By K. Scott (auth.), Ralph E. White, J. O’M. Bockris, B. E. Conway (eds.)
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Extra info for Modern Aspects of Electrochemistry
It is instructive to see how these expressions compare with the general rate equation for the reaction mechanism (Eqs. 35-38) that is obtained by applying the stationary-state approximation to Rl, 0'1, and 01. a (48) where the fraction of sites unoccupied is given by 1 kbl kp. + kaCF,. (J /'. -Q /, /'. /'. a) - (kp. a) ktJ + /q,2 This· is a complicated equation which represents tlte rate for, in principle, a simple two-electron-transfer reaction. Clearly, the rds limiting forms are more convenient, both for engineering use and in experimental data analysis.
Clearly, either of these approximations ignores the aspect of both the current and potential varying along the reactor, which for some circumstances must be considered. In industrial electrochemical reactors, the preferred operating mode is generally specified by supplying a known overall current at a prescribed voltage. Thus, it is often assumed that galvanostatic operation exists in that there is no local variation of current density. , electrode potential is uniform along the reactor). (v) The Recycle Plug Flow Reactor The model of the recycle plug flow reactor will be developed using an example of the classic ECE mechanism to stress the important difference between a reactor with and without recycle.
It is the transient behavior of current or potential that is of importance in such experiments, and use of the unsteady-state techniques can reveal many details that are of interest. There is other work which has dealt with steady-state experiments on a longer time scale which is intended mainly as an electroanalytical too1. Gelb and Meites48 derived analytical solutions for a number of systems involving series of consecutive electrochemical and chemical reactions. Their work included the calculation of concentration-time profiles and so could be adapted to the purpose of obtaining expected product distributions in industrial reactors.
Modern Aspects of Electrochemistry by K. Scott (auth.), Ralph E. White, J. O’M. Bockris, B. E. Conway (eds.)