期刊
FLUID PHASE EQUILIBRIA
卷 513, 期 -, 页码 -出版社
ELSEVIER
DOI: 10.1016/j.fluid.2020.112546
关键词
Kirkwood-buff formalism; Correlation function integrals; Solvation at infinite dilution; Statistical thermodynamics; Henry's law; Lewis-Randall rule; Ostwald coefficient; Rigorous links between intermolecular asymmetry and non-idealities
We present a novel approach for the calculation of the Krichevskii parameter A(Kr) of solutes in dilute mixtures according to a universal thermodynamic expression that links the solute-solvent intermolecular asymmetry, as described by the Henry's law constant of the solute species in a pure solvent, to the desired A(Kr). The derived expression obeys two key thermodynamic constraints, i.e., corresponding to the behavior of either an ideal gas solute or a solute behaving as a solvent species representing a special case of Lewis-Randall ideal solution. Then, we provide a comparison between the thermodynamically consistent A(Kr) values generated by this approach and those reported in the literature, from diverse experimental sources, and for a variety of aqueous solutes. Finally, we discuss how the A(Kr) = 0 line divides the P - T plane of the pure solvent into two regions characterized by unambiguous solute-solvent intermolecular asymmetries, and provide additional microscopic as well as macroscopic interpretations for A(Kr). (C) 2020 Elsevier B.V. All rights reserved.
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