Crystallization of Keggin Heteropolyanions via a Two-Step Process in Aqueous Solutions
Although the analytical simplicity of the one-step classical theory of nucleation facilitates its use to understand crystallization processes, recent experiments and simulations have shown that many occur via multiple steps. According to the contemporary two-stage theory of nucleation, the onset of...
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Published in | Journal of the American Chemical Society Vol. 138; no. 23; pp. 7282 - 7288 |
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Main Authors | , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
15.06.2016
American Chemical Society (ACS) |
Subjects | |
Online Access | Get full text |
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Summary: | Although the analytical simplicity of the one-step classical theory of nucleation facilitates its use to understand crystallization processes, recent experiments and simulations have shown that many occur via multiple steps. According to the contemporary two-stage theory of nucleation, the onset of crystallization in a solution is preceded by large density fluctuations in the mother liquor that results in the formation of dense liquid-like correlated structures of the constituent solute particles. Here we report the observation of dense liquid-like correlated structures of heteropolyacid salts of α-Keggin anions (heteropolyanions) in aqueous solutions as volume is decreased long before the onset of crystallization by in situ time-dependent small-angle X-ray scattering measurements. Experiments were performed on drying drops of solutions of heteropolyacids to monitor their ordering before and during the onset of their crystallization. A continuous change in the density of the correlated structures is observed up to the onset of crystallization. Moreover, the correlated structures and the onset of crystallization are found to depend upon the charge of the heteropolyanions. The crystals formed within the drying drops of solutions during the crystallization process are found to be metastable polymorphic structures that are different from the stable crystal structures obtained after complete drying of the drops. Our results support a two-step process and Ostwald’s rule of stages for the crystallization of heteropolyanions in their aqueous solutions upon evaporation. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 AC02-06CH11357 USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division |
ISSN: | 0002-7863 1520-5126 |
DOI: | 10.1021/jacs.5b13375 |