Title
Solutions, in Particular Dilute Solutions of Nonelectrolytes: A Review
Abstract
The liquid state is one of the three principal states of matter and arguably the most important one; and liquid mixtures represent a large research field of profound theoretical and practical interest. This topic is of importance in many areas of the applied sciences, such as in chemical engineering, geochemistry, the environmental sciences, biophysics and biomedical technology. First, I will concisely present a review of important concepts from classical thermodynamics of nonelectrolyte solutions; this will be followed by a survey of (semi-)empirical approaches to representing the composition and temperature dependence of selected thermodynamic mixture properties, and finally the focus will be on dilute binary nonelectrolyte solutions where one component, a supercritical solute, is present in much smaller quantity than the other component, called the solvent. Partial molar properties in the limit of infinite dilution (indicated by a superscript ∞) are of particular interest. For instance, activity coefficients (Lewis–Randall (LR) convention) are customarily used to characterize mixing behavior, and infinite-dilution values γLR,∞iprovide a convenient route for obtaining binary parameters for several popular solution models. When discussing solute (j)—solvent (i) interactions in solutions where the solute is supercritical, the Henry fugacity hj,i(T,P), also known as Henry’s law (HL) constant, is a measurable thermodynamic key quantity. Its temperature dependence yields information on the partial molar enthalpy change on solution ΔH∞j(T,P), while its pressure dependence yields information on the partial molar volume VL,∞j(T,P) of solute j in the liquid phase (superscript L). I will clarify issues frequently overlooked, touch upon solubility data reduction and correlation, report a few recent high-precision experimental results on dilute aqueous solutions of supercritical nonelectrolytes, and show the equivalency of results for caloric quantities (e.g. ΔH∞j) obtained via van ’t Hoff analysis of high-precision solubility data with directly measured calorimetric data.
Keywords
Mixtures/solutionsResidual propertiesExcess molar propertiesLewis–Randall (LR) rule/Henry’s law (HL)Activity coefficientsGeneralized Kohler equationSolubility of gases in liquids/van 't Hoff analysis
Object type
Language
English [eng]
Persistent identifier
https://phaidra.univie.ac.at/o:1584406
Appeared in
Title
Journal of Solution Chemistry
Volume
51
Issue
6
ISSN
0095-9782
Issued
2021
From page
626
To page
710
Publisher
Springer Science and Business Media LLC
Date issued
2021
Access rights
Rights statement
© The Author(s) 2021

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