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Electric Double Layer on a Renewable Liquid (Cd–Ga) Electrode in Acetonitrile Solutions

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Abstract

Parameters that characterize the electric double layer structure on a renewable liquid (Cd–Ga) (0.3 at % Cd) electrode in solutions of surface-inactive electrolytes in a solvent with the low donor number, namely, acetonitrile (AN), are obtained. For the (Cd–Ga) electrode in AN, the following parameters: the potential of zero charge (PZC) unaffected by specific adsorption of ions, the value of “corrected electrochemical work function,” and the potential drop due to chemisorption of solvent, are obtained and compared with analogous results at Hg/AN, Ga/AN, (Cd–Ga)/gamma-butyrolactone (GBL), and (Cd–Ga)/dimethylformamide (DMF) interfaces. The AN chemisorption shifts the potential in the negative direction, which suggests that chemisorbed AN dipoles are oriented with their negative (nitrogen) ends to the metal surface. It is demonstrated that the solvent chemisorption potential drop on the (Cd–Ga) electrode increases in the series AN < GBL < DMF, i.e., with the increase in solvent’s donor number. The energy of chemisorption interaction metal–AN increases when going from (Cd–Ga) to Ga, i.e., with the increase in the work function. Based on the PZC shifts observed in 0.1 М LiBr and LiI solutions with respect to the PZC in solution of a surfaceinactive electrolyte, the adsorbability of halide ions on the (Cd–Ga)/AN interface is studied. The close values of the adsorption potential shift are obtained for Br– and I– ions, which suggests the stronger (Cd–Ga)–Br– interaction as compared with (Cd–Ga)–I–.

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References

  1. Emets, V.V., Mel’nikov, A.A., and Damaskin, B.B., Electrical double layer in surface-inactive electrolyte solution and adsorption of halide ions from 0.1M solutions on liquid Cd–Ga and In–Ga alloys in gammabutyrolactone, Russ. J. Electrochem., 2016, vol. 52, p. 10.

    Article  CAS  Google Scholar 

  2. Emets, V.V., Mel’nikov, A.A., and Damaskin, B.B., Electric double layer on renewable liquid (Cd–Ga) electrode in dimethylformamide solutions, Russ. J. Electrochem., 2017, vol. 53, p. 117.

    Article  CAS  Google Scholar 

  3. Emets, V.V. and Damaskin, B.B., The relation between the potential of zero charge and work function for spmetals, Russ. J. Electrochem., 2009, vol. 45, p. 45.

    Article  CAS  Google Scholar 

  4. Emets, V.V. and Damaskin, B.B., Chemisorption interaction of liquid electrodes of gallium and In–Ga, Cd–Ga and Tl–Ga alloys with solvents in a wide range of their donor numbers, J. Electroanal. Chem., 2007, vol. 600, p. 191.

    CAS  Google Scholar 

  5. Emets, V.V., Mel’nikov, A.A., and Damaskin, B.B., Effect of metal nature on energy of specific adsorption of chloride ions from dimethyl formamide solutions, Russ. J. Electrochem., 2017, vol. 53, p. 248.

    Article  CAS  Google Scholar 

  6. Emets, V.V., Melnikov, A.A., and Damaskin, B.B., Electric double layer in the solution of surface-inactive electrolyte and specific adsorption of Cl–, Br–and I–ions on liquid (Cd–Ga) electrode in dimethylformamide, J. Electroanal. Chem., 2016, vol. 768, p. 145.

    CAS  Google Scholar 

  7. Emets, V.V. and Damaskin, B.B., Comparative study of Cl–, Br–, and I–ions adsorption from dimethyl formamide at Hg-and Ga-electrodes, Russ. J. Electrochem., 2010, vol. 46, p. 1036.

    CAS  Google Scholar 

  8. Emets, V.V. and Damaskin, B.B., Comparison study of adsorption of Cl–, Br–, and I–-ions from dimethyl formamide on In–Ga and Tl–Ga electrodes, Russ. J. Electrochem., 2011, vol. 47, p. 89.

    CAS  Google Scholar 

  9. Emets, V.V. and Damaskin, B.B., Specific adsorption of Cl–, Br–, and I–ions on liquid In–Ga electrode from dimethyl formamide solutions with a constant ionic strength, Russ. J. Electrochem., 2015, vol. 51, p. 1149.

    CAS  Google Scholar 

  10. Emets, V.V. and Damaskin, B.B., Specific adsorption of Cl–, Br–, and I–ions on liquid Ga electrode from dimethylformamide solutions, J. Electroanal. Chem., 2015, vol. 752, p. 82.

    CAS  Google Scholar 

  11. Ivanova, R.V., Ganzhina, I.M., and Damaskin, B.B., Comparison of surface activity of anions on mercurydimethylformamide and mercury–water interfaces, Elektrokhymiya, 1970, vol. 6, p. 709.

    Google Scholar 

  12. Damaskin, B.B., Ganzhina, I.M., and Ivanova, R.V., The structure of the electrical double layer at the mercury/dimethylformamide interface at specific adsorption of anions, Elektrokhymiya, 1970, vol. 6, p. 1540.

