Deliquescence of NaCl Confined in Nanoporous Silica

The deliquescence behavior of salt nanocrystals is different from that of bulk crystals. Here, we report the first systematic measurements of the deliquescence relative humidity (DRH) of sodium chloride crystals confined in various nanoporous silica materials with pore diameters ranging from 8 to 89 nm. Deliquescence humidities were determined by water vapor sorption measurements. In comparison to the DRH of bulk NaCl crystals (75.3% RH), the DRH decreases from 73 to 58% as the pore size decreases from 89 to 8 nm. In contrast, according to literature data, the DRH of NaCl aerosol nanoparticles increases with decreasing crystal size. A thermodynamic model approach, based on the combined use of an ion-interaction model, the Laplace equation, and the Kelvin equation, is used to calculate the influence of the confinement in nanopores on the solid-liquid and liquid-vapor phase equilibria. These calculations reveal that the main reason for the decrease in the DRH in nanopores is the concave curvature of the liquid-vapor interface that is formed during deliquescence. The same model approach shows that the increase in DRH of nanosized aerosol particles is due to the convex curvature of the liquid-vapor interface, whereas the effect of increases in solubility with decreasing crystal size is small.