Reconciliation of Kinetic Data for Organic Crystal Growth in Supercritical-CO2: Exploiting a Molecular Collision Theory Viewpoint, with Implications for Precipitator Process Design

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• 作者：Daniel E. Rosner
• 刊名：Crystal Growth & Design
• 出版年：2014
• 出版时间：August 6, 2014
• 年：2014
• 卷：14
• 期：8
• 页码：3783-3790
• 全文大小：312K
• ISSN：1528-7505

文摘

Exploiting a molecular 鈥渃ollision-theory鈥?viewpoint, we reformulate and correct for systematic effects of fluid-phase solute diffusion, reported growth-rate data for {001} naphthalene single crystal surfaces under supercritical CO₂-conditions at low supersaturations, S. By considering dimensionless incorporation probabilities, 蔚(S, T, ...;{hkl}) for this prototypical organic crystal, we initiate the process of quantifying the environment-dependence of 蔚 as a rational route to crystal growth rate predictions at molecular volume fractions, , ranging all the way from ideal vapors ( 1) to liquid-like densities ( 0.64). Our rational 鈥渁nsatz鈥?for predicting growth species collision fluxes enables a two-stage data-reduction process. First we infer 鈥渁pparent鈥?incorporation probabilities, 蔚_app, ignoring fluid-phase solute diffusion effects. Second, we recover their intrinsic counterparts, using 蔚_app and invoking rational transport estimates for the prevailing crystal size/flow conditions. Treating available data near 318 K at 77鈥?1 bar (Tai, C. Y.; Cheng, C.-S. AIChE J. 1995, 41, 2227鈭?236) and 150鈥?00 bar (Uchida et al. Cryst. Growth Des. 2004, 4, 937鈭?42), we conclude that 蔚 decreases significantly with (CO₂-) pressure鈥攚ith important mechanistic and anti-solvent precipitation (ASP) process modeling implications.