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Predictive models for the phase behaviour and solution properties of weak electrolytes: nitric, sulphuric, and carbonic acids.
Phys Chem Chem Phys. 2020 Jul 21; 22(27):15248-15269.PC

Abstract

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.

Authors+Show Affiliations

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. a.galindo@imperial.ac.uk.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

32609107

Citation

Kohns, Maximilian, et al. "Predictive Models for the Phase Behaviour and Solution Properties of Weak Electrolytes: Nitric, Sulphuric, and Carbonic Acids." Physical Chemistry Chemical Physics : PCCP, vol. 22, no. 27, 2020, pp. 15248-15269.
Kohns M, Lazarou G, Kournopoulos S, et al. Predictive models for the phase behaviour and solution properties of weak electrolytes: nitric, sulphuric, and carbonic acids. Phys Chem Chem Phys. 2020;22(27):15248-15269.
Kohns, M., Lazarou, G., Kournopoulos, S., Forte, E., Perdomo, F. A., Jackson, G., Adjiman, C. S., & Galindo, A. (2020). Predictive models for the phase behaviour and solution properties of weak electrolytes: nitric, sulphuric, and carbonic acids. Physical Chemistry Chemical Physics : PCCP, 22(27), 15248-15269. https://doi.org/10.1039/c9cp06795g
Kohns M, et al. Predictive Models for the Phase Behaviour and Solution Properties of Weak Electrolytes: Nitric, Sulphuric, and Carbonic Acids. Phys Chem Chem Phys. 2020 Jul 21;22(27):15248-15269. PubMed PMID: 32609107.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Predictive models for the phase behaviour and solution properties of weak electrolytes: nitric, sulphuric, and carbonic acids. AU - Kohns,Maximilian, AU - Lazarou,Georgia, AU - Kournopoulos,Spiros, AU - Forte,Esther, AU - Perdomo,Felipe A, AU - Jackson,George, AU - Adjiman,Claire S, AU - Galindo,Amparo, Y1 - 2020/07/01/ PY - 2020/7/2/pubmed PY - 2020/7/2/medline PY - 2020/7/2/entrez SP - 15248 EP - 15269 JF - Physical chemistry chemical physics : PCCP JO - Phys Chem Chem Phys VL - 22 IS - 27 N2 - 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. SN - 1463-9084 UR - https://www.unboundmedicine.com/medline/citation/32609107/Predictive_models_for_the_phase_behaviour_and_solution_properties_of_weak_electrolytes:_nitric,_sulphuric,_and_carbonic_acids L2 - https://doi.org/10.1039/c9cp06795g DB - PRIME DP - Unbound Medicine ER -
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