Freezing of water and aqueous NaCl droplets coated by organic monolayers as a function of surfactant properties and water activity

Abstract

This study presents heterogeneous ice nucleation from water and aqueous NaCl droplets coated by 1-nonadecanol and 1-nonadecanoic acid monolayers as a function of water activity (aw) from 0.8 to 1 accompanied by measurements of the corresponding pressurearea isotherms and equilibrium spreading pressures. For water and aqueous NaCl solutions of ̃0-20 wt % in concentration, 1-nonadecanol exhibits a condensed phase, whereas the phase of 1-nonadecanoic acid changes from an expanded to a condensed state with increasing NaCl content of the aqueous subphase. 1-Nonadecanol-coated aqueous droplets exhibit the highest median freezing temperatures that can be described by a shift in aw of the ice melting curve by 0.098 according to the a w-based ice nucleation approach. This freezing curve represents a heterogeneous ice nucleation rate coefficient (Jhet) of 0.85 ± 0.30 cm-2 s-1. The median freezing temperatures of 1-nonadecanoic acid-coated aqueous droplets decrease less with increasing NaCl content compared to the homogeneous freezing temperatures. This trend in freezing temperature is best described by a linear function in aw and not by the aw-based ice nucleation approach most likely due to an increased ice nucleation efficiency of 1-nonadecanoic acid governed by the monolayer state. This freezing curve represents Jhet = 0.46±0.16 cm-2 s -1. Contact angles (R) for 1-nonadecanol- and 1-nonadecanoic acid-coated aqueous droplets increase as temperature decreases for each droplet composition, but absolute values depend on employed water diffusivity and the interfacial energies of the ice embryo. A parametrization of log[J het(Δaw)] is presented which allows prediction of freezing temperatures and heterogeneous ice nucleation rate coefficients for water and aqueous NaCl droplets coated by 1-nonadecanol without knowledge of the droplet's composition and R. © 2011 American Chemical Society.