Cyclic voltammogram defining terms

Further increasing the scan rate in the case of the initial ErevCrev mechanism yields cyclic voltammograms with identical characteristics to those shown in Fig. II. 1.21 a for the ErevCinev mechanism. Indeed, the operational rather than the absolute definition of the terms reversible and irreversible is revealed in this example as clearly an ErevCrev process as defined at slow scan rate becomes an Er evCirrev or Erev (or even Emev) process as the voltammetric timescale becomes progressively decreased. There is abundant experimental evidence [95] to testify to the importance of the ErevCrev mechanistic chemical process. A related and recently extensively studied mechanism has been denoted ErevCdim [96] (Eq. II. 1.23) (or more correctly ErevCdim.irrev)-... 

Figure 1) in terms of their reduction potential peaks (Ep, obtained from their cyclic voltammograms) their ESR parameters (obtained from the ESR spectra) and their antitumor activity (measured by ICso as defined in Methods). Table 2 shows the relationship between ICso values and Ep and An. In general, there is no correlation between drug activity and the two physicochemical parameters obtained. This is in contrast with previous findings by Lin and Sartorelli for a different set of bioreductive alkylators. 

Using a computer, carry out simulations of cyclic voltammetry for a quasireversible system. Let = 50 and Dm = 0.45, Take a = 0.5 and let the diffusion coefficients of the oxidized and reduced forms be equal. Cast your dimensionless intrinsic rate parameter in terms of the function ij/ defined in (6.5.5), and carry out calculations for ip = 20, I, and 0.1. Compare the peak splittings in your simulated voltammograms with the values in Table 6.5.2. 

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