Electrical Double Layer at a Metal-Dilute Electrolyte Solution Interface

ISBN-13: 9783540119951 / Angielski / Miękka / 1983 / 176 str.

G. a. Martynov; R. R. Salem

Opis

Most of the properties of a metal-electrolyte interface, even the spe- cific nature of an electrode reaction, proneness of a metal to cor- rosion, etc., are primarily determined by the electrical double layer (EDL) at this boundary. It is therefore no surprise that for the last, at least, one hundred years intent attention should have been centered on EDL. So much of material has been gathered to date that we are easi- ly lost in this maze of information. A substantial part of the attempts to systematize these facts is made at present within the framework of thermodynamics. Such a confined approach is undoubtedly inadequate. The Gouy-Chapman theory and the Stern-Grahame model of the dense part of EDL developed 40-70 years ago, tailored appropriately to suit the occasion, inevitably underlie any description of EDL. This route is rather too narrow to explain all the facts at our disposal. A dire necessity has thus arisen for widening the principles of the micros- copic theory. This is precisely the objective of our monograph. Fur- thermore, we shall dwell at length on the comparison of the theory with experiment: without such a comparative analysis, any theory, however elegant it may be, is just an empty drum.

Spis treści

I. Ionic Part of the Double Layer.- I. Classical theories of electrical double layer.- 1. Capacity of the double layer.- 2. The Gouy-Chapman theory of continuous double layer.- 3. Comparison of the Gouy-Chapman theory with experiments.- 4. The Wagner-Onsager-Samaras theory of discrete double layer.- 5. The Stern theory of specific adsorption.- 6. Comparison of the Stern theory with experiments.- 7. The Grahame model.- II. Physical principles of the statistical theory of the double layer.- 8. Formulation of the problem.- 9. Equations for the chemical potentials.- 10. Dilute electrolyte solutions.- III. Electrostatic adsorption in the Gouy layer.- 11. Solution of the equations.- 12. Comparison with experiments.- IV. Specific adsorption in the Stern layer.- 13. Adsorption isotherm and electroneutrality equation.- 14. Analysis of the electroneutrality equation.- 15. Double layer capacity and specific adsorption.- 16. Comparison with experiments.- II. Electronic Part of the Double Layer.- V. Experimental data.- 17. Electrocapillary curves and zero-charge potentials.- 18. Integral capacity.- VI. Molecular capacitor.- 19. Theory.- 20. Zero-charge point of an electrode.- 21. Integral capacity.- VII. Electronic capacitor.- 22. Electron distribution inside the electronic capacitor.- 23. Potential distribution inside the electronic capacitor.- 24. Electron work function for a metal-vacuum interface.- 25. Contact potential difference.- 26. Surface tension of the metal-vacuum interface.- 27. Qualitative analysis of the properties of the electronic capacitor at the metal-electrolyte interface.- 28. Dielectric permittivity of a solvent.- 29. Dipole potential drop.- 30. Dependence of surface tension of mercury on the zero-charge potential.- 31. Integral capacity of the electronic capacitor.- 32. The outer plate of the electronic capacitor.- Conclusions.- References.