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A thermodynamically consistent kinetic framework for binary nucleation

Flagan, Richard C. (2007) A thermodynamically consistent kinetic framework for binary nucleation. Journal of Chemical Physics, 127 (21). Art. No. 214503. ISSN 0021-9606. doi:10.1063/1.2800001.

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The traditional theory for binary homogeneous nucleation follows the classical derivation of the nucleation rate in the supposition of a hypothetical constrained-equilibrium distribution in the calculation of the cluster evaporation rate. This model enables calculation of the nucleation rate, but requires evaluation of the cluster distribution and cluster properties for an unstable equilibrium with supersaturated vapor. An alternate derivation of the classical homomolecular nucleation rate eliminated the need for this nonphysical approximation by calculating the evaporative flux at full thermodynamic equilibrium. The present paper develops that approach for binary nucleation; the framework is readily extended to ternary nucleation. In this analysis, the evaporative flux is evaluated by applying mass balance at full thermodynamic equilibrium of the system under study. This approach eliminates both the need for evaluating cluster properties in an unstable constrained-equilibrium state and ambiguity in the normalization constant required in the nucleation-rate expression. Moreover, it naturally spans the entire composition range between the two pure monomers. The cluster fluxes derived using this new model are similar in form to those of classical derivations, so previously developed methods for evaluation of the net nucleation rate can be applied directly to the new formulation.

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Flagan, Richard C.0000-0001-5690-770X
Additional Information:© 2007 American Institute of Physics. Received: 30 July 2007; accepted: 26 September 2007; published: 5 December 2007. The author gratefully acknowledges insightful discussions with Professor John Seinfeld, Professor Zhen-Gang Wang, and Professor George Gavalas of the California Institute of Technology, and Professor Joseph Katz of the Johns Hopkins University. This work was supported in part by the National Science Foundation Grant No. ATM-0340832.
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Subject Keywords:molecular clusters, nucleation
Issue or Number:21
Record Number:CaltechAUTHORS:FLAjcp07
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:9275
Deposited By: Archive Administrator
Deposited On:05 Dec 2007
Last Modified:08 Nov 2021 20:57

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