Modulated temperature DSC (MTDSC) has been performed on phenyl glycidyl ether (PGE) + aniline in order to obtain the non-reversing heat flow and heat capacity profiles simultaneously in a wide range of cure temperatures and mixture compositions. The epoxy (PGE) conversion as determined from the former signal corresponds to the one obtained from separate high performance liquid chromatography (HPLC), while the latter signal contains information on the individual reaction steps. Optimized kinetic parameters using a mechanistic approach, including both reactive and non-reactive complexes can successfully simulate MTDSC measurements for isothermal reaction temperatures ranging from 50 to 120degreesC and for non-isothermal experiments with mixture compositions corresponding to concentrations of aniline in a range from 1.68 to 6.53 mol kg(-1). Concentration profiles for three mixture compositions as obtained from HPLC are also well predicted. The activation energies for the primary amine and secondary amine-epoxy reaction catalyzed by hydroxyl groups are 50 and 52 kJ mol(-1), respectively, while the initiation of the reaction corresponds to the primary amine-epoxy reaction catalyzed by primary amine groups with an activation energy of 72 kJ mol(-1). A negative substitution effect can be calculated at 0.18 from the ratio of secondary amine to primary amine-epoxy reaction rate constants. (C) 2003 Elsevier B.V All rights reserved.