By Stal G. Mairanovskii

As our wisdom of the mechanism of electrode techniques raises, it turns into progressively more obvious that the kinetic currents first saw by way of R. Brdicka and by way of ok. Wiesner within the 1940's are very extensively encountered. Very many electrode professional­ cesses comprise a chemical level. * this can be real essentially of elec­ trode procedures that contain natural compounds. for that reason, to appreciate the mechanism of electrode approaches and, specific­ ly, to properly interpret the result of polarographic investiga­ tions, you will need to understand the features and relationships controlling the chemical reactions happening on the electrode floor. normally, those reactions are considerably assorted from traditional chemical reactions happening within the bulk of the answer, because the reactions on the electrodes are usually plagued by the electrical box of the electrode and the adsorption of the par­ ticipating compounds . the truth that hydrogen ions frequently participate in the electro­ chemical aid of natural compounds makes attainable using electrochemical equipment, relatively polarography, for the examine of protolytic reactions. those reactions play a massive function in natural chemistry: the vast majority of reactions of natural compounds in suggestions battle through a degree within which a hydrogen ion is got rid of or extra (see, for instance, [1, 2]). as a result, the polarographic learn of protolytic reactions can offer a lot vital details to theoretical natural chemistry.

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CURRENTS LIMITED BY THE RATE OF CHEMICAL REACTION 45 This was the case [218] in Koryta's experiment on the streaming electrode. It was already mentioned that if the eurrent intensity is limited by the rate of a chemical reaction, the dependenee of the half-wave potential (for a reversible electrode process) of the kinetie wave or the added eomplex-forming reagent is different from that obtained with diffusion eurrents. The dissociation constants of eomplexes ean be determined from the reversible diffusion waves on the basis of the dependenee of the half-wave potential on the concentration of the added reagent.

Basically, such a compound, a proton transfer agent from the donor (which is the acid) to the electrode, can be any organic or inorganic compound which can exist in the solution in two forms: a protonated or acid form and an unprotonated basic form. Under the specifieq. conditions only the protonated form can take part in the electrode reaction. The value of the limiting current under these conditions is determined by the rate of protonation of this compound introduced into the solution by interaction with the acids that are present in the solution.

30)]; (2) the height of preceding waves also depends on the rate of the processes that determine the subsequent waves on the polarograms. For example, the wave limited by the rate of the A- + H + reaction is affected to a certain degree by the rate of formation of A- inthe A 2- + H+ reaction; (3) with the pH of the solution increasing the wave is usually shifted toward more negative potentials; this changes the character of the influence of the structure of the double layer and adsorption of reactants on the kinetic currents (this will be discussed in detail in Chapters V and VI).

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Catalytic and Kinetic Waves in Polarography by Stal G. Mairanovskii
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