Skip to main content

Advertisement

Log in

Polarization and adsorption effects on the wettability of a gold electrode by lithium, sodium, potassium, and cesium chloride melts

  • Original Paper
  • Published:
Ionics Aims and scope Submit manuscript

Abstract

To establish the patterns of the wettability of solid surfaces by ionic melts, the wetting energy of a gold electrode by lithium, sodium, potassium, and cesium chloride melts was studied as a function of the electrical potential applied to the electrode. It was established that when the potential was shifted in the positive direction relative to the zero-charge potential of gold in the corresponding melt, the shape of the curve that defined the dependence of the wetting energy on the electrical potential varied according to the salt composition: for lithium and sodium chlorides, the wetting energy increased monotonically, while in potassium and cesium chloride melts there was a maxima. This phenomenon was explained from the standpoint of the mutual polarization of gold and chlorine ions in the place of their direct contact. At a certain electric field strength in the double electric layer and at a certain binding energy of the melt particles, the resultant mutual ion polarization led to the formation of ordered layers of ionic associations (presumably AuCln(n − 1)-) on the anode surface, which shielded the electrode charge.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. (2013) Molten Salts Chemistry. In: Lantelme F, Groult H (eds) From lab to applications, Elsevier, Amsterdam, 354 p

  2. Adamson AW (1990) Physical chemistry of surfaces, 5th edn. Wiley, New York

    Google Scholar 

  3. De Gennes PG (1985) Wetting: statics and dynamics. Rev Mod Phys 57:827–863

    Article  Google Scholar 

  4. Vogt H (1999) The anode effect as a fluid dynamic problem. J Appl Electrochem 29:137–145

    Article  CAS  Google Scholar 

  5. Meunier P, Welch B, Skillas-Kasacos M, Sahajwalla V (2009) Effect of dopands on wetting properties and electrochemical behaviour of graphite anodes in molten Al2O3-cryolite melts. J Appl Electrochem 39:837–847

    Article  CAS  Google Scholar 

  6. Frolov AV, Gusev AO, Shurov NI, Kulik NP, Sitnikov LV, Babushkina LM, Stepanov VP, Zaykov YP, Khramov AP, Malkov VB (2006) Wetting and cryolite bath penetration in graphitized cathode materials. Light metals TMS (The Minerals, Metals & Materials Soc):645–649

  7. Baumli P, Kaptay G (2008) Wettability of carbon surfaces by pure molten alkali chlorides and their penetration into a porous graphite substrate. Mater Sci Eng A 495:192–196

    Article  CAS  Google Scholar 

  8. Kavase M, Mugikura Y, Watanabe T (2000) An electrolyte distribution model in consideration of the electrode wetting in molten carbonate fuel cell. J Electrochem Soc 147:854–860

    Article  Google Scholar 

  9. Altomare M, Truong NN, Schmuki P (2016) Templated dewetting: designing entirely self-organized platforms for photocatalysis. Chem Sci 7:6865–6886

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  10. Mugele F, Baret J-C (2005) Electrowetting: from basics to applications. J Phys Condens Matter 17:R705–R774

    Article  CAS  Google Scholar 

  11. Stepanov VP, Yakshevich IV, Belyaev VS (2000) Adsorption activity of Cu, Au and Ni solid electrodes in molten carbonates. Z Phys Chem 214:359–377

    Article  CAS  Google Scholar 

  12. Puddephatt RJ (1978) The chemistry of gold. Elsevier Scientific, Amsterdam

    Google Scholar 

  13. Warren RW (1965) Procedures and apparatus for zone purification of the alkali halides. Rev Sci Instrum 36:731–737

    Article  CAS  Google Scholar 

  14. Smirnov MV, Aleksandrov KA, Khokhlov VA (1977) Diffusion potentials and transport number in molten alkali chlorides and their binary mixtures. Electrochim Acta 22:543–550

    Article  CAS  Google Scholar 

  15. Smirnov MV, Stepanov VP (1979) Zero-point potential of metals in molten alkali halides and their binary mixtures. Electrochim Acta 24:651–655

