Abstract
The Kolbe electrosynthesis on polycrystalline platinum in 1 M acetic acid/1 M potassium acetate electrolyte at 30 ° C was studied by using potentiostatic, low-frequency potentiodynamic and impedance techniques. Reaction products and their distribution as a function of potential were determined. There is a good correspondence in the potential ranges where changes in both stationary and non-stationary kinetic data, electrode resistance, electrode capacitance and reaction products were found. Results confirm the existence of different electrochemical reactions and correspondingly different reaction intermediates in the various Tafel regions.
Highlights
The term Kolbe electrosynthesis covers a series of reactions involving the electrooxidation of the anion of a carboxylic acid in the presence of the conjugated acid yielding the corresponding hydrocarbon and carbon dioxide [l-3]
The most extensively studied reaction is the electroformation of ethane from the acetic acid/potassium acetate buffer at acid pH values on platinum [4-181
The present paper presents kinetic data on the Kolbe reaction obtained from potentiostatic, low-frequency potentiodynamic and impedance techniques where the operational variables were systematically changes
Summary
The term Kolbe electrosynthesis covers a series of reactions involving the electrooxidation of the anion of a carboxylic acid in the presence of the conjugated acid yielding the corresponding hydrocarbon and carbon dioxide [l-3]. The most extensively studied reaction is the electroformation of ethane from the acetic acid/potassium acetate buffer at acid pH values on platinum [4-181. The kinetics of the Kolbe reaction under steady-state conditions is characterized by a Tafel relationship with a slope considerably greater than 2RT/F This result was interpreted in terms of the formation of a barrier layer on the electrode surface associated with adsorbed radicals [21]. Despite the many different techniques employed to investigate the Kolbe electrosynthesis, there are some aspects of the reaction which still remain unclear The complexity of this reaction arises both from the solution side and the metal side of the electrochemical interface [22]. The solution resistance value measured in the double layer potential region was substracted from the total electrode impedance
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