Nagy, Gabor and Denuault, Guy
Three-dimensional random walk simulation of diffusion controlled electrode processes: (II) Arrays of growing hemispheres
Journal of Electroanalytical Chemistry, 433, (1-2), . (doi:10.1016/S0022-0728(97)00286-6).
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A series of random walk simulations of diffusion controlled electrodeposition processes following instantaneous nucleation were performed to predict chronoamperometric current transients. At short times the current increases due to the growth of individual deposits, while at long times the current drops under the control of linear diffusion towards the surface. The current transient exhibits a maximum at intermediate times soon after the diffusion zones of the growing centres overlap. Relating the positions and heights of the peaks to simulation parameters we found that, apart from the chemical characteristics of the system, the current depends only on bulk concentration and nuclear number density. After rescaling the current transients according to these relations we were able to derive a simple analytical expression that characterises the whole process with sufficient accuracy. Comparing our results with existing analytical theories, we found certain conditions when they agree with our simulations. In this way, we were able to define the concentration range where these theories work satisfactorily. (C) 1997 Elsevier Science S.A.
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