VII5. Relaxationsspektren chemischer Umwandlungen (Metallkomplexe und protolytische Reaktionen in wäßriger Lösung)

Abstract When a reaction system in equilibrium is disturbed by change of an external parameter (e.g. pressure, temperature, or electric field strength), the system attempts to adjust its internal equilibrium by the shortest possible path. This adjustment ‐ ‘chemical relaxation’ ‐ takes place with a characteristic spectrum of time constants which are related to the rate constants of the individual steps in the transformation. An analysis of the relaxation spectrum allows the determination of the absolute rate constants and gives information concerning the mechanism of the overall reaction. The methods which make use of these principles are discussed in detail in the papers of L. De Maeyer and K. Tamm. The velocity and mechanism of very fast reactions as measured with these methods is discussed. The results allow the development of some general principles governing several important types of reactions.