Kinetics of Discharge of Metal Ion Complexes with Preceding Chemical Reaction

Alternating Current Polarography of Electrode Processes wih Coupled Homogeneous Chemical Reactions. I. Theory for Systems with First-Order Preceding, Following, and Catalytic Chemical Reactions.

“…The faradaic series capacity, c8, is derived from mass transfer only and is the sum of mass transfer capacities of 0 and R. The frequency dependence of the resistive and capacitive components of the faradaic impedance with preceding reactions has been discussed by Delahay, et al (5,6,26). Specific application of their arguments to phase angles for such systems is considered here for completeness.…”

“…Specific adaptation of equations presented here for more complex :*eaction schemese.g., dissociation of a metallic complex followed by reduction to metal-can be accomplished mithoL t difficulty (6,26).…”

“…Systems not obeying theoretical predictions can be interpreted as involving rate determining steps in addition to diffusion and charge transfer [cf., e.g., (6) for references]. Matsuda (%$) and Matsuda and Delahay (26) have extended theory to account for specific effects of the electrical double layer.…”

“…The only case discussed in the literature has been the system with a preceding chemical reaction, initially treated theoretically by Gerischer (IO) and later, in more detail, by Matsuda. Delahay, and Kleinerman (26) and Delahay ( 5 , 6 ) . X communication by Satyanarayana,Reddy,and Doss (32), presenting equations without derivation, is the only other contribution knon n to this author.…”

“…Consider the electrode reaction kl Y 0 + ne R (1) ÍC2 where reactants present in large excess are neglected for simplicity, their concentrations being incorporated in the rate and equilibrium constants. Specific adaptation of equations presented here for more complex reaction schemese.g., dissociation of a metallic complex followed by reduction to metal-can be accomplished withoi.t difficulty (6,26).…”