Dissolution of crystallites: surface energetic control and size effects.
Traditional understanding of dissolution assumes that the reaction is spontaneous and continues until equilibrium is reached. This paper presents theoretical and experimental data to support a dissolution mechanism that involves the existence of critical conditions for dissolution, in which the reaction is accompanied by the formation of pits and the subsequent displacement of pit steps. The accompanying increase in surface roughness leads to changes in surface energy with losses of crystal mass that are positive rather than negative and the existence of critical dissolution conditions. Critical pits and dissolution steps are verified experimentally and a relationship between the size and rate of displacement of steps is also demonstrated, in which the rate decreases with size and approaches zero at a critical size, r*. These microscopic step dynamics are consistent with the observed size-effects in bulk dissolution, which cannot be explained using traditional dissolution theories. The observed size effects include self-inhibition, in which the dissolution rate decreases with extent of reaction, dissolution suppression, and periodic resumption. These interesting dissolution phenomena are only readily displayed when the sizes of dissolving crystallites fall in the same range as the critical size (i.e., within 50r*). It is interesting to note that natural biominerals and many nanoparticles fall into this category, so that their suspensions can be dynamically stabilized without dissolution in undersaturated supporting media. The current research implies that dissolution kinetics cannot be understood well without appealing to fundamental physical concepts about the energetic control of dissolution steps on a molecular level. A new dissolution model for crystallites is introduced systemically.
Tang
Ruikang
R
Department of Chemistry, Natural Sciences Complex, University at Buffalo, State University of New York, Buffalo, New York 14260, USA.
Orme
Christine A
CA
Nancollas
George H
GH
D002627:Chemistry, Physical / Q000379:methods*; D003460:Crystallization; D004058:Diffusion; D007700:Kinetics; D018625:Microscopy, Atomic Force; D008855:Microscopy, Electron, Scanning; D008956:Models, Chemical; D010316:Particle Size; D012995:Solubility; D013816:Thermodynamics; D013997:Time Factors