title: 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 (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.
authors.affiliation: Institute for Terrestrial and Planetary Atmospheres/School of Marine and Atmospheric Sciences, Stony Brook University, Stony Brook, New York 11794, USA. Daniel.Knopf@Stonybrook.edu
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Knopf
authors.forename: Seanna M
authors.initials: SM
authors.lastname: Forrester