THERMODYNAMIC CONJUGATION OF THE PARTIAL PROCESSES OF METAL CORROSIONIN THE PRESENCE OF OXIDIZERS

The formalism of the thermodynamics of irreversible processes was used for describing the reciprocal effects of the partial reactions of met al corrosion that proceeds in the presence of oxidizers. The effect of a nonequilibrium surface layer on the thermodynamics of electrode rea ctions was considered. A deviation of the surface layer from the equil ibrium state was found to result in free-energy transfer between vario us electrodic processes and, thus, in the thermodynamic conjugation of the processes. The particles that provide conjugation may be as follo ws: final or intermediate products of the cathodic reactions, metallic ad-atoms, surface complexes, vacancies, and other structural defects. The approach proposed can be applied to describing so-called ''anomal ous'' dissolution of metals under cathodic polarization as well as of the effect of oxidizers on the passivation potential and the kinetics of dissolution of metals. The limitations imposed on the applicability of the principle of independently proceeding electrodic processes are considered as being caused by a nonequilibrium state of the metal-ele ctrolyte boundary under conditions of anodic dissolution and metal cor rosion.