Electrochemistry and Photopotentials of Phenazine in Methanol Solutions

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Abstract
Linear‐potential‐scan voltammetry and coulometry have been used to study the electrochemistry of phenazine in methanol solutions. Parallel work (reported elsewhere) was done on the photochemistry of this compound and the combined results led to elucidation of the species involved in the development of photopotentials which occurred upon illumination of phenazine solutions. Acid‐base processes dominated the electrochemistry; in acid solution the reactant at a cathode was the diprotonated phenazine, yielding a stable semiquinone radical which was further reduced in a separate step to dihydrophenazine. Oxidation of the products proceeded readily. In buffered solutions of the neutral range, the reactant was monoprotonated phenazine and the over‐all rate was strongly influenced by the protonation step; a single reduction wave of two electrons occurred and reoxidation yielded phenazine. Photopotentials in acid solution were due to diprotonated phenazine and photochemically produced semiquinone radical of the same species. In neutral buffered solutions the photochemical product was dihydrophenazine and the photopotential was due to this species and monoprotonated phenazine.

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