Ionic diffusion in naturally-occurring aqueous solutions: use of activity coefficients in transition-state models

Details Ionic diffusion in naturally-occurring aqueous solutions: use of activity coefficients in transition-state models Ionic diffusion in naturally-occurring aqueous solutions: use of activity coefficients in transition-state models

Mar 1978

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1978gecoa..42..251a&link_type=abstract

Geochimica et Cosmochimica Acta, vol. 42, Issue 3, pp.251-262

Physics

Scientific paper

The model of and ( Can. J. Chem . 43 , 1812-1828, 1965; 44 , 477-485, 1966) for estimating diffusion coefficients in aqueous electrolyte solutions from limiting ionic conductances is rederived for a system of n salts with a common anion, by utilizing the equations of ( J. Chem. Phys . 71, 616-632, 1967b; 71 , 3588-3592, 1967c). Salt and water activities are used, and it is of necessity assumed that the diffusion mechanism does not change with concentration. The revised model predicts the on-diagonal D v ik of a 3 M solution in NaCl-KCl-H 2 O to within 5%, compared with errors of 20-30% for the original model. Errors remain constant or decrease as concentrations increase to 3 M, so that predictions of these D v ik at even higher concentrations appear promising. Relatively large errors persist in our estimates of the small, off-diagonal coefficients in this system. Measured diffusion coefficients in MgCl 2 -NaCl-H 2 O extend over only a limited concentration range and are of only moderate accuracy. Nevertheless, the revised model predicts D v 11 D v 22 , and D v 21 , the larger of the off-diagonal coefficients, with errors of only 5-20%.

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