By Stal G. Mairanovskii
As our wisdom of the mechanism of electrode methods raises, it turns into an increasing number of obvious that the kinetic currents first saw by way of R. Brdicka and by way of okay. Wiesner within the 1940's are very extensively encountered. Very many electrode seasoned cesses comprise a chemical degree. * this is often real essentially of elec trode strategies that contain natural compounds. for that reason, to appreciate the mechanism of electrode procedures 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 occurring on the electrode floor. usually, those reactions are considerably various from usual chemical reactions happening within the bulk of the answer, because the reactions on the electrodes are usually suffering from 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 big function in natural chemistry: nearly all of reactions of natural compounds in options battle through a level during which a hydrogen ion is got rid of or additional (see, for instance, [1, 2]). for that reason, the polarographic research of protolytic reactions can provide a lot very important details to theoretical natural chemistry.
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Extra info for Catalytic and Kinetic Waves in Polarography
The temperature coefficient of the limiting current is 20%/deg. Similarly to aliphatic haloaldehydes, dichlorocyclohexanone is more completely hydrated than the monochloro-derivatives . Two waves can be observed on the polarographic curves of gem-dichlorocyclohexanone corresponding to the gradual cleavage of both carbon-chlorine bonds. It was shown spectroscopically that the degree of hydration of the carbonyl group of mono- and di- G-chlorocyclohexanones decreases in the following order: trans> cis> gern> monochloro-derivatives.
A very interesting type of catalytic current was described by Kastening . The anion radicals, formed in alkaline medium in the presence of camphor by reversible, single-electron reduction of aromatic nitro compounds, can be oxidized in the solution chemically. In the presence of oxidants [copper(II)-tartarate,IOi], they are oxidized to the original nitro compounds which can be again reduced on the electrode gi ving an additional kinetically limited current. The anion radicals also are able to take part in disproportionation reactions, which lead to formation of the corresponding hydroxylamine derivatives, and the original nitro compounds are regenerated .
In reality, these authors dealt with the overall rate of transfer of protons from acids present in the solutions to the molecules of the catalyst; this transfer resulted in catalytic hydrogen formation or production of p-nitroaniline, which they used as proton-transfer agent rather than azobenzene. Wolf [179, 180] used the dependence of the height of the kinetic wave on the drop period for the determination of the rate constant of an antecedent reaction. The drop period in these experiments was regulated by a periodic tapping on the end of the capillary; this kept the rate of mercury flow practically constant.