TY - JOUR
T1 - Probability of Nucleation in a Metastable Zone
T2 - Induction Supersaturation and Implications
AU - Bhamidi, Venkateswarlu
AU - Kenis, Paul J.A.
AU - Zukoski, Charles F.
N1 - Funding Information:
We acknowledge Prof. R. D. Braatz (Massachusetts Institute of Technology), Prof. Baron Peters (University of California, Santa Barbara), Dr. Ryan Larsen (University of Illinois at Urbana-Champaign) Dr. Sameer Talreja (BP, Naperville, USA), and Dr. Guangwen He (Procter & Gamble, Singapore) for stimulating discussions. V.B. thanks Dr. Meenesh Singh (University of Illinois at Chicago) and Dr. Debangshu Guha (Eastman Chemical Company) for inspiring conversations. High quality graphics from Microsoft Excel plots were generated using Daniel's XL Toolbox add-in for Excel (v 6.6), a free utility created by Daniel Kraus, Wurzburg, Germany. We gratefully acknowledge financial support from University of Illinois and Institute of Chemical and Engineering Sciences (ICES), Singapore.
Publisher Copyright:
© 2017 American Chemical Society.
Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 2017/3/1
Y1 - 2017/3/1
N2 - The metastable zone in solution crystallization is typically defined as a region of the phase diagram in which no appreciable nucleation occurs. Existing theoretical explanations attribute the appearance of this zone to the low probability of nucleation brought forth by the path-dependency of the nucleation rate. In this work, for the first time we present experimental data for several compounds that contradict this description. We show that the widely adopted theoretical approach which considers a time-dependent nucleation rate does not capture the observed stochastic nature of nucleation in these experiments. Instead, the experimental results are successfully explained through a probability analysis based solely on the energy barrier to nucleation. In this context, for a system that is slowly supersaturated, we develop the idea of an "induction supersaturation" as a lower boundary of metastability that does not depend on the path of the experiment. This work critically examines the limitations of the existing stochastic methods that describe nucleation under variable supersaturation and calls for a fundamental shift in the traditional view of the processes responsible for the manifestation of the metastable zone.
AB - The metastable zone in solution crystallization is typically defined as a region of the phase diagram in which no appreciable nucleation occurs. Existing theoretical explanations attribute the appearance of this zone to the low probability of nucleation brought forth by the path-dependency of the nucleation rate. In this work, for the first time we present experimental data for several compounds that contradict this description. We show that the widely adopted theoretical approach which considers a time-dependent nucleation rate does not capture the observed stochastic nature of nucleation in these experiments. Instead, the experimental results are successfully explained through a probability analysis based solely on the energy barrier to nucleation. In this context, for a system that is slowly supersaturated, we develop the idea of an "induction supersaturation" as a lower boundary of metastability that does not depend on the path of the experiment. This work critically examines the limitations of the existing stochastic methods that describe nucleation under variable supersaturation and calls for a fundamental shift in the traditional view of the processes responsible for the manifestation of the metastable zone.
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U2 - 10.1021/acs.cgd.6b01529
DO - 10.1021/acs.cgd.6b01529
M3 - Article
AN - SCOPUS:85014183727
SN - 1528-7483
VL - 17
SP - 1132
EP - 1145
JO - Crystal Growth and Design
JF - Crystal Growth and Design
IS - 3
ER -