Catalytic and Kinetic Waves in Polarography by Stal G. Mairanovskii

By Stal G. Mairanovskii

As our wisdom of the mechanism of electrode techniques raises, it turns into an increasing number of obvious that the kinetic currents first saw via R. Brdicka and via okay. Wiesner within the 1940's are very greatly encountered. Very many electrode professional­ cesses include a chemical level. * this is often precise essentially of elec­ trode strategies that contain natural compounds. as a result, to appreciate the mechanism of electrode strategies and, specific­ ly, to properly interpret the result of polarographic investiga­ tions, it is very important understand the features and relationships controlling the chemical reactions happening on the electrode floor. typically, those reactions are considerably various from traditional chemical reactions occurring within the bulk of the answer, because the reactions on the electrodes are frequently plagued by the electrical box of the electrode and the adsorption of the par­ ticipating compounds . the truth that hydrogen ions often participate in the electro­ chemical relief of natural compounds makes attainable using electrochemical tools, rather polarography, for the learn of protolytic reactions. those reactions play a huge function in natural chemistry: the vast majority of reactions of natural compounds in ideas battle through a level within which a hydrogen ion is got rid of or extra (see, for instance, [1, 2]). consequently, the polarographic learn of protolytic reactions can offer a lot very important info to theoretical natural chemistry.

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Kinetic Currents Limited by the Rate of Recombination of Acid Anions The most widespread variety of kinetic currents with antecedent reactions are those that are limited by the rate of recombination of acid anions with hydrogen ions. It is more difficult to reduce anions than undissociated molecules of the same acids. This is caused by the difficulty of electron transfer to negatively charged particles and by the reduced concentration of anions at the surface of the cathode due to electrostatic repulsion.

CURRENTS LlMlTED BY THE RATE OF CHEMICAL REACTION 23 Even oxalic acid can be an oxidant, giving a catalytic wave in the presence of uranyl ions, as was shown by Grabowski and Grabowska (112]. ) at low concentrations of oxalic acid, increases linearly with the acid concentration, has a diffusion character, and corresponds to the transfer of two electrons. In an excess of oxalic acid the wave becomes kinetic. A complex in which two molecules of oxalic acid are bound on a uranium ion takes part in the electrode reaction.

He showed, on the basis of the value determined, that in the discharge of cadmium ions in an excess of nitrilotriacetic acid on a streaming electrode (the contact time with the solution is 8 • 10- 4 sec) the kinetic component of the currerit should not play any role [217]. The physical meaning of this observation is that if the time of electrolysis is reduced the effective thickness of the diffusion layer decreases and becomes of the same order of magnitude or smaller than the re action layer. The current becomes independent of the re action rate and is determined only by the diffusion of electrochemically active compounds to the electrode.

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