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Origins of Discrepancies Between Kinetic Rate Law Theory and Experiments in the Na2O-B2O3-SiO2 System

  • B. P. McGrail (a1), J. P. Icenhower (a1) and E. A. Rodriguez (a1)


Discrepancies between classical kinetic rate law theory and experiment were quantitatively assessed and found to correlate with macromolecular amorphous separation in the sodium borosilicate glass system. A quantitative reinterpretation of static corrosion data and new SPFT data shows that a recently advanced protective surface layer theory fails to describe the observed dissolution behavior of simple and complex silicate glasses under carefully controlled experimental conditions. The hypothesis is shown to be self-inconsistent in contrast with a phase separation model that is in quantitative agreement with experiments.



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1. Aagaard, P. and Helgeson, H.C., Am. J. Sci. 282, 237285 (1982).
2. Grambow, B.E., Mat. Res. Soc. Symp. Proc. 44, 1527 (1985).
3. Lasaga, A.C., in Chemical Weathering Rates of Silicate Minerals, Reviews in Mineralogy, 31, edited by White, A.F. and Brantley, S.L., (Mineralogical Society of America, Washington D. C., 1995), pp. 2386.
4. Strachan, D.M., Bourcier, W.L., and McGrail, B.P., Radioactive Waste Management and Environmental Restoration 19, 129145 (1994).
5. McGrail, B.P., Bacon, D.H., Icenhower, J.P., Mann, F.M., Puigh, R.J., Schaef, H.T., and Mattigod, S.V., J. Nuc. Mat. 298 (1–2), 95111 (2001).
6. Jégou, C., Gin, S., and Larché, F., J. Nuc. Mat. 280, 216229 (2000).
7. McGrail, B.P., Ebert, W.L., Bakel, A.J., and Peeler, D.K., J. Nuc. Mat. 249, 175189 (1997).
8. Wolery, T.J., EQ3NR, A Computer Program for Geochemical Aqueous Speciation-Solubility Calculations: Theoretical Manual, User's Guide, and Related Documentation (Version 7.0), UCRL-MA-110662 PT III, Lawrence Livermore National Laboratory, Livermore, California (1992).
9. McGrail, B.P., Icenhower, J.P., Bacon, D.H., Schaef, H.T., Martin, P.F., Rodriguez, E.A., and Steele, J.L., Low-Activity Waste Glass Studies: FY2001 Summary Report, PNNL-13761, Pacific Northwest National Laboratory, Richland, Washington (2001).
10. Vernaz, E., Gin, S., Jégou, C., and Ribet, I., J. Nuc. Mat. 298 (1–2), 2736 (2001).
11. Crank, J., in The Mathematics of Diffusion, (Clarendon Press, Oxford, United Kingdom, 1975), p. 414.
12. Haller, W., Blackburn, D.H., Wagstaff, F.E., and Charles, R.J., J. Am. Ceram. Soc. 53, 3438 (1970).
13. Polyakova, I.G., Glass Phys. Chem. 23 (1), 4557 (1997).
14. Jantzen, C.M. and Brown, K.G., in Environmental Issues and Waste Management Technologies in the Ceramic and Nuclear Industries, Ceramic Transactions 107, edited by Chandler, G.T., (American Ceramic Society, Westerville, Ohio, 2000), pp. 289300.
15. Tomozawa, M., J. Am. Ceram. Soc. 82 (11), 206208 (1999).
16. Dell, W.J., Bray, P.J., and Xiao, S.Z., J. Non-Cryst. Solids 58 (1), 116 (1983).
17. Yazawa, T., Kuraoka, K., Akai, T., Umesaki, N., and Du, W.-F., J. Phys. Chem. B 104 (9), 21092116 (2000).
18. Ramsey, W.G., Jantzen, C.M., and Taylor, T.D., in Environmental and Waste Management Issues in the Ceramic Industry, Ceramic Transactions 39, (American Ceramic Society, Westerville, Ohio, 1994), pp. 325332.
19. Aertsens, M., Ceram.-Silik. 43 (4), 175180 (1999).
20. McGrail, B.P., Icenhower, J.P., Shuh, D.K., Liu, P., Darab, J.G., Baer, D.R., Thevuthasen, S., Shutthanandana, V., Engelhard, M.H., Booth, C.H., and Nachimuthu, P., J. Non-Cryst. Solids 296 (1–2), 1026 (2001).
21. McGrail, B.P., Icenhower, J.P., Darab, J.G., Shuh, D.K., Baer, D.R., Shutthanandan, V., Thevusathan, S., Engelhard, M.H., Steele, J.L., Rodriguez, E.A., Liu, P., Ivanov, K.E., Booth, C.H., and Nachimuthu, P., Ion-Exchange Processes and Mechanisms in Glasses, PNNL-13717, Pacific Northwest National Laboratory, Richland, Washington (2001).

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Origins of Discrepancies Between Kinetic Rate Law Theory and Experiments in the Na2O-B2O3-SiO2 System

  • B. P. McGrail (a1), J. P. Icenhower (a1) and E. A. Rodriguez (a1)


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