    Article  CAS  Google Scholar 

  16. Bukun NG, Alekseeva RA (1975) The double layer capacity of gold in a chloride melt. Elektrokhimiya (in Russian) 11:1738–1741

    CAS  Google Scholar 

  17. Lockett V, Sedev R, Ralston J, Rodopoulos T, Horne M (2008) Differential capacitance of the electrical double layer in imidazolium-based ionic liquids: influence of potential, cation size, and temperature. J Phys Chem 112:7486–7495

    CAS  Google Scholar 

  18. Lockett V, Horne M, Sedev R, Rodopoulos T, Ralston J (2010) Differential capacitance of the double layer at the electrode/ionic liquids interfaces. Phys Chem Chem Phys 12:12499–12512

    Article  CAS  PubMed  Google Scholar 

  19. Kirillova EV, Dokashenko SI, Stepanov VP (2008) The capacity and the impedance of the interface between the polycrystalline gold and alkali chloride melts. Rasplavy (in Russian) 4:74–79

    Google Scholar 

  20. Kirillova EV, Stepanov VP (2016) Capacitance of the double electrical layer on the copper-group metals in molten alkali metal halides. Russian Metallurgy (Metally) 2016(8):691–697

    Article  Google Scholar 

  21. Pastukhov YG, Stepanov VP (1989) The study of a gold electrode in molten potassium halides by the estance method. Doklady Akademii Nauk SSSR (in Russian) 307:648–652

    CAS  Google Scholar 

  22. Tazi S, Salanne M, Simon C, Turq P, Pounds M, Madden PA (2010) Potential-induced ordering transition of the adsorbed layer at the ionic liquid / electrified metal interface. J Phys Chem B 114:8453–8459

    Article  CAS  PubMed  Google Scholar 

  23. Melendres CA, Hahn F (1999) In situ observation of halide ion adsorption on a gold electrode using synchrotron far infrared spectroscopy. J Electroanal Chem 463:258–261

    Article  CAS  Google Scholar 

  24. Loo BH (1982) In situ identification of halide complexes on gold electrode by surface-enhanced Raman spectroscopy. J Phys Chem 86:433437

    Article  Google Scholar 

  25. Sitnikov LV, Zakir’yanova ID, Ev K (2016) Study of the chlorine anion interaction with surface of the gold electrode by GRS spectroscopy under electric polarization. Rasplavy (Melts) (in Russian) 5:455–463

    Google Scholar 

  26. Liu XJ, Moritomo Y, Nakamura A, Kojima N (1999) Pressure-induced phase transition in mixed-valence gold complexes Cs2Au2X6 (X=Cl and Br). J Chem Phys 110:9174–9178

    Article  CAS  Google Scholar 

  27. Saltykova NA, Pecherskaya LS, Baraboshkin AN, Kotovsky SN, Kosikhin LT (1986) Salt passivation during anodic dissolution of iridium chloride melts. Elektrokhimiya (in Russian) 22:579–584

    CAS  Google Scholar 

  28. Salyulev AB, Vovkotrub EG (2014) Investigation of the chlorination products of palladium in the presence of alkali and alkaline earth chlorides by Raman spectroscopy. Problemy spektroskopii I spektrometrii (in Russian) 33:99–105

    Google Scholar 

Download references

Acknowledgements

The authors would like to thank Vovkotrub E.G, PhD for performing the Raman analyses of samples using the facilities in the shared access center “Composition of compounds” IHTE, UB RAS.

Funding

This work was partially funded by programs of the Ural Branch of the RAS (project 18-5-3-12).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Victor P. Stepanov.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Stepanov, V.P., Kirillova, E.V. Polarization and adsorption effects on the wettability of a gold electrode by lithium, sodium, potassium, and cesium chloride melts. Ionics 25, 2763–2768 (2019). https://doi.org/10.1007/s11581-018-2755-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11581-018-2755-4

Keywords

Navigation