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A Consistance Model for Anion Exclusion and Surface Diffusion

Published online by Cambridge University Press:  10 February 2011

J. Lehikoinent ,
A. Muurinen  and
M. Valkiainen
J. Lehikoinent
Affiliation:
VTT Chemical Technology, P.O. Box 1404, FIN-02044 VTT, Finland
A. Muurinen
Affiliation:
VTT Chemical Technology, P.O. Box 1404, FIN-02044 VTT, Finland
M. Valkiainen
Affiliation:
VTT Chemical Technology, P.O. Box 1404, FIN-02044 VTT, Finland
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Abstract

A decomposition of the diffusion flux equation for an electrostatically bound and mobile hydrated ion into two components is proposed. The first component includes the effects arising solely from the irregular pore shape and increase in solvent viscosity in the proximity of negatively charged pore walls. Apart from these effects, the second flux component includes an additional contribution from an increased (decreased) concentration for cations (anions) close to the pore walls. Defining the distribution coefficient, K d, in a fashion that allows negative values for co-ions readily accounts for their exclusion without the need to introduce somewhat artificial quantities like the “effective co-ion porosity”. In this study, it is thus possible to retain the purely volumetric meaning of the porosity and to maintain consistency throughout the conceptualization for anions, cations and electrically neutral species. Furthermore, the decomposition of the flux equation provides support for surface diffusion, a subject of great controversy and lively debate in the literature. In this connection, the role of concentration to regulate the diffusive flux for ions in relation to neutral species is emphasized. Implications for the theoretical apparent and effective diffusivities in compacted montmorillonite clay are also discussed and a modified form of the macroscopic theory is proposed.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 556: Symposium QQ – Scientific Basis for Nuclear Waste Management XXII , 1999 , 663
Copyright
Copyright © Materials Research Society 1999

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References

REFERENCES

1. Kato, H., Muroi, M., Yamada, N., Ishida, H., and Sato, H., in Scientific Basis for Nuclear Waste Management XVIII, edited by Murakami, T., and Ewing, R.C. (Mater. Res. Soc. Proc. 353, Pittsburgh, PA, 1995), pp. 277–284.Google Scholar
2. Olin, M., Lehikoinen, J., Muurinen, A., and Valkiainen, A., to be published.Google Scholar
3. Hiemenz, P.C., Principles of Colloid and Surface Chemistry, 2nd ed. (Marcel Dekker, Inc., New York, 1986), p. 815.Google Scholar
4. Lyklema, J., Rovillard, S., and Coninck, J. De, Langmuir, 14, 5659 (1998).Google Scholar
5. Lyklema, J., and Minor, M., Coll. Surf, A140, 33 (1998).Google Scholar
6. Werner, C., Körber, H., Zimmermann, R., Dukhin, S., and Jacobasch, H.-J., J. Colloid Interface Sci., 208, 329 (1998).Google Scholar
7. Haan, F.A.M. De, and Bolt, G.H., Soil Sci. Soc. Am. Proc., 27, 636 (1963).Google Scholar
8. Sposito, G., The Chemistry of Soils (Oxford University Press, New York, 1989), p. 277.Google Scholar
9. Muurinen, A., Lehikoinen, J., and Pusch, R., Report YJT-94-22, 1994.Google Scholar
10. Muurinen, A., VTT Publications 168, 1994.Google Scholar
11. Eriksen, T., and Jansson, M., Report SKB TR 96-16, 1996.Google Scholar
12. Kozaki, T., Sato, H., Fujishima, A., Sato, S., and Ohashi, H., J. Nuci. Sci. Technol., 33, 522 (1996).Google Scholar
13. Kozaki, T., Sato, H., Fujishima, A., Saito, N., Sato, S., and Ohashi, H., in Scientific Basis for Nuclear Waste Management XX, edited by Gray, W.J., and Triay, I.R. (Mater. Res. Soc. Proc. 465, Pittsburgh, PA, 1997), pp. 893–900.Google Scholar
14. Kozaki, T., Fujishima, A., Sato, S., and Ohashi, H., Nuclear Technology, 121, 63 (1998).Google Scholar
15. Kozaki, T., personal communication. Google Scholar
16. Khan, S.A., Rehman, R.-U., and Khan, M.A., Waste Management, 14, 629 (1994).Google Scholar
17. Shainberg, I., and Kemper, W.D., Soil Sci. Soc. Am. Proc., 30, 707 (1966).Google Scholar
18. Put, M.J., Radioactive Waste Management and the Nuclear Fuel Cycle, 16, 69 (1991).Google Scholar
19. Pusch, R., Karnland, O., and Hökmark, H., Report SKB TR 90-43, 1990.Google Scholar
20. Herbert, H.-J., and Moog, H.C., presented at the Workshop on Microstructural Modelling of Natural and Artificially Prepared Clay Soils with Special Emphasis on the Use of Clays for Waste Isolation, Lund, Sweden, 1998 (to be published).Google Scholar