title: Fast thermal desorption spectroscopy study of H/D isotopic exchange reaction in polycrystalline ice near its melting point.
abstract: Using fast thermal desorption spectroscopy, a novel technique developed in our laboratory, we investigated the kinetics of HD isotopic exchange in 3 microm thick polycrystalline H2O ice films containing D2O layers at thicknesses ranging from 10 to 300 nm at a temperature of -2.0+/-1.5 degrees C. According to our results over the duration of a typical fast thermal desorption experiment (3-4 ms), the isotopic exchange is confined to a 50+/-10 nm wide reaction zone located at the boundary between polycrystalline H2O and D2O ice. Combining these data with a theoretical analysis of the diffusion in polycrystalline medium, we establish the range of possible values for water self-diffusion coefficients and the grain boundary widths characteristic of our ice samples. Our analysis shows that for the grain boundary width on the order of a few nanometers, the diffusivity of D2O along the grain boundaries must be at least two orders of magnitude lower than that in bulk water at the same temperature. Based on these results, we argue that, in the limit of low concentrations of impurities, polycrystalline ice does not undergo grain boundary premelting at temperatures up to -2 degrees C.
authors.affiliation: Department of Chemistry, The George Washington University, Washington, DC 20052, USA.
authors.forename: Haiping
authors.initials: H
authors.lastname: Lu
authors.forename: Stephanie A
authors.initials: SA
authors.lastname: McCartney
authors.forename: Vlad
authors.initials: V
authors.lastname: Sadtchenko