Kohns Maximilian, Lazarou Georgia, Kournopoulos Spiros, Forte Esther, Perdomo Felipe A, Jackson George, Adjiman Claire S, Galindo Amparo
Department of Chemical Engineering, Centre for Process Systems Engineering and Institute for Molecular Science and Engineering, South Kensington Campus, Imperial College London, London SW7 2AZ, UK.
Phys Chem Chem Phys. 2020 Jul 21;22(27):15248-15269. doi: 10.1039/c9cp06795g. Epub 2020 Jul 1.
The distribution of ionic species in electrolyte systems is important in many fields of science and engineering, ranging from the study of degradation mechanisms to the design of systems for electrochemical energy storage. Often, other phenomena closely related to ionic speciation, such as ion pairing, clustering and hydrogen bonding, which are difficult to investigate experimentally, are also of interest. Here, we develop an accurate molecular approach, accounting for reactions as well as association and ion pairing, to deliver a predictive framework that helps validate experiment and guides future modelling of speciation phenomena of weak electrolytes. We extend the SAFT-VRE Mie equation of state [D. K. Eriksen et al., Mol. Phys., 2016, 114, 2724-2749] to study aqueous solutions of nitric, sulphuric, and carbonic acids, considering complete and partially dissociated models. In order to incorporate the dissociation equilibria, correlations to experimental data for the relevant thermodynamic equilibrium constants of the dissociation reactions are taken from the literature and are imposed as a boundary condition in the calculations. The models for water, the hydronium ion, and carbon dioxide are treated as transferable and are taken from our previous work. We present new molecular models for nitric acid, and the nitrate, bisulfate, sulfate, and bicarbonate anions. The resulting framework is used to predict a range of phase behaviour and solution properties of the aqueous acids over wide ranges of concentration and temperature, including the degree of dissociation, as well as the activity coefficients of the ionic species, and the activity of water and osmotic coefficient, density, and vapour pressure of the solutions. The SAFT-VRE Mie models obtained in this manner provide a means of elucidating the mechanisms of association and ion pairing in the systems studied, complementing the experimental observations reported in the literature.
