Absolute values of the rate constant for isopropyl radical combination have been determined over the temperature range 683-808°K. The value log kr (M~1 sec-1) = 9.5 ± 0.2 fits all the data, leading to the conclusion that the temperature dependence, if any, is slight. The compatibility of this value with other values determined either directly or from the reverse process via thermochemical data depends on the particular model chosen to represent the transition state since the temperatures of the various determinations differ. It has been found that
Infrared emission intensities from HCl and DCl products in high vibrational levels have been used to measure energy partitioning in the reactions of H and D atoms with SCl2 and S2Cl2. The results are compared to the infrared chemiluminescence from the H and D atom reactions with Cl2. The relative vibrational level populations were measured under experimental conditions such that vibrational relaxation was minimized. The H atom reactions with SCl2 and S2Cl2 partitioned >37% and >36% of the available energy into vibrational energy of the hydrogen chloride product. Within our experimental error the fraction of energy partitioned to vibration was the same for the H and D atom reactions. In the reactions of H and D with SCl2 and S2Cl2 the distribution of rate constants for formation of HCl† and DCl† into the vibrational levels apparently peaks at levels intermediate between υ = 0 and the maximum possible level of vibrational excitation. The distributions are similar to those from the H and D atom reactions with Cl2. The additional internal degrees of freedom in S2Cl2 relative to SCl2 did not greatly affect the partitioning of energy to the HCl† product.
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