Steady-state behavior rate-constant sensitivities

The voltammetric behavior of the first-order catalytic process in DDPV for different values of the kinetic parameter Zi(= ( 1 + V) Ti) at spherical and disc electrodes with radius ranging from 1 to 100 pm can be seen in Fig. 4.25. For this mechanism, the criterion for the attainment of a kinetic steady state is %2 > 1-5 (Eq. 4.232) [73-75]. In both transient and stationary cases, the response is peakshaped and increases with j2. h is important to highlight that the DDPV response loses its sensitivity toward the kinetics of the chemical step as the electrode size decreases (compare the curves in Fig. 4.25a, c). For the smallest electrode (rd rs 1 pm, Fig. 4.25c), only small differences in the peak current can be observed in all the range of constants considered. Thus, the rate constants that can... 

The exponential decay of transfer rate indicates that the exchange interaction is very sensitive to distance. The exchange transfer prefers the nearest or the second nearest D-A pairs. Such a behavior of exchange interaction is similar to the Perrin model, in which the transfer rate is assumed to be constant if A exists within a critical distance and is zero outside the range. This model is thought to be the most applicable to the exchange interaction. In the Perrin model, the steady-state luminescence of D as a function of concentration of A is simply written as [4]... 

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