Comment: Supersaturation in binary solid solution-Aqueous solution systems: (Comment on "Crystallization kinetics in binary solid solution aqueous solution systems" by Alexander G. Shtukenberg, Yurii O. Punin and Pavel Azimov, American Journal of Science, v. 306, p. 553 574.)

Clicks: 4
ID: 304936
2007
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Abstract
Shtukenberg and others (2006) present a general model for predicting growth rates in solid solution -aqueous solution (SS-AS) systems.The key parameter for such a model is the supersaturation, which is particularly stressed and discussed throughout the text.The paper starts with a review of the equilibrium thermodynamics in SS-AS systems on the basis of the Lippmann "total solubility product" (Lippmann, 1980; Glynn and Reardon, 1990; Glynn and others, 1990;Glynn, 2000).Then, the authors discuss the so-called "quasi-equilibria", defined as those states where "the driving force for the ionic fluxes of one or both components between aqueous solution and solid solution can be negligible".Finally, the approach is completed by considering the misfit strain arising at the interface between the crystal surface and a newly deposited solid-solution layer of different composition.According to Shtukenberg and coworkers, this strain is expected to have a strong effect on the physical-chemistry of crystal growth, and their model promises to predict the growth and dissolution behavior of solid-solution crystals from aqueous solutions.Whereas the proposed model contains interesting ideas and most of the derived equations are formally correct, some conclusions and, particularly, the underlying terminology are misleading and may result in a wrong interpretation of SS-AS physical-chemistry.There are two main parts to this discussion.The first disputes the concept of "quasi-equilibrium" as defined by Shtukenberg and others (2006) and the second revises the expressions of supersaturation applied to these kinds of systems.In addition, we introduce some remarks on other aspects of the model that are directly or indirectly affected by the concept of quasi-equilibrium and supersaturation of Shtukenberg and co-workers.The physical-chemistry of SS-AS systems is a complex issue that has generated a number of controversies during the last three decades (Thorstenson and Plummer, 1977; Lafont, 1978;Garrels and Wollast, 1978; Thorstenson and Plummer, 1978; Stoessell, 1992; Glynn and others, 1992;Ko ¨nigsberger and Gamsja ¨ger, 1992; Glynn and Reardon, 1992).At present (Glynn, 2000), most of those controversies can be considered as ended, but many kinetic aspects remain unsolved and it is therefore not unusual that new controversies arise.In our opinion, one of the key factors to progress in the understanding of the growth/dissolution behavior in SS-AS systems is to avoid the use of misleading concepts.This is the approach that we mean to give to the present criticism.
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Authors Manuel Prieto Rubio, José Manuel Astilleros, Carlos M. Pina, Lurdes Fernández-Dı́az, Andrew Putnis
Journal american journal of science
Year 2007
DOI
10.2475/07.2007.04
URL
https://ajs.scholasticahq.com/article/61648.pdf
Keywords Keywords not found

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