Electrode reaction, kinetics, magnetic

IV. THE MAGNETIC FIELD EFFECT ON ELECTRODE REACTION KINETICS... 

It follows from Equation 6.12 that the current depends on the surface concentrations of O and R, i.e. on the potential of the working electrode, but the current is, for obvious reasons, also dependent on the transport of O and R to and from the electrode surface. It is intuitively understood that the transport of a substrate to the electrode surface, and of intermediates and products away from the electrode surface, has to be effective in order to achieve a high rate of conversion. In this sense, an electrochemical reaction is similar to any other chemical surface process. In a typical laboratory electrolysis cell, the necessary transport is accomplished by magnetic stirring. How exactly the fluid flow achieved by stirring and the diffusion in and out of the stationary layer close to the electrode surface may be described in mathematical terms is usually of no concern the mass transport just has to be effective. The situation is quite different when an electrochemical method is to be used for kinetics and mechanism studies. Kinetics and mechanism studies are, as a rule, based on the comparison of experimental results with theoretical predictions based on a given set of rate laws and, for this reason, it is of the utmost importance that the mass transport is well defined and calculable. Since the intention here is simply to introduce the different contributions to mass transport in electrochemistry, rather than to present a full mathematical account of the transport phenomena met in various electrochemical methods, we shall consider transport in only one dimension, the x-coordinate, normal to a planar electrode surface (see also Chapter 5). 

The experimental apparatus for a potentiometric titration can be quite simple only a pH or millivolt meter, a beaker and magnetic stirrer, reference and indicator electrodes, and a burette for titrant delivery are really needed for manual titrations and point-by-point plotting. Automatic titrators are available that can deliver the titrant at a constant rate or in small incremental steps and stop delivery at a preset endpoint. The instrument delivers titrant until the potential difierence between the reference and indicator electrodes reaches a value predetermined by the analyst to be at, or very near, the equivalence point of the reaction. Alternatively, titrant can be delivered beyond the endpoint and the entire titration curve traced. Another approach to automatic potentiometric titration is to measure the amount of titrant required to maintain the indicator electrode at a constant potential. The titration curve is then a plot of volume of standard titrant added versus time, and is very useful, for example, for kinetic studies. The most extensive use of this approach has been in the biochemical area with so-called pH-stats—a combination of pH meter, electrodes, and automatic titrating equipment designed to maintain a constant pH. Many enzymes consume or release protons during an enzymatic reaction therefore, a plot of the volume of standard base (or acid) required to maintain a constant pH is a measure of the enzyme activity, the amount of enzyme present. 

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