Thermodynamic and kinetic effect of organic solvent on the nucleation of nesquehonite

Nesquehonite crystallization experiments were conducted in H2O and water/dimethylformamide (DMF) mixture to examine solvent effect on the nucleation kinetics. Results show a reduction of nucleation induction time in the presence of DMF and a positive correlation between nucleation rate and DMF concentration. Analysis in the context of the classical nucleation theory reveals an unexpected increase in the surface energy of nesquehonite upon the solvent change, implying that kinetic factors, rather than surface energetics, is the driving force behind the resultant enhancement in nucleation rate. Further analyses suggest that kinetic acceleration under higher surface energy conditions is possible if nucleation proceeds through a cluster aggregation mechanism instead of critical nucleus formation. Fitting the Smoluchowski’s coagulation theory to the experimental data seems to provide support to the operation of the non-classical nucleation mechanism as it shows that the cluster association rate is independent of the sizes of the precursors but positively correlated to the DMF concentration, consistent with the scenario of growing population of sub-critical nuclei and ensuing higher probability of cluster collision/aggregation leading to an accelerated nucleation.