Abstract
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.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Abbreviations
- J i :
-
flux of speciesi
- X i :
-
generalized forces
- L ij :
-
Onsagar coefficient
- η 1 :
-
electrochemical potential of ions
- η 2 :
-
electrochemical potential of electrons
- T :
-
absolute temperature
- U *1 :
-
total energy of transfer of the ion
- \(\bar H_1 \) :
-
partial molar enthalpy of the ion
- Q *1 :
-
heat of transport of the ion
- Z 1 :
-
charge on the ion
- F :
-
Faraday constant
- Φ:
-
electrostatic potential
- μ 2 :
-
chemical potential of the electron
- μ 1 :
-
chemical potential of the ion
- \(\bar S_1 \) :
-
partial entropy of the ion
- E SE :
-
EMF developed across the solid electrolyte
- E Pt :
-
EMF developed across the platinum lead
- (μ 2)Pt :
-
chemical potential of electrons in platinum
- \((\bar S_2 )_{Pt} \) :
-
partial entropy of electrons in platinum
- (Q *2 )Pt :
-
heat of transport of electrons in platinum
- E cell :
-
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
- R :
-
universal gas constant
- \(P_{O_2 } \) :
-
partial pressure of oxygen
- \(\Delta \mu _{O_2 } \) :
-
relative chemical potential of oxygen
- Δμ M :
-
relative chemical potential of metal M
- a M :
-
activity of metal M
References
D. Janke, in ‘Science and Technology of Zirconia II’ (edited by N. Claussen, M. Rühle and A. H. Heuer), Advances of Ceramics, Vol. 12, Am. Ceram. Soc., Ohio, USA (1984) p. 636.
K. S. Goto,Trans. Iron Steel Inst. Japan 16 (1976) 469.
C. Gatellier and M. Olette,Compt. Rend. 226C (1968) 1133.
K. H. Ulrich and K. Borowski,Arch. Eisenhüttenwes 39 (1968) 259.
W. A. Fischer and D. Janke,Arch. Eisenhüttenwes 42 (1971) 249.
S. M. Shveikin, B. A. Kamaev, N. F. Bakhcheev, G. P. Zakharov and V. A. Kovylin,Steel in the USSR 3 (1973) 905.
E. Forster and H. Richter,Arch. Eisenhüttenwes 40 (1969) 475.
C. Wagner,Prog. Solid State Chem 7 (1972) 1.
C. B. Alcock, K. Fitzner and K. T. Jacob,J. Chem. Thermodyn. 9 (1977) 1011.
B. C. H. Steele, in ‘Electromotive Force Measurements in High Temperature Systems’ (edited by C. B. Alcock), Inst. Min. Met., London (1968) 3.
K. T. Jacob and J. H. E. Jeffes,Trans. Inst. Min. Met. 80C (1971) C32.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Ramasesha, S.K., Jacob, K.T. Studies on nonisothermal solid state galvanic cells — effect of gradients on EMF. J Appl Electrochem 19, 394–400 (1989). https://doi.org/10.1007/BF01015242
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF01015242