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ToolsDutcher, C.S., Ge, X., Wexler, A.S. and Clegg, S.L. (2013) An isotherm-based thermodynamic model of multicomponent aqueous solutions, applicable over the entire concentration range. The Journal of Physical Chemistry A, 117 (15). pp. 3198-3213. ISSN 1089-5639
Full text not available from this repository. (Request a copy)Abstract
In previous studies (Dutcher et al. J. Phys. Chem. C 2011, 115, 16474-16487; 2012, 116, 1850-1864), we derived equations for the Gibbs energy, solvent and solute activities, and solute concentrations in multicomponent liquid mixtures, based upon expressions for adsorption isotherms that include arbitrary numbers of hydration layers on each solute. In this work, the long-range electrostatic interactions that dominate in dilute solutions are added to the Gibbs energy expression, thus extending the range of concentrations for which the model can be used from pure liquid solute(s) to infinite dilution in the solvent, water. An equation for the conversion of the reference state for solute activity coefficients to infinite dilution in water has been derived. A number of simplifications are identified, notably the equivalence of the sorption site parameters r and the stoichiometric coefficients of the solutes, resulting in a reduction in the number of model parameters. Solute concentrations in mixtures conform to a modified Zdanovskii-Stokes-Robinson mixing rule, and solute activity coefficients to a modified McKay-Perring relation, when the effects of the long-range (Debye-Hückel) term in the equations are taken into account. Practical applications of the equations to osmotic and activity coefficients of pure aqueous electrolyte solutions and mixtures show both satisfactory accuracy from low to high concentrations, together with a thermodynamically reasonable extrapolation (beyond the range of measurements) to extreme concentration and to the pure liquid solute(s).
| Item Type: | Article |
|---|---|
| Faculty \ School: | Faculty of Arts and Humanities > School of Language and Communication Studies (former - to 2014) Faculty of Science > School of Environmental Sciences |
| UEA Research Groups: | Faculty of Science > Research Groups > Marine and Atmospheric Sciences (former - to 2017) Faculty of Science > Research Groups > Climate, Ocean and Atmospheric Sciences (former - to 2017) Faculty of Science > Research Groups > Centre for Ocean and Atmospheric Sciences |
| Related URLs: | |
| Depositing User: | Pure Connector |
| Date Deposited: | 23 Oct 2013 20:32 |
| Last Modified: | 24 Oct 2022 04:48 |
| URI: | https://ueaeprints.uea.ac.uk/id/eprint/43738 |
| DOI: | 10.1021/jp310860p |
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