gibbs energy reproducing the experimental results quite successfully. A qualitative agreement in the entropy of solvation predictions was also observed.

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Section: Introductionmentioning

confidence: 99%