    CAS  Google Scholar 

  13. Petyarv, E.K. and Palm, U.V., Specific adsorption of anions from dimethylformamide solutions onto bismuth electrode, Sov. Electrochem., 1975, vol. 11, p. 1480.

    Google Scholar 

  14. Petyarv, E.K. and Palm, U.V., Specific adsorption of anions, and structure of compact part of double-layer at bismuth/dimethylformamide interface, Sov. Electrochem., 1976, vol. 12, p. 595.

    Google Scholar 

  15. Gutmann, V., Coordination Chemistry in Non-Aqueous Solutions, Vienna; Springer, 1968.

    Book  Google Scholar 

  16. Minc, S., Jastrzebska, J., and Brzostowska, M., Properties of the electrical double layer in solutions of electrolytes in some organic solvents, J. Electrochem. Soc., 1961, vol. 108, p. 1160.

    Article  CAS  Google Scholar 

  17. Fawcett, W.R., Ikeda, B.N., and Sellan, J.B., Double layer structure at the mercury dimethylformamide interface, Can. J. Chem., 1979, vol. 57, p. 2268.

    Article  CAS  Google Scholar 

  18. Borkowska, Z. and Fawcett, W.R., Non-aqueous solvent structure at polarizable interfaces, Sov. Electrochem., 1980, vol. 16, p. 1387.

    Google Scholar 

  19. Lust, E., Analysis of electric double-layer structure at bismuth single-crystal faces in acetonitrile solutions, Sov. Electrochem., 1991, vol. 27, p. 389.

    Google Scholar 

  20. Lust, E.I., Yanes, A.A., and Lust, K.K., The structure of the electrical double layer at the faces of bismuth, antimony, or cadmium single crystals in surface-inactive electrolytes, Russ. J. Electrochem., 1996, vol. 32, p. 552.

    CAS  Google Scholar 

  21. Trasatti, S. and Lust, E., in Modern Aspects of Electrochemistry, White, R.E., Bockris, J.O’M., and Conway, B.E. (Eds.), New York: Kluwer Academic/Plenum, 1999, vol. 33, p. 1.

    CAS  Google Scholar 

  22. Bagotskaya, I.A., Fateev, S.A., Grigoriev, N.B., and Frumkin, A.N., The structure of a double electrical layer on the eutectic alloy In–Ga in aqueous and acetonitrile solutions. III. Structure of a double electric layer in acetonitrile solutions, Elektrokhymiya, 1973, vol. 9, p. 1676.

    CAS  Google Scholar 

  23. Bagotskaya, I.A. and Kalyuzhnaya, A.M., Comparison of zero-charge potential differences between liquid gallium and mercury in water and in acetonitrile, Sov. Electrochem., 1976, vol. 12, p. 964.

    Google Scholar 

  24. Emets, V.V., Damaskin, B.B., and Kazarinov V.E., Effects caused by an unequal approach of acetonitrile dipoles to the mercury surface and the surface of the gallium metals, Russ. J. Electrochem., 1997, vol. 33, p. 1193.

    CAS  Google Scholar 

  25. Emets, V.V. and Damaskin, B.B., The electrical double layer at the Bi–Ga liquid alloy in the acetonitrile electrolyte solutions, Russ. J. Electrochem., 2004, vol. 40, p. 1066.

    Article  CAS  Google Scholar 

  26. Emets, V.V. and Damaskin, B.B., Double electric layer on liquid Sn-Ga alloy in acetonitrile solutions of electrolytes, Russ. J. Electrochem., 2005, vol. 41, p. 1038.

    Article  CAS  Google Scholar 

  27. Petrii, O.A., Khomchenko, I.G., and Zelinskii, A.G., Electrochemical properties of the platinum metals in non-aqueous solvents. Electric double layer capacity of renewable platinum and palladium electrodes in LiClO4 solutions in acetonitrile, Sov. Electrochem., 1979, vol. 15, p. 339.

    Google Scholar 

  28. Petrii, O.A. and Khomchenko, I.G. Electrochemical properties of platinum electrodes in acetonitrile solutions, J. Electroanal. Chem., 1980, vol. 106, p. 277.

    CAS  Google Scholar 

  29. Levi, M.D., Boitsov, V.G., and Bagotskaya, I.A., Quantitative data on the adsorption of Br–and I–anions from acetonitrile on In–Ga eutectic alloy, Sov. Electrochem., 1979, vol. 15, p. 493.

    Google Scholar 

  30. Bagotskaya, I.A., Hai, C.N., Boitsov, V.G., and Kazarinov, V.E., Solvent effects in halide ion adsorption on different metals, Sov. Electrochem., 1988, vol. 24, p. 248.

    Google Scholar 

  31. Emets, V.V., Damaskin, B.B., Bagotskaya, I.A., and Mishuk, V.Ya., Electrical double layer structure at a model liquid cadmium electrode in aqueous surfaceinactive electrolytes, Russ. J. Electrochem., 2000. vol. 36. p. 661.

