Comparison of High- and Low-Temperature Data for the Cl2⇋2Cl Reaction

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Abstract
The radical–molecule mechanism for the three‐body recombination reaction was applied to the reaction 2Cl+Ar→Cl2+Ar and 2Cl+Cl2→2Cl2. It was found that the interaction potentials between Cl atom and either Cl2 or Ar are approximately 2 kcal/mol. The interaction potential in the Cl–Ar complex is 8–10 times deeper than the potential between the two argon atoms. Using the same radical–molecule mechanism, it was possible to extrapolate the recombination rate constant data up to shock wave temperature. The extrapolation yielded a plausible comparison of the low‐temperature (below 500°K) Cl recombination data, and the high‐temperature shock‐tube Cl2dissociation data above 1500°K. The available experimental Cl2dissociationrate constants show a scatter among data of various investigations by a factor of 20. Our extrapolation strongly favors the newer shock wave data which are therefore thought to be more reliable. On the other hand, the extrapolation is in distinct disagreement with the results of some earlier investigators.

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