Irreversible Thermodynamic Analysis of the Cross Effect between Electron and Ion Currents in Ionic Compounds with Electronic Conduction Prevailing

전자 전도체 이온결합 화합물에서 전자 흐름과 이온 흐름간 간섭 현상의 비가역 열역학적 분석

  • 유한일 (서울대학교 공과대학 무기재료공학과)
  • Published : 1988.03.01


The cross effect between an ion flux and an electronic current in a nonstoichiometric binary oxide, $A_{1-\delta}O_\mu$, has been analyzed in the light of irreversible thermodynamics. It has been shown that a net flux of the mobile cation vacancy is induced through the system in an electrical potential gradient applied across a pair of the reversible electrodes, which makes the Fick frame shift relative to the laboratory frame. As a consequence, the relative shift is a measure of the effective charge responsible for the cross effect. Two experiments are proposed to measure the shift.



  1. Reactivity of Solids v.1 Behavior of(Semiconducting) Oxide Crystals in Oxygen Potential Gradients H. Schmalzried
  2. Ann. Rev. Mater. Sci. v.17 Transport in Chemical Potential Gradients of Multicomponent Oxides H. Schmalzried
  3. Reactivity of Solids v.1 Instability of Ternary Compounds in an Oxygen Potential Gradient W. Laqua;H. Schmalzried;K. Dyrek(ed.);J. Haber(ed.);J. Nowotny(ed.)
  4. Z. Naturforsch. v.34a Crystalline Oxide Solid Solutions in Oxygen Potential Gradients H. Schmalzried;W. Laqua;P.L. Lin
  5. Rep. Prog. Phys. v.27 Matter Transport in Solids R.E. Howard;A.B. Lidiard
  6. Rep. Prog. Phys. v.50 Statistical Theories of Atomic Transport in Crystalline Solids A.R. Allnatt;A.B. Lidiard
  7. Prog. Solid-State Chem. v.10 Equations for Transport in Solid Oxides and Sulfides of Transition Metals C. Wagner
  8. Diffusion Electro- and Thermo-migration in Metals H.B. Huntington
  9. Encyclopedia of Semiconductor Technology Electromigration F.M. D'Heurle;D.T. Peterson;M. Grayson(ed.)
  10. J. Appl. Phys. v.60 Activation Energy for Electromigration Failure in Al-Cu Conductor Strips Covered with Polyimide J.R. Lloyd;R.N. Steagall
  11. Ber. Bunsenges. Phys. Chem. v.91 Impurity Diffusion in a Chemical Potential Gradient(Ⅰ): Theoretical Results M. Martin
  12. Ber. Busenges. Phys. Chem. v.91 Impurity Diffusion in a Chemical Potential Gradient(Ⅱ): Iron Tracer Diffusion in Cobalt Oxide in an Oxygen Potential Gradient M. Martin;S. Doriis
  13. Solid State Ionics v.20 Tracer Diffusion in Chemical Potential Gradients M. Martin;H. Schmalzried
  14. Mass Transport in Solids Diffusion in Stoichiometric Closed-Packed Oxides B.J. Wuensch;F. Beniere(ed.);C.R.A. Catlow(ed.)
  15. Thermodynamics of Irreversible Processes S.R. de Groot
  16. Non-Equilibrium Thermodynamics S.R. de Groot;P. Mazur
  17. Introduction to Thermodynamics of Irreversible Processes I. Prigogine
  18. Thermodynamics of Irreversible Processes R. Haase
  19. J. Phys. Chem. Solids v.49 Irreversible Thermodynamic Analysis of Nonisothermal Isotopic Interdiffusion in Ionic Solids H.-I. Yoo;B.J. Wuensch
  20. Nonstoichimetry, Diffusion, and Electrical Conductivity in Binary Oxides P. Kofstad
  21. Free Energy of Formation of Binary Compounds T.B. Reed
  22. Ber. Bunsenges. Phys. Chem. v.89 cobaltous Oxide in an Oxygen Potential Gradient: Morphological Stability of the Phase Boundaries M. Martin;H. Schmalzried
  23. Ber. Bunsenges. Phys. Chem. v.89 Morphological Stability in the Course of solid State Reactions: The System Fe₃O₄-Mn₃O₄-Cr₂O₃ M. Backhanus-Ricoult;H. Schmalzried
  24. The Mathematics of Diffusion(2nd ed.) J. Crank
  25. Adv. Ceram. v.10 Secondary Ion Mass Spectrometric Analysis of Oxygen Self-Diffusion in Single Crystal MgO H.-I. Yoo;B.J. Wuensch;W.T. Petuskey