A QuantumMechanical Calculation of the Rates of Some Chemical Reactions
Abstract
The rates of many simple chemical reactions of the type AB+C→A+BC are empirically known to be of the form k_{OF}=PZ exp(—E_{A}/kT). On the theory that the reactions take place through the interchange of translational and vibrational energy, a qualitative quantummechanical calculation of the rate k_{OF} is made for the simple model of collinear collisions. The empirical values of the activation energy E_{A} are employed to fix the interaction potential for a given reaction. On identifying the quantummechanical expression for the rate k_{OF} with the empirical expression above and on using the gas kinetic expression for the mean number of collisions Z, it is possible to calculate the probability factor P. Numerical calculations have been carried out for the two reactions H_{2}+X→HX+H, where X is Cl or Br. In both cases, P is found to be about 8×10^{3}.
 Publication:

Journal of Chemical Physics
 Pub Date:
 April 1953
 DOI:
 10.1063/1.1698999
 Bibcode:
 1953JChPh..21..726B