Competitive Reaction Rates of Hydrogen Atoms with HCl and Cl2. Entropy Considerations of the HCl2 Transition State

The relative rates of the reactions H+HCl→ lim k3H2+Cl and H+Cl2→ lim k6HCl+Cl, were determined in the temperature range of 0° to 62°C and found to be given by k3/k6=(0.143±0.033) exp−(1540±130/RT). The temperature‐independent factor in the above expression is interpreted in terms of the structure and the vibrational frequencies of the HCl2 transition state. The doubly degenerate bending frequency of this transition state is found to have a value of about 105 cm−1.