On the solubility of gases in dilute solutions: Organic food for thoughts from a molecular thermodynamic perspective

Despite the long history behind the experimental determinations of gas solubility and the consequent wealth of experimental data for binary systems we are still confronted with lingering issues regarding their reliability, the approximations behind their modeling, and the consistency among resulting solvation quantities. In the present effort we discuss cautiously these issues through the thermodynamic scrutiny of the coexistence phase equilibrium equations involving sparingly soluble species according to the recently proposed rigorous molecular-based solvation formalism [Chialvo: Fluid Phase Equilibria https://doi.org/10.1016/j.fluid.2017.10.031 and Journal of Chemical Physics, 148 (2018)]. We address the fundamentals underlying the isothermal-isobaric phase equilibria associated specifically with the solubility of carbon dioxide in aqueous systems, their thermodynamic limit of stability, as well as the link between the latter and the microstructure of the pair of incipient phases. Moreover, we show how the resulting equilibrium phase composition can provide relevant solvation quantities to test the thermodynamic consistency of the experimental data. Finally, we illustrate the arguments explicitly through the analysis of experimental evidence from a few selected sources in the literature, and discuss the implications behind the findings. (C) 2018 Published by Elsevier B.V.