Abstract
Using ultra-high vacuum methods and a photometric technique, the kinetics of the chlorination of vacuum-deposited sodium films have been determined in the temperature range 228–298° K. The functional form of the kinetics is shown to be in accord with the Mott-Cabrera model applied to film growth by cation vacancy migration. Fitting the experimental data to this model yields a value of 2.2±0.2 volt for the potential drop across the NaCl film and an activation energy for migration of 0.6±0.2 electron volt. These values agree respectively with the contact potential difference for the system measured by Anderson and Clark, 2.05±0.05 volt, and the accepted activation energy for cation vacancy migration in NaCl, 0.8 electron volt. The reaction rate appears to be independent of Cl2 pressure for NaCl film thicknesses less than about 200 Å, but approximately proportional to\({\text{p}}_{Cl_{\text{2}} }^{{\text{1/2}}} \) for greater thicknesses. Such behavior is predicted by the modelon the assumption of saturation adsorption of chlorine on the NaCl film.
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Shiu, W.Y., Young, D.J. & Dignam, M.J. Kinetics of chlorination of metallic sodium at low temperatures. Oxid Met 7, 77–93 (1973). https://doi.org/10.1007/BF00611449
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DOI: https://doi.org/10.1007/BF00611449