A thermodynamically consistent kinetic framework for binary nucleation.
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.
Flagan
Richard C
RC
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA. flagan@caltech.edu