Solute-rich clusters as nucleation medium of small organic molecules: a
case of p-nitrobenzoic acid
Abstract
Solute-rich clusters, which generally exist stably in solution, are
necessary intermediates for the formation of crystal nuclei. Studying
the properties of these pre-nucleation species is very important for
understanding and controlling the nucleation process of crystals. In
this work, clusters as nucleation medium were studied using
p-nitrobenzoic acid (PNBA) in acetonitrile as model system, and the
observed PNBA clusters were characterized and analyzed by using DLS, NTA
and 1H NMR. It was found that the clusters were thermodynamically stable
and were spatially heterogeneous mixtures of PNBA monomers, PNBA
homodimers and acetonitrile molecules. The existence of dimers is an
important factor for the formation and stable existence of clusters.
Clusters can be formed under the combined effect of monomer-dimer
reaction and diffusion. The spatial distributions of monomer and dimer
density at different concentrations were obtained by reaction-diffusion
kinetics, and the different effects of filtration on clusters were
theoretically explained.