AbstractChemical reactions on polymers in homogeneous medium were used to characterize the structure of the macromolecules. The polymer was in the form of polyamide fibers dissolved inm‐cresol to give a fairly highly concentrated solution (approximately 6). Kinetic studies of hydrolysis, acetylation, and deamination reactions on the polyamide fibers were carried out in homogeneous medium at different temperatures. All the three reactions studied followed first‐order kinetics. Rate constants and apparent activation energies were determined for these reactions, which show two rates—an initial fast rate followed by a slow one. A new microfibrillar model of the polymer dissolved inm‐cresol is proposed, and the existence of two rates is explained on the basis of the two‐phase structure of the proposed microfibril. The fast rate is attributed to the free chain segments, and the slow rate is shown to correspond to the regions which are strongly hydrogen bonded and which hold the various chains together to give the microfibrillar structure of the polymer in the homogeneous phase. The apparent activation energy for hydrolysis was 3.20 and 0.18 kcal/mole for the fast and slow rates, respectively. The apparent activation energy values for acetylation were 1.50 and 0.80 kcal/mole, while those for the apparent deamination reaction were 6.90 and 4.60 kcal/mole, respectively. Lower values of apparent activation energies are attributed to the ease of reaction in the difficult‐to‐penetrate regions of the microfibril due to the role played by the solvent of the homogeneous phase in carrying the reacting species inside these regions while simultaneously breaking the hydrogen bonds between the polypeptide chains. The apparent deamination reaction is shown to be a resultant reaction of simultaneous deamination and “amination” through hydrolytic breakdown of the
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