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Hydration Effects on the Stability of Calcium Carbonate Pre-Nucleation Species

Mineralogy and Petrology Department, University of Granada, 18071 Granada, Spain
Institut für Mineralogie, University of Münster, 48149 Münster, Germany
Department of Chemistry, Curtin University, Perth 6845, Australia
Author to whom correspondence should be addressed.
Minerals 2017, 7(7), 126;
Received: 1 June 2017 / Revised: 1 July 2017 / Accepted: 14 July 2017 / Published: 20 July 2017
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Recent experimental evidence and computer modeling have shown that the crystallization of a range of minerals does not necessarily follow classical models and theories. In several systems, liquid precursors, stable pre-nucleation clusters and amorphous phases precede the nucleation and growth of stable mineral phases. However, little is known on the effect of background ionic species on the formation and stability of pre-nucleation species formed in aqueous solutions. Here, we present a systematic study on the effect of a range of background ions on the crystallization of solid phases in the CaCO3-H2O system, which has been thoroughly studied due to its technical and mineralogical importance, and is known to undergo non-classical crystallization pathways. The induction time for the onset of calcium carbonate nucleation and effective critical supersaturation are systematically higher in the presence of background ions with decreasing ionic radii. We propose that the stabilization of water molecules in the pre-nucleation clusters by background ions can explain these results. The stabilization of solvation water hinders cluster dehydration, which is an essential step for precipitation. This hypothesis is corroborated by the observed correlation between parameters such as the macroscopic equilibrium constant for the formation of calcium/carbonate ion associates, the induction time, and the ionic radius of the background ions in the solution. Overall, these results provide new evidence supporting the hypothesis that pre-nucleation cluster dehydration is the rate-controlling step for calcium carbonate precipitation. View Full-Text
Keywords: background electrolytes; dehydration kinetics; calcium carbonate; calcite; clusters; nucleation; vaterite; ACC background electrolytes; dehydration kinetics; calcium carbonate; calcite; clusters; nucleation; vaterite; ACC

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Burgos-Cara, A.; Putnis, C.V.; Rodriguez-Navarro, C.; Ruiz-Agudo, E. Hydration Effects on the Stability of Calcium Carbonate Pre-Nucleation Species. Minerals 2017, 7, 126.

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