Secondary Nucleation by Interparticle Energies. III. Nucleation Rate Model

Abstract

A nucleation rate model for describing the kinetics of secondary nucleation caused by interparticle energies (SNIPEs) is derived theoretically, verified numerically, and validated experimentally. The theoretical derivation reveals that the SNIPE mechanism can be viewed as enhanced primary nucleation, i.e., primary nucleation with a lower thermodynamic energy barrier (for nucleation) and a smaller critical nucleus size, both caused by the interparticle interactions and the associated energy between the surface of a seed crystal and a molecular cluster in solution, as shown in part I of this series. In the case of a sufficiently agitated suspension, the model depends on four parameters: two reflecting primary nucleation kinetics and the other two accounting for the intensity and effective spatial range of the interparticle interactions. As a numerical verification of the model, we show that the nucleation kinetics described by the SNIPE rate model is in quantitative agreement with those given by the kinetic rate equation model developed in part II of this series. A sensitivity analysis of the SNIPE rate model is conducted to present the effect of key model parameters on the nucleation kinetics. Moreover, the SNIPE rate model is validated by fitting the model to the time-resolved data of secondary nucleation experiments as well as to two other, well-known secondary nucleation rate models. Importantly, all of the estimated parameter values for the SNIPE model were consistent with the theoretical estimates, while some of the estimated parameter values for one of the well-known secondary nucleation models deviated from the corresponding theoretical values significantly.