Extended electron transfer and the Frumkin correction

It is now well established that the rate constant for electron transfer between a metal electrode and a given redox moiety (at distance x from the electrode) decays according to exp[ - betax]; values of beta are of the order of 10(8) cm(-1) and depend primarily upon the nature of the intervening medium. The present work demonstrates how this 'extended' electron transfer can modify the Frumkin correction for diffuse layer effects in the measurement of heterogeneous rate constants. We quantify the effect of this 'extended' electron transfer by comparing the electron transfer rate constants deduc

Resistance‚ capacitance‚ and electrode kinetic effects in Fourier−transformed large−amplitude sinusoidal voltammetry: Emergence of powerful and intuitively obvious tools for recognition of patterns of behavior

Large-amplitude sinusoidal ac voltammetric techniques, when analyzed in the frequency domain using the Fourier transform-inverse Fourier transform sequence, produce the expected dc and fundamental harmonic ac responses in addition to very substantial second, third, and higher ac harmonics that arise from the presence of significant nonlinearity. A full numerical simulation of the process, Red reversi

Controlled Potential techniques in amperometric sensing

Thermodynamics should strictly govern every reliable surement supposedly performed in equilibrium conditions, as it is the case of potentiometry, in such a way that a measure that is not in agreement with thermodynamics is actually of poor meaning, if any. On the other hand, if an external power source controls the occurrence of a redox process at an electrode, as it happens in the controlled potential techniques, thermodynamics tries to manage what is going on, though not always successfully. Sometimes it happens that it does, sometimes that the system “runs after” equilibrium conditions, only approaching them more or less closely