Journal of Applied Electrochemistry

, Volume 19, Issue 3, pp 394–400 | Cite as

Studies on nonisothermal solid state galvanic cells — effect of gradients on EMF

  • S. K. Ramasesha
  • K. T. Jacob


An expression for the EMF of a nonisothermal galvanic cell, with gradients in both temperature and chemical potential across a solid electrolyte, is derived based on the phenomenological equations of irreversible thermodynamics. The EMF of the nonisothermal cell can be written as a sum of the contributions from the chemical potential gradient and the EMF of a thermocell operating in the same temperature gradient but at unit activity of the neutral form of the migrating species. The validity of the derived equation is confirmed experimentally by imposing nonlinear gradients of temperature and chemical potential across galvanic cells constructed using fully stabilized zirconia as the electrolyte. The nature of the gradient has no effect on the EMF.


Physical Chemistry Zirconia Solid State Temperature Gradient Galvanic Cell 
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flux of speciesi


generalized forces


Onsagar coefficient


electrochemical potential of ions


electrochemical potential of electrons


absolute temperature


total energy of transfer of the ion

\(\bar H_1 \)

partial molar enthalpy of the ion


heat of transport of the ion


charge on the ion


Faraday constant


electrostatic potential


chemical potential of the electron


chemical potential of the ion

\(\bar S_1 \)

partial entropy of the ion


EMF developed across the solid electrolyte


EMF developed across the platinum lead


chemical potential of electrons in platinum

\((\bar S_2 )_{Pt} \)

partial entropy of electrons in platinum


heat of transport of electrons in platinum


EMF developed across the whole cell

\(\mu _{{\rm O}_2 } \)

chemical potential of oxygen

\(\mu _{{\rm O}_2 }^0 \)

chemical potential of oxygen in its standard state


universal gas constant

\(P_{O_2 } \)

partial pressure of oxygen

\(\Delta \mu _{O_2 } \)

relative chemical potential of oxygen


relative chemical potential of metal M


activity of metal M


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Copyright information

© Chapman and Hall Ltd. 1989

Authors and Affiliations

  • S. K. Ramasesha
    • 1
  • K. T. Jacob
    • 1
  1. 1.Department of MetallurgyIndian Institute of ScienceBangaloreIndia

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