Initial stages of gypsum nucleation: The role of “nano/microdust”

Abstract

The primary nucleation mechanism of the gypsum in a bulk aqueous medium was identified as a heterogeneous one for 0.05 and 0.03 mol·L−1 CaSO4·2H2 O solutions and 25◦ C. By means of a particle counter and dynamic light scattering (DLS) technique, solid nano/microimpurities were found, and controlled in stock brines for gypsum supersaturated solutions preparation. It is demonstrated that the common procedure of reagent grade 0.10 mol·L−1 CaCl2 and Na2 SO4 aqueous solutions filtration via 200 nm membranes is capable to reduce the foreign solid microimpurities content (size > 100 nm) from 106 to 103 units in 1 mL, but fails to affect the more numerous nanofraction (size < 100 nm). Thus, the gypsum nucleation takes place in presence of a significant amount of “nano/microcodust” templates, and has a heterogenous character. The induction time, measured by conductivity for the similar supersaturation levels, reveals a well detectable dependence on nano/microdust concentent: an increasing background particle concentration substantially decreases the induction period at a constant saturation state and temperature, and thus increases the nucleation rate. Therefore, the gypsum nucleation reaction starts tentatively through the fast heterogeneous formation of well-defined, primary nuclei via [Ca2+ ], [SO42− ], and [CaSO4 ]o species sorption on the surface of “nano/microdust” particles. Thus, the “nano/microdust”, naturally occurring in any high purity chemical, plays a key role in sparingly soluble salts nucleation in the bulk aqueous medium.