    Google Scholar 

  32. Emets, V.V. and Damaskin, B.B., Electrical double layer on the Cd–Ga liquid alloy in solutions of surfaceinactive electrolytes in water, methanol and propylene carbonate, J. Electroanal. Chem., 2000, vol. 491, p. 30.

    Article  CAS  Google Scholar 

  33. Gouy, G., Sur la contribution de la charge electrique a la surface d’electrolyte, J. Phys. Radium, 1910, vol. 9, p. 457.

    CAS  Google Scholar 

  34. Chapman, D., A contribution of the charge to the theory of electrocapillarity, Phil. Mag., 1913, vol. 25, p. 475.

    Article  Google Scholar 

  35. Grahame, D., The electrical double layer and the theory of electrocapillarity, Chem. Rev., 1947, vol. 41, p. 441.

    Article  CAS  PubMed  Google Scholar 

  36. Parsons, R. and Zobel, F.G.K., The interface between mercury and aqueous sodium dihydrogen phosphate, J. Electroanal. Chem., 1965, vol. 9, p. 333.

    CAS  Google Scholar 

  37. Emets, V.V. and Damaskin, B.B., Decrease in the tension at the electrode-solution interface caused by a chemisorption interaction between solvent and metal, Russ. J. Electrochem., 2000, vol. 36, p. 668.

    Article  CAS  Google Scholar 

  38. Emets, V.V., Kazarinov, V.E., and Bagotskaya, I.A., The influence of the metal lyophilicity on the structure of the electrical double layer in the solvents with a large dielectric constant: The structure of the electrical double layer on the gallium metals in N-methylformamide, Russ. J. Electrochem., 1996, vol. 32, p. 1069.

    CAS  Google Scholar 

  39. Emets, V.V., Damaskin, B.B., and Kazarinov V.E., Electrical double-layer structure on metals of the gallium subgroup in various solvents that takes into account the metal electronic configuration, Russ. J. Electrochem., 1995, vol. 31, p. 103.

    CAS  Google Scholar 

  40. Emets, V.V., Damaskin, B.B., and Kazarinov V.E., Phenomena of the specific interaction of metal with solvent and constituents of the adsorption potential drop, Russ. J. Electrochem., 1995, vol. 31, p. 722.

    CAS  Google Scholar 

  41. Emets, V.V., Damaskin, B.B., and Kazarinov V.E., A modified model for the metal/solution interface, allowing for hydrophilicity of the Ag(111) single crystal face: An analysis of the capacitance intrinsic to the compact part of the electrical double layer at mercury, gallium, and an indium-gallium alloy in three different solvents, Russ. J. Electrochem., 1996, vol. 32, p. 1313.

    CAS  Google Scholar 

  42. Bagotskaya, I.A., Damaskin, B.B., Emets, V.V., and Kazarinov, V.E., The role of metal and solvent in the structure of the electrode/surface-inactive electrolyte solution interface, J. Electroanal. Chem., 1998, vol. 448, p. 229.

    Article  CAS  Google Scholar 

  43. Emets, V.V., Damaskin, B.B., and Kazarinov, V.E., Difference between reciprocal capacitances on mercury and the gallium subgroup metals (Ga, In–Ga, TI–Ga) in the absence of the metal–solvent chemisorption interaction in aqueous solutions of sulfates of lithium, sodium, and potassium, Russ. J. Electrochem., 1999, vol. 35, p. 499.

    CAS  Google Scholar 

  44. Emets, V.V. and Damaskin, B.B., The structure of the electrical double layer on the liquid Pb–Ga alloy in aqueous, propylene carbonate and formamide solutions of electrolytes, J. Electroanal. Chem., 2002, vol. 528, p. 57.

    Article  CAS  Google Scholar 

  45. Amokrane, S. and Badiali, J.P., A new analysis of the differential capacitance of an ideally polarized electrode, J. Electroanal. Chem., 1989, vol. 266, p. 21.

    Article  CAS  Google Scholar 

  46. Amokrane, S. and Badiali, J.P., A model for the determination of the distance of closest approch of a solvent molecule to a metal surface—application to a silver electrode, Electrochim. Acta, 1989, vol. 34, p. 39.

    Article  CAS  Google Scholar 

  47. Amokrane, S. and Badiali, J.P., A new analysis of the differential capacitance of an ideally polarized electrode. Part II. Non aqueous solvents, J. Electroanal. Chem., 1991, vol. 297, p. 377.

    Article  CAS  Google Scholar 

  48. Amokrane, S. and Badiali, J.P., Analysis of the capacitance of the metal–solution interface: role of the metal and the metal–solvent coupling, in Modern Aspects of Electrochemistry, Bockris, J.O’M, Conway, B.E., and White, R.E. (Eds.), New York: Plenum, 1992, vol. 21, p. 1.

    Google Scholar 

  49. Frumkin, A.N., Potentsialy nulevogo zaryada (The Potentials of Zero Charge), Moscow: Nauka, 1982 [in Russian].

    Google Scholar 

  50. Andersen, T.N. and Bockris, J.O’M., Forces involved in the “specific” adsorption of ions on metals from aqueous solution, Electrochim. Acta, 1964, vol. 9, p. 347.

    Article  CAS  