Mixture potentials: The systems ferricyanide-ferrocyanide and iodine-iodide at platinum electrodes

Spiro, Melford E.; Johnston, Ryan; Wagner, Elżbieta

doi:10.1016/0013-4686(61)85002-0

Cited by 3 publications

(2 citation statements)

References 6 publications

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“…Although, in late 1940 s it was speculated that a catalytic chemical reaction may also follow an electrochemical pathway, [6][7][8][9][10] the first quantitative support to this idea was provided by the works of Spiro et al spanning almost three decades. 1,11,12 Further, Spiro et al 1 observed that the mixed potential developed at the electrode does indeed correspond to that for the equilibrium mixture. Further analysis revealed that the reaction can be analyzed as an electron transfer mechanism where at steady state, electrons are transferred from one chemical species to another.…”

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confidence: 91%

“…This particular nomenclature of mixed potential is given to the "potential developed by an electrode when it is subjected to the influence of more than one redox reactions that are not in chemical equilibrium". 1 That the mixed potential theory can be used to understand metal catalyzed chemical reactions opens up a new avenue in catalysis with a number of important implications. The first is that although the overall reaction is non-electrochemical in nature, the partial reactions, which constitute the overall reaction, are electrochemical in nature and hence can be studied using electrochemical means.…”

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confidence: 99%

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Correlation of Chemical and Electrochemical Catalysis-Importance of Half Reactions: The Case of Catalytic Oxidation of Ferrous Sulfate by Molecular Oxygen

Chauhan

Dameera

Juvekar

et al. 2018

J. Electrochem. Soc.

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Catalytic oxidation of ferrous sulfate with molecular oxygen in 0.5 M H 2 SO 4 has been studied on carbon supported platinum catalyst. Analysis of this catalytic chemical reaction as two distinct electrochemical half reactions proceeding on the catalyst surface is presented. Further, it is proposed that the catalytic chemical reaction can be studied based on mixed potential theory. Pertinent results for the proposal are presented in terms of conversions to ferric ions and the potential acquired by the electrode when immersed in an oxygen saturated solution of ferrous sulfate (mixed potential). The two individual half reactions have been studied separately to obtain key electrochemical parameters through rotating disk electrode experiments. A theoretical approach is also presented that would enable analysis of the catalytic chemical reaction through few electrochemical parameters. The results obtained clearly demonstrate that a greater understanding of various mechanistic aspects of a catalytic chemical reaction can be achieved if it is studied as two or more distinct electrochemical half reactions connected through an electron transfer mechanism.

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