Kinetic and mechanistic studies of reactions of aniline and substituted anilines with chloramine T

Rates of reactions of aniline and substituted anilines with chloramine T (CAT) to form N-chloroanilines have been measured. Each reaction showed first-order dependence on CAT and fractional order dependence on the amine. The latter observation indicates that the reaction involves formation of a complex in a fast equilibrium step followed by slow decomposition of the complex. The equilibrium constant (K) for the formation of the complex and its decomposition rate constant (k₂) in each case have been calculated from the plot of 1/K_obs versus 1/[amine]. In addition, the reaction constant (p-0.976. obtained from a Hammett plot) and thermodynamic parameters have been evaluated, and mechanisms are proposed.