An isotherm-based thermodynamic model of multicomponent aqueous solutions, applicable over the entire concentration range

Cari S. Dutcher, Xinlei Ge, Anthony S. Wexler, Simon L. Clegg

Research output: Contribution to journalArticle

23 Citations (Scopus)

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).

Original languageEnglish (US)
Pages (from-to)3198-3213
Number of pages16
JournalJournal of Physical Chemistry A
Volume117
Issue number15
DOIs
StatePublished - Apr 18 2013

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Activity coefficients
Isotherms
solutes
isotherms
Thermodynamics
Gibbs free energy
aqueous solutions
thermodynamics
Dilution
Liquids
Water
Coulomb interactions
Adsorption isotherms
Extrapolation
Hydration
Electrolytes
Sorption
coefficients
dilution
liquids

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

An isotherm-based thermodynamic model of multicomponent aqueous solutions, applicable over the entire concentration range. / Dutcher, Cari S.; Ge, Xinlei; Wexler, Anthony S.; Clegg, Simon L.

In: Journal of Physical Chemistry A, Vol. 117, No. 15, 18.04.2013, p. 3198-3213.

Research output: Contribution to journalArticle

Dutcher, Cari S. ; Ge, Xinlei ; Wexler, Anthony S. ; Clegg, Simon L. / An isotherm-based thermodynamic model of multicomponent aqueous solutions, applicable over the entire concentration range. In: Journal of Physical Chemistry A. 2013 ; Vol. 117, No. 15. pp. 3198-3213.
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