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Dissociation constants and speciation in aqueous Li2SO4 and K2SO4 from measurements of electrical conductance to 673 K and 29 MPa
Authors:Andrei V Sharygin  Robert H Wood  Victor N Balashov
Institution:a General Electric Company, GE Plastics, Specialty Film and Sheet, 1 Lexan Lane, Mount Vernon, IN 47620, USA
b Exxon Mobil, Research and Engineering Company, Fairfax, VA, USA
c GE Water and Process Technologies 4636 Somerton Road, Trevose, PA 19053, USA
d The Energy Institute, Pennsylvania State University, University Park, PA 16802, USA
e Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA
Abstract:The electrical conductivities of aqueous solutions of Li2SO4 and K2SO4 have been measured at 523-673 K at 20-29 MPa in dilute solutions for molalities up to 2 × 10−2 mol kg−1. These conductivities have been fitted to the conductance equation of Turq, Blum, Bernard, and Kunz with a consensus mixing rule and mean spherical approximation activity coefficients. In the temperature interval 523-653 K, where the dielectric constant, ε, is greater than 14, the electrical conductance data can be fitted by a solution model which includes ion association to form View the MathML source, View the MathML source, and View the MathML source, where M is Li or K. The adjustable parameters of this model are the first and second dissociation constants of the M2SO4. For the 673 K and 300 kg m−3 state point where the Coulomb interactions are the strongest (dielectric constant, ε = 5), models with more extensive association give good fits to the data. In the case of the Li2SO4 model, including the multi-ion associate, View the MathML source, gave an extremely good fit to the conductance data.
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