JCP Nameplate
  • Volume/Page
  • Keyword
  • DOI
  • Citation
  • Advanced
   
 
 
 

You Tube Flickr Twitter UniPHY Group iResearch App Facebook

Journal of Chemical Physics / Volume 130 / Issue 23 / ARTICLES / Surfaces, Interfaces, and Materials

J. Chem. Phys. 130, 234704 (2009); doi:10.1063/1.3152847 (10 pages)

Standard electrode potential, Tafel equation, and the solvation thermodynamics

Dmitry V. Matyushov

Center for Biological Physics, Arizona State University, P.O. Box 871504, Tempe, Arizona 85287-1504, USA

View MapView Map

(Received 11 April 2009; accepted 20 May 2009; published online 18 June 2009)

Equilibrium in the electronic subsystem across the solution-metal interface is considered to connect the standard electrode potential to the statistics of localized electronic states in solution. We argue that a correct derivation of the Nernst equation for the electrode potential requires a careful separation of the relevant time scales. An equation for the standard metal potential is derived linking it to the thermodynamics of solvation. The Anderson–Newns model for electronic delocalization between the solution and the electrode is combined with a bilinear model of solute-solvent coupling introducing nonlinear solvation into the theory of heterogeneous electron transfer. We therefore are capable of addressing the question of how nonlinear solvation affects electrochemical observables. The transfer coefficient of electrode kinetics is shown to be equal to the derivative of the free energy, or generalized force, required to shift the unoccupied electronic level in the bulk. The transfer coefficient thus directly quantifies the extent of nonlinear solvation of the redox couple. The current model allows the transfer coefficient to deviate from the value of 0.5 of the linear solvation models at zero electrode overpotential. The electrode current curves become asymmetric in respect to the change in the sign of the electrode overpotential.

© 2009 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. ELECTRONIC CHEMICAL POTENTIAL IN SOLUTION
  3. FREE ENERGY SURFACES OF HETEROGENEOUS ELECTRON TRANSFER
  4. NONLINEAR SOLVATION
  5. DISCUSSION

RELATED DATABASES

To view database links for this article, you need to log in.

KEYWORDS and PACS

Keywords

charge exchange, chemical equilibrium, electrochemical electrodes, free energy, oxidation, reaction kinetics theory, reduction (chemical), solvation, thermochemistry

PACS

  • 82.60.Lf

    Thermodynamics of solutions

  • 82.20.-w

    Chemical kinetics and dynamics

  • 82.30.Nr

    Association, addition, insertion, cluster formation

  • 82.45.Fk

    Electrodes

  • 82.30.Fi

    Ion-molecule, ion-ion, and charge-transfer reactions

  • 82.60.Hc

    Chemical equilibria and equilibrium constants

ARTICLE DATA

Permalink
http://link.aip.org/link/doi/10.1063/1.3152847

PUBLICATION DATA

ISSN:

0021-9606 (print)  
1089-7690 (online)

Publisher:

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
    R. A. Marcus, J. Chem. Phys. 24, 966 (1956)JCPSA6000024000005000966000001.

    D. V. Matyushov and G. A. Voth, J. Chem. Phys. 113, 5413 (2000)JCPSA6000113000013005413000001.

    J. B. Straus, A. Calhoun, and G. A. Voth, J. Chem. Phys. 102, 529 (1995)JCPSA6000102000001000529000001.

    A. M. Kuznetsov, I. G. Medvedev, and V. V. Sokolov, J. Chem. Phys. 120, 7616 (2004)JCPSA6000120000016007616000001.

    H. Keiter, Phys. Rev. B 2, 3777 (1970).

    P. W. Anderson, Phys. Rev. 124, 41 (1961).

    N. S. Hush, J. Chem. Phys. 28, 962 (1958)JCPSA6000028000005000962000001.

    D. N. LeBard and D. V. Matyushov, Phys. Rev. E 78, 061901 (2008).

    D. R. Martin and D. V. Matyushov, Phys. Rev. E 78, 041206 (2008).

    S. Garde, G. Hummer, A. E. García, M. E. Paulaitis, and L. R. Pratt, Phys. Rev. Lett. 77, 4966 (1996).


Figures (6) Tables (1)

Access to article objects (figures, tables, multimedia) requires a subscription; log in to view available files.
(Access to supplementary files, where available, is free for this journal.)

Access to article objects (figures, tables, multimedia) requires a subscription; log in to view available files.
(Access to supplementary files, where available, is free for this journal.)



Close

Google Calendar

ADVERTISEMENT

Your Recent History Recent History Help

Recently Viewed

  1. Standard electrode potential, Tafel equation, and the solvation thermodynamics
  2. On the relationship between two popular lattice models for polymer melts
  3. A multicenter numerical integration scheme for polyatomic molecules
Go to AIP Home
Copyright © American Institute of Physics
close