Structural and biomimetic chemical kinetics: Kinetic magnitudes include structural information

Abstract

Electrochemical reactions in films of conducting polymers involve reactive chains, exchanging ions and solvent with the electrolyte under current flow. The reaction induces structural changes: conformational movements in chains and swelling, shrinking, compaction, and relaxation processes in the reactive dense gel. Conformational movements and structural changes induced by reactions are not included by today's chemical kinetic models. Using different packed conformations as initial states for the study of the reaction kinetics in films of different conducting polymers, rate coefficients, activation energies, and reaction orders related to the concentration of active centers in the film change with the structure of the selected initial state. The kinetic magnitudes include and quantify conformational and structural energetic states. Therefore, the reaction activation energy includes the constant reaction activation energy and the conformational energy of the initial packed state. The electrochemically stimulated conformational relaxation model describes the empirical variation of the kinetic magnitudes. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.