Freezing of Water and Aqueous NaCl Droplets Coated by Organic Monolayers as a Function of Surfactant Properties and Water Activity

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 (a w) from 0.8 to 1 accompanied by measurements of the corresponding pressure–area 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 a w 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 (J het) 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 a w and not by the a w-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 J het = 0.46 ± 0.16 cm–2 s–1. Contact angles (α) 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(Δa w)] 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 α.