Pulse polarography: Part V. on the theory for the kinetic currents with an ece mechanism |
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Authors: | J. Galvez A. Molina |
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Affiliation: | Laboratory of Physical Chemistry, Faculty of Science, Murcia, Spain |
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Abstract: | We have derived an equation for the instantaneous limiting current in pulse polarography with an ECE mechanism. That equation has been derived for the expanding sphere electrode model (and also for the expanding plane electrode model) with the condition (k1+k2)>>1, k1 and k2 being the rate constants of the chemical reaction. We show that by an adequate choice of the time of application of the potential and time of the drop growth prior to potential application, it is possible — if the equilibrium constant for chemical reaction is known — to widen the interval of values for k1 and k2 that may be determined using this technique. At the same time, we also show that if the electrode sphericity is not taken into account, the values obtained for k1 and k2 are always lower than the real ones. |
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