Journal of Chemical Physics, Vol.121, No.23, 11980-11992, 2004
The vaporization rate of ice at temperatures near its melting point
The first study of free vaporization kinetics of ice at temperatures near its melting point is reported. The experimental approach employed is based on a unique combination of thermal desorption spectroscopy, microcalorimetry, and time-of-flight mass spectrometry, making it possible to overcome challenges associated with the introduction of volatile solids into a high vacuum environment. Measurements of the vaporization rate of polycrystalline ice demonstrate that the vaporization kinetics deviate dramatically from those predicted by a simple mobile precursor mechanism. The vaporization rate follows Arrhenius behavior from -40 to 0 degreesC with an effective activation energy of 50+/-4 kJ/mol, which is significantly higher than the value predicted by the simple mobile precursor mechanism. Extrapolation of earlier measurements conducted below -40 degreesC yields a value of approximately 0.02 at 0 degreesC for the vaporization coefficient alpha(v). In contrast, experimentally determined vaporization coefficient is found to be 0.7+/-0.3 and shows a weak dependence on temperature up to the bulk melting point. The role of possible surface phase transitions in the mechanisms of release and uptake of H2O and other chemical species by ice surfaces is discussed. (C) 2004 American Institute of Physics.