Kinetic study of the decay of EDA complexes of aniline and 2,4- dimethylaniline with naphthalene- 1,4,5,8-tetracarboxylic dianhydride

Abstract

The heats of formation of the 2:1 electron donor-acceptor (EDA) complexes of naphthalene-1,4,5,8- tetracarboxylic dianhydride with aniline and 2,4- dimethylaniline in three different solvents are reported. The enthalpies and entropies of activation of these EDA complexes for their decomposition into secondary products in these solvents(CCI₄, CHCI₃ and CH₃CN) are also determined. It is found that the decomposition rates of both the EDA complexes decrease with increase in solvent polarity, but the entropies of activation do not follow a systematic trend. An attempt has been made to explain such anomalous variation of rS* in terms of a change in geometry in the process of activation.