Convolution potential sweep voltammetr

The heterogeneous rates of electron transfer in eq 7 were measured by two independent electrochemical methods cyclic voltammetry (CV) and convolutive potential sweep voltammetry (CPSV). The utility of the cyclic voltammetric method stems from its simplicity, while that of the CPSV method derives from its rigor. 

Pilo, Maria I., Sanna, G. and Seeber, R. (1992) Analysis of cyclic voltammetric responses by Fourier transform-based deconvolution and convolution procedures , J.Electroanal.Chem. 323, 103-115. See references therein for semiintegral and semidifferential electroanalysis, as well as for convolutive potential sweep voltammetry. 

By proper treatment of the linear potential sweep data, the voltammetric i-E (or i-t) curves can be transformed into forms, closely resembling the steady-state voltammetric curves, which are frequently more convenient for further data processing. This transformation makes use of the convolution principle, (A.1.21), and has been facilitated by the availability of digital computers for the processing and acquisition of data. The solution of the diffusion equation for semi-infinite linear diffusion conditions and for species O initially present at a concentration Cq yields, for any electrochemical technique, the following expression (see equations 6.2.4 to 6.2.6) ... 

The convolution technique offers a number of advantages in the treatment of linear sweep data (and perhaps also in other electrochemical techniques). For a reversible reaction in a cyclic voltammetric experiment, the curves of l(t) vs. E for the forward and backward scans superimpose, with l(t) returning to zero at sufficiently positive potentials [where Cr(0, 0 = 0]. This behavior has been verified experimentally (20, 25, 28) (Figure 6.13a). 

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