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

The heats of formation of the 2:1 electron donor-acceptor (EDA) complexes o f naphthalene-1,4,5,8-tetracarboxylic dianhydride with aniline and 2,4-dime thylaniline in three different solvents are reported. The enthalpies and en tropies of activation of these EDA complexes for their decomposition into s econdary products in these solvents (CCl4, CHCl3, and CH3CN) are also deter mined. It is found that the decomposition rates of both the EDA complexes d ecrease 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 Delta S* in terms of a change in geometry in the pro cess of activation.