Abstract
In the case of a single-electron reaction with account for slow diffusion of reagents, equations for actual (experimentally determined) activation energies of two types were derived and analyzed: real energy A f, i.e., the energy measured at a constant electrode polarization value η = const) and formal energy (Ωf, i.e., the value measured at a constant value of potential vs. an ambiguously chosen reference electrode E = const). It is found that under the conditions of a sufficiently significant deviation from equilibrium, the actual activation energy A f is the weighted arithmetic mean of the diffusion activation energy and the sum of A 0 + αFη (where A 0 is the real activation energy of the discharge stage at polarization of η = 0); herewith, the weighting coefficients are the corresponding values of the current of the discharge stage and the limiting diffusion current. A similar relationship is also obtained for Ωf. It is found that the A f, η- and Ωf, E-curves can in a number of cases feature regions with the negative A f and Ωf values in the mixed kinetics range.
Similar content being viewed by others
References
Tomilov, B.I. and Loshkarev, M.A., Dokl. Akad. Nauk SSSR, 1963, vol. 151, p. 894.
Gorbacheev, S.V., Tr. Mosk. Khim. Tekhnol. Inst., 1959, no. 26, p. 3.
Kublanovskii, V.S., Nikitenko, V.N., and Chornen’kaya, N.V., Ukr. Khim. Zh., 2002, vol. 68, no. 4, p. 101.
Temkin, M.I., Zh. Fiz. Khim., 1948, vol. 22, p. 1081.
Krishtalik, L.I., Kinetika slozhnykh elektrokhimicheskikh reaktsii (The Kinetics of Complex Electrochemical Reactions), Moscow: Nauka, 1981.
Danilov, F.I. and Protsenko, V.S., Elektrokhimiya, 2009, vol. 45, no. 9 [Russ. J. Electrochem. (Engl. Transl.), vol. 45, no. 9].
Kaazik, Yu.Ya., Matematicheskii slovar’ (Mathematical Dictionary), Tallinn: Valgus, 1985.
Damaskin, B.B. and Petrii, O.A., Vvedenie v elektrokhimicheskuyu kinetiku (The Introduction to Electrochemical KInetics), Moscow: Vyssh. Shkola, 1975.
Tomilov, B.I., Cand. Sci. (Chem.) Dissertation, Dnepropetrovsk: DKhTI, 1962.
Gorbachev, S.V., Zh. Fiz. Khim., 1950, vol. 24, no. 7, p. 888.
Gorbachev, S.V. and Starostenko, E.P., Zh. Fiz. Khim., 1952, vol. 26, p. 624.
Gorbachev, S.V. and Starostenko, E.P., Zh. Fiz. Khim., 1952, vol. 26, p. 787.
Gorbachev, S.V. and Starostenko, E.P., Zh. Fiz. Khim., 1952, vol. 26, p. 802.
Demidovich, B.P. and Maron, I.A., Osnovy vychislitel’noi matematiki (Basics of Computational Mathematics), Moscow: Nauka, 1966.
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © F.I. Danilov, V.S. Protsenko, 2009, published in Elektrokhimiya, 2009, Vol. 45, No. 10, pp. 1187–1196.
The paper was prepared for the issue devoted to M.I. Temkin centenary.
Rights and permissions
About this article
Cite this article
Danilov, F.I., Protsenko, V.S. Actual activation energy of electrode process under mixed kinetics conditions. Russ J Electrochem 45, 1105–1114 (2009). https://doi.org/10.1134/S1023193509100012
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S1023193509100012