13
electron is transferred by tunneling without any change in total energy, accomplished by thermal fluctuation in the solvent molecules. If as a result of solvent
fluctuation energy is equal for the initial and final states, the tunneling of the electrons from the metal to the reactant can take place. Levich and Dogonadze [19]
using quantum-mechanical treatment have shown that the variation of potential
energy with displacement is parabolic, equivalent to a simple harmonic oscillation
of the solvent.
A simple treatment of the role of solvent fluctuations is due to Marcus [20]. He
used classical statistical thermodynamics. His treatment works reasonably well for
homogenous electron-transfer reactions involving single electron and to a lesser
extent for heterogeneous redox reactions.
References
1. B.E. Conway, Theory and Principles of Electrode Processes (Ronald, London, 1965)
2. S. Trasatti, The electrode potential, in Comprehensive Treatise of Electrochemistry, ed. by
J. O. M. Bockris, B. E. Conway, E. Yeager, vol. 1, (Plenum Press, New York, 1980), pp. 45–81
3. J.O.M. Bockris, Reddy AKN, Gamboa-Aldeco M (2000) Modern Electrochemistry, 2nd
Kluwer Academic/Plenum Publishers New York. vol. 2A
4. R.R. Adzic, E.B. Yeager, Encyclopedia of Applied Physics, vol 5 (VCH Publishers, New York,
1993). Trigg GL (ed.)
5. H. Helmholtz, Ueber einige Gesetze der Vertheilung elektrischer Ströme in körperlichen
Leitern mit Anwendung auf die thierisch-elektrischen Versuche. Annalen der Physik und
Chemie 165(6), 211–233., Bibcode:1853 AnP...165..211H (in German) (1853). https://doi.
org/10.1002/andp.18531650603
6. G. Gouy, Ann. Chim. Phys. 29, 145 (1903)
7. D.L. Chapman, Phylos. Mag. 25, 475 (1913)
8. O. Stern, Zur Theorie der Elektrolytischen Doppelschicht. Zeitschrift für Elektrochemie. 30,
508 (1924). https://doi.org/10.1002/bbpc.192400182
9. A. Hamelin. In Modern Aspects of Electrochemistry, ed. by J.O.M. Bockris, B.E. Conway, vol
16. (Pergamon, New York, 1985). A. Hamelin, T. Vitanotv, E. Sevastyanov, The electrochemical double layer on sp metal single crystals: The current status of data. J. Electroanal. Chem.
145, 225 (1983)
10. A. Cuesta, D.M. Kolb, The structure of bromide and chloride adlayers on Au(100) electrodes:
An in situ STM study. Surf. Sci. 465, 310–316 (2000)
11. A.M. Bond, C. Coomber Darren, W. Feldberg Stephen, K.B. Oldham, T. Vu, An experimental evaluation of cyclic voltammetry of multicharged species at macrodisk electrodes in the
absence of added supporting electrolyte. Anal. Chem. 73(2), 352–359 (2001)
12. K. Sasaki, N.S. Marinkovic, H. Isaacs, R.R. Adzic, Synchrotron-based in situ characterization of carbon-supported platinum and platinum monolayer electrocatalysts. ACS Catal. 6, 69
(2016)
13. S. Strbac, R.R. Adzic, A. Hamelin, Oxide formation on gold single crystal stepped surfaces.
J. Electroanal. Chem. 249, 291–310 (1988)
14. D.M. Kolb, J. Schneider, Surface reconstruction in electrochemistry: Au(100)-(5x20),
Au(111)-(1x23) and Au(110)-(1x2). Electrochim Acta 31, 929–936 (1986)
15. M.A. Schneeweiss, D.M. Kolb, Oxide formation on Au(111) an in situ STM study. Solid State
Ionics 94, 171–179 (1997)
References
electron is transferred by tunneling without any change in total energy, accomplished by thermal fluctuation in the solvent molecules. If as a result of solvent
fluctuation energy is equal for the initial and final states, the tunneling of the electrons from the metal to the reactant can take place. Levich and Dogonadze [19]
using quantum-mechanical treatment have shown that the variation of potential
energy with displacement is parabolic, equivalent to a simple harmonic oscillation
of the solvent.
A simple treatment of the role of solvent fluctuations is due to Marcus [20]. He
used classical statistical thermodynamics. His treatment works reasonably well for
homogenous electron-transfer reactions involving single electron and to a lesser
extent for heterogeneous redox reactions.
References
1. B.E. Conway, Theory and Principles of Electrode Processes (Ronald, London, 1965)
2. S. Trasatti, The electrode potential, in Comprehensive Treatise of Electrochemistry, ed. by
J. O. M. Bockris, B. E. Conway, E. Yeager, vol. 1, (Plenum Press, New York, 1980), pp. 45–81
3. J.O.M. Bockris, Reddy AKN, Gamboa-Aldeco M (2000) Modern Electrochemistry, 2nd
Kluwer Academic/Plenum Publishers New York. vol. 2A
4. R.R. Adzic, E.B. Yeager, Encyclopedia of Applied Physics, vol 5 (VCH Publishers, New York,
1993). Trigg GL (ed.)
5. H. Helmholtz, Ueber einige Gesetze der Vertheilung elektrischer Ströme in körperlichen
Leitern mit Anwendung auf die thierisch-elektrischen Versuche. Annalen der Physik und
Chemie 165(6), 211–233., Bibcode:1853 AnP...165..211H (in German) (1853). https://doi.
org/10.1002/andp.18531650603
6. G. Gouy, Ann. Chim. Phys. 29, 145 (1903)
7. D.L. Chapman, Phylos. Mag. 25, 475 (1913)
8. O. Stern, Zur Theorie der Elektrolytischen Doppelschicht. Zeitschrift für Elektrochemie. 30,
508 (1924). https://doi.org/10.1002/bbpc.192400182
9. A. Hamelin. In Modern Aspects of Electrochemistry, ed. by J.O.M. Bockris, B.E. Conway, vol
16. (Pergamon, New York, 1985). A. Hamelin, T. Vitanotv, E. Sevastyanov, The electrochemical double layer on sp metal single crystals: The current status of data. J. Electroanal. Chem.
145, 225 (1983)
10. A. Cuesta, D.M. Kolb, The structure of bromide and chloride adlayers on Au(100) electrodes:
An in situ STM study. Surf. Sci. 465, 310–316 (2000)
11. A.M. Bond, C. Coomber Darren, W. Feldberg Stephen, K.B. Oldham, T. Vu, An experimental evaluation of cyclic voltammetry of multicharged species at macrodisk electrodes in the
absence of added supporting electrolyte. Anal. Chem. 73(2), 352–359 (2001)
12. K. Sasaki, N.S. Marinkovic, H. Isaacs, R.R. Adzic, Synchrotron-based in situ characterization of carbon-supported platinum and platinum monolayer electrocatalysts. ACS Catal. 6, 69
(2016)
13. S. Strbac, R.R. Adzic, A. Hamelin, Oxide formation on gold single crystal stepped surfaces.
J. Electroanal. Chem. 249, 291–310 (1988)
14. D.M. Kolb, J. Schneider, Surface reconstruction in electrochemistry: Au(100)-(5x20),
Au(111)-(1x23) and Au(110)-(1x2). Electrochim Acta 31, 929–936 (1986)
15. M.A. Schneeweiss, D.M. Kolb, Oxide formation on Au(111) an in situ STM study. Solid State
Ionics 94, 171–179 (1997)
References