H/D exchange kinetics in pure and HCl doped polycrystalline ice at temperatures near its melting point: structure, chemical transport, and phase transitions at grain boundaries.

We report the results of a fast thermal desorption spectroscopy study of the H/D isotopic exchange kinetics in a few micrometer thick, pure polycrystalline ice film and in ice films doped with HCl. Using the isotopic exchange reaction as a probe of transport processes in ice, we determined the effective H/D interdiffusion coefficients, D(eff), in pure and doped polycrystalline ice at temperatures ranging from -18 to -1 degree C. In the case of pure polycrystalline ice, D(eff) demonstrates an Arrhenius dependence on temperature with an effective activation energy of 69+/-3 kJ mol(-1) and a pre-exponential of 10(9+/-0.5) microm(2) ms(-1) up to -2 degrees C. According to our analysis, H/D interdiffusion coefficient at the grain boundaries also shows an Arrhenius dependence on temperature with an activation energy of 69+/-3 kJ mol(-1) and a pre-exponential of 10(11+/-1) microm(2) ms(-1). However, the addition of 0.04% of HCl results in a marked deviation of D(eff) from Arrhenius law at -8 degrees C, which is attributed to premelting at intersections of grain boundaries. We discuss the structure and transport properties of condensed aqueous phase at grain boundaries in polycrystalline ice at various temperatures.