Abstract
Oxygen reduction on bright platinum in concentrated H3PO4 has been investigated with the rotating disc electrochemical technique at temperatures from 25 to 250° C and oxygen pressures up to 1.77 MPa. Cyclic voltammetry has been employed to study the anodic film formed on platinum in concentrated H3PO4 and the possible electroreduction of H3PO4 on platinum. The apparent transfer coefficient for the oxygen reduction has been found to be approximately proportional to temperature rather than independent of temperature. Such behaviour is difficult to reconcile with accepted theories for the effect of electrode potential on the energy barriers for electrode processes. It is of importance to establish an understanding of this phenomenon. Possible factors which can contribute to the temperature dependence of the transfer coefficient but which would not necessarily result in a direct proportionality to temperature include potential dependent adsorption of solution phase species, restructuring of the solution in the compact layer, proton and electron tunnelling, a shift in rate-determining step, changes in the symmetry of the potential energy barrier, penetration of the electric field into the electrode phase, insufficient correction for ohmic losses, and impurity effects.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Abbreviations
- α:
-
transfer coefficient
- β:
-
symmetry factor
- β′:
-
temperature independent component of β
- ν:
-
stoichiometric number
- ω:
-
rotation rate (r.p.m.)
- a,c :
-
constant and temperature coefficient in Equation 4 (no unit and K−1, respectively)
- B :
-
slope of Koutecky-Levich plot (mA cm−2 (r.p.m.)1/2)
- b :
-
Tafel slope (V dec.−1)
- E :
-
potential (V)
- F :
-
Faraday (C mol−1)
- i :
-
current density (A cm−2)
- i L :
-
diffusion limiting current density (A cm−2)
- K :
-
temperature independent component of Tafel slope (V dec−1.)
- R :
-
gas constant (J mol−1 K−1)
- T :
-
temperature (K)
- n :
-
number of electrons
- \((^{\ddag } ){\rm O}\) :
-
standard free energy of activation for forward process (J mol−1)
- \((^{\ddag } ){\rm O}\) :
-
standard enthalpy of activation for forward process (J mol−1)
- \((^{\ddag } ){\rm O}\) :
-
standard entropy of activation for forward process (J mol−1 K−1)
References
B. E. Conway and D. J. MacKinnon,J. Electrochem. Soc. 116 (1969) 1665.
B. E. Conway, D. J. MacKinnon and B. V. Tilak,Trans. Faraday Soc. 73 (1969) 1203.
B. E. Conway, in ‘Modern Aspects of Electrochemistry’, (edited by B. E. Conway, J. O'M. Bockris and R. White), Vol. 16, Plenum, New York (1986), Chapter 2, p. 103
J. N. Agar,Disc. Faraday Soc. (1947) 81.
W. Roiter and R. Jampolskaja,Acta Physiochim. 7 (1937) 247.
B. R. Scharifker, P. Zelenay and J. O'M. Bockris,J. Electrochem. Soc. 134 (1987) 2714.
E. Kirowa-Eisner, M. Schwarz and E. Gileadi,Electrochim. Acta 34 (1989) 1103.
S. J. Clouser, Ph.D. thesis, Department of Chemistry, Case Western Reserve University, Cleveland, OH, (1982).
W. M. Vogel and J. M. Baris,Electrochim. Acta 23 (1968) 463.
A. Damjanovic, D. B. Sepa and M. V. Vojnovic,ibid. 24 (1979) 887.
E. Custidiano, T. Kessler, W. E. Triaca and A. J. Arvia,ibid. 31 (1986) 1671.
J. C. Huang, R. K. Sen and E. Yeager,J. Electrochem. Soc. 126 (1979) 736.
J. O'M. Bockris and S. U. M. Khan, ‘Quantum Electrochemistry’, Plenum, New York, (1979).
B. E. Conway, D. F. Tessier and D. P. Wilkinson,J. Electroanal. Chem. 199 (1986) 249.
R. Parsons,J. Electroanal. Chem. 21 (1969) 35.
M. Ghoneim, S. Clouser and E. Yeager,J. Electrochem. Soc. 132 (1985) 1160.
Author information
Authors and Affiliations
Additional information
This paper is dedicated to Professor Brian E. Conway on the occasion of his 65th birthday, and in recognition of his outstanding contribution to electrochemistry.
Rights and permissions
About this article
Cite this article
Clouser, S.J., Huang, J.C. & Yeager, E. Temperature dependence of the Tafel slope for oxygen reduction on platinum in concentrated phosphoric acid. J Appl Electrochem 23, 597–605 (1993). https://doi.org/10.1007/BF00721951
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00721951