By Stal G. Mairanovskii
As our wisdom of the mechanism of electrode tactics raises, it turns into an increasing number of obvious that the kinetic currents first saw by means of R. Brdicka and by means of okay. Wiesner within the 1940's are very commonly encountered. Very many electrode seasoned cesses comprise a chemical degree. * this is often actual basically of elec trode techniques that contain natural compounds. consequently, to appreciate the mechanism of electrode methods and, specific ly, to properly interpret the result of polarographic investiga tions, it is very important recognize the features and relationships controlling the chemical reactions occurring on the electrode floor. regularly, those reactions are considerably diversified from usual chemical reactions occurring within the bulk of the answer, because the reactions on the electrodes are usually tormented 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 aid of natural compounds makes attainable using electrochemical tools, quite polarography, for the examine of protolytic reactions. those reactions play an enormous function in natural chemistry: the vast majority of reactions of natural compounds in recommendations wade through a level during which a hydrogen ion is got rid of or extra (see, for instance, [1, 2]). accordingly, the polarographic learn of protolytic reactions can provide a lot vital details to theoretical natural chemistry.
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Extra resources for Catalytic and Kinetic Waves in Polarography
For this reason, a change in pH, which affects both the ratio of the hydrated acid and its anion concentrations in the solution and also affects the rate of the protolytic reactions, causes a change of wave height. The increase in the wave height in strongly acidic solutions was explained by these authors by the enolization of the keto group. It must be mentioned here that Müller and Baumberger , who first observed the change of wave height of such compounds with pH, explained it by the keto-enol tautomerism.
The first stage to appear corresponds to the discharge of the undissociated acid; the second corresponds to the reduction of its anion. 0 only one wave of anion reduction remains that is limited by the rate of dehydration. 32; then it begins to decrease. The increase of the wave height in strongly acidic and basic solutions is caused by the acid - base catalysis of the dehydration reaction of the undissociated acid and its anions, respectively. The reduction of the wave height in a strongly alkaline medium is caused by the acidic dissociation of the aldehyde group .
Chronopotentiometric measurements showed that the current is of catalytic nature. The authors  assumed that the catalytic character of the process is caused by discharge of the subcompound MCl which is later regenerated in the re action of the electrode product (metal) with the electrolyte: M + MCl 2 - 2MCl. The theoretically interesting catalytic hydrogen evolution wave observed in the polarography of tellurium (IV) compounds [121-125] takes the form of a sharp maximum on the reduction wave of TeO~-.
Catalytic and Kinetic Waves in Polarography by Stal G. Mairanovskii