Integrated Kinetic and Thermodynamic Model Describing the Nitrosation of Aniline and Its Derivatives under Reaction- and Encounter-Controlled Conditions

Abstract

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 kin..