Ionic diffusion in naturally-occurring aqueous solutions: transition-state models that use either empirical expressions or statistically-derived relationships to predict mutual diffusion coefficients in the concentrated-solution regions of 8 binary systems

Details Ionic diffusion in naturally-occurring aqueous solutions: transition-state models that use either empirical expressions or statistically-derived relationships to predict mutual diffusion coefficients in the concentrated-solution regions of 8 binary systems Ionic diffusion in naturally-occurring aqueous solutions: transition-state models that use either empirical expressions or statistically-derived relationships to predict mutual diffusion coefficients in the concentrated-solution regions of 8 binary systems

Nov 1983

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1983gecoa..47.1985g&link_type=abstract

Geochimica et Cosmochimica Acta, vol. 47, Issue 11, pp.1985-1998

Mathematics

Probability

Scientific paper

Mutual diffusion coefficients for the systems NaCl-H 2 O, KCl-H 2 O, CaCl 2 -H 2 O, SrCl 2 -H 2 O, BaCl 2 -H 2 O, MgCl 2 -H 2 O, Na 2 SO 4 -H 2 O, and MgSO 4 -H 2 O are computed using a model that postulates exchanges between ions and water molecules. Limiting ionic equivalent conductances, a solution-density function, and a mean ionic activity-coefficient function are required as input. A region of changing solution structure extends up to concentrations ranging from about 0.01 molar in MgCl 2 -H 2 O to about 0.2 molar in KCl-H 2 O. In the remaining concentration range to saturation, a single expression in each system containing one variable parameter can be fitted empirically to reproduce selected sets of experimentally measured D v 12 with maximum errors for individual compositions ranging from about 0.25% in KCl-H 2 O and Na 2 SO 4 -H 2 O to about 4% in MgCl 2 -H 2 O. The experimentally measured D v 12 can be reproduced with errors comparable to those of the empirical fits by further postulating that individual ion-water molecule exchanges are coupled to yield hydrated neutral exchange complexes (the activated complexes), and defining probability expressions that describe the following exchanges: Ba 2+ + 2 Cl - for 3H 2 O, 2 Ca 2+ + 4 Cl - for 6H 2 O, 2 Sr 2+ + 4 Cl - for 6H 2 O, Na + + Cl - for 3H 2 O, 2 K + + 2 Cl - for 5H 2 O, NaSO - 4 + Na + for 5H 2 O, Mg 2+ + SO 2- 4 (+MgSO 0 4 ) for 4H 2 O, and MgCl + + Cl - for 2H 2 O. This calculation also contains one variable parameter. Solute transport between exchange sites is by movement of ions, except for the ion-pair contribution indicated in parentheses.

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