Integrated kinetic and thermodynamic model describing the nitrosation of aniline and its derivatives under reaction- and encounter-controlled conditions

A kinetic model has been developed that describes the rate of reaction (nitrosation) of aniline and its derivatives with a range of nitrosating agents. This model was derived by first developing a thermodynamic description of the system based on the basicity of the substrate and the nucleophilicity of the nitrosating agent. A kinetic model was obtained by combining the thermodynamic description of the system with experimentally observed kinetics via the transition state theory. The final model exhibited a good correlation with experimental results across a wide range of reactivities. The encounter-controlled regime was also modeled from mass-transfer theory, which was integrated with the kinetic model to describe the rate of nitrosation during the transition regime. Through application of the kinetic model, the intrinsic barrier to reaction was estimated as 15 kJ mol(-1).