AbstractIn a study aimed at process optimization of caprolactam polymerization, particular reference has been paid to the competing role of water in caprolactam hydrolysis and endgroup polycondensation. The dependence of the apparent equilibrium constant for polycondensation on water concentration indicated that there is a strong effect of the medium on the activities of the reacting species which can not be neglected in a kinetic study of the polycondensation reaction. The effect of a variation of the medium was taken into account by using a polycondensation rate constant which included a function of the water present at any given time. With the aid of analog computer curve‐fitting techniques, good agreement with second‐order kinetics was found. The validity of a second‐order mechanism was confirmed in a kinetic study of the chain amide linkage hydrolysis. The hydrolysis of caprolactam follows substantially different kinetics, where the generation of carboxyl groups reduces the activation energy of the reaction, which follows predominantly a third‐order me