The polarographic reduction of conjugated hydrocarbons: IV. The mechanism of the reduction of various alternant and non‐alternant hydrocarbons

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Abstract
The current‐voltage curves of various alternant and non‐alternant hydrocarbons were measured in 75% and 96 % dioxane‐water. In many cases the limiting current of the first reduction wave corresponds to the overall addition of one electron. From the effect of the increase of the percentage of water and the addition of hydrogen iodide on the limiting current and on the half‐wave potential of the first and the second wave, evidence was obtained about the reduction mechanism. The primary steps of the reduction are: R + e →← R′ and R′ + e →← R″ the standard potential determined by the first electron addition is less negative than that of the second step.When the rate of proton addition to R′ is low with respect to the rate of diffusion of R′, the first wave is a one‐electron wave and the second wave involves the reduction to R″. When R′ reacts with a proton in the electrode surface layer, the reduction proceeds according to: magnified image The reduction mechanism is discussed in detail and compared with the experimental results reported in this paper or found by other investigators.

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