Kinetics of thermal reaction HOCl ⇄ H(2 S) + OCl(X 2Π i ) in gas phase

Abstract

The kinetics of gas reaction $$HOCl\underset{{k_r }}{\overset{{k_f }}{\longleftrightarrow}}H(^2 S) + OCl(X^2 \Pi _i )$$ was analyzed by the MP4 method. In the temperature range of 100–373 K the rate constants k f and k r and equilibrium constant K were changed from 1.10 × 10−220 to 1.17 × 10−52 s−1, from 2.89 × 10−16 to 1.68 × 10−5s−1 and from 3.80 × 10−205 to 6.96 × 10−48 respectively. In the above temperature range, the activation energy of the forward reaction (E f) is 105.05 kcal/mol. In the same temperature interval there are two kinetic domains for the reverse reaction with activation energies (E r1 = 5.53 kcal/mol when T is 100–273 K and E r2 = 14.50 kcal/mol when T is 273–373 K, respectively.