Imperial College London
Alternate

Prof Amparo Galindo

Faculty of Engineering, Department of Chemical Engineering

Co-Director Institute for Molecular Science and Engineering
 
 
 
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Contact

 

+44 (0)20 7594 5606a.galindo

 
 
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Location

 

604Roderic Hill BuildingSouth Kensington Campus

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Summary

 

Publications

Citation

BibTex format

@article{Kohns:2020:10.1039/C9CP06795G,
author = {Kohns, M and Lazarou, G and Forte, E and Perdomo, Hurtado F and Kournopoulos, S and Jackson, G and Adjiman, C and Galindo, A},
doi = {10.1039/C9CP06795G},
journal = {Physical Chemistry Chemical Physics},
pages = {15248--15269},
title = {Predictive models for the phase behaviour and solution properties of weak electrolytes: nitric, sulfuric and carbonic acid},
url = {http://dx.doi.org/10.1039/C9CP06795G},
volume = {22},
year = {2020}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - 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 the 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 acid, 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. Here 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.
AU  - Kohns,M
AU  - Lazarou,G
AU  - Forte,E
AU  - Perdomo,Hurtado F
AU  - Kournopoulos,S
AU  - Jackson,G
AU  - Adjiman,C
AU  - Galindo,A
DO  - 10.1039/C9CP06795G
EP  - 15269
PY  - 2020///
SN  - 1463-9076
SP  - 15248
TI  - Predictive models for the phase behaviour and solution properties of weak electrolytes: nitric, sulfuric and carbonic acid
T2  - Physical Chemistry Chemical Physics
UR  - http://dx.doi.org/10.1039/C9CP06795G
UR  - http://hdl.handle.net/10044/1/77577
VL  - 22
ER  -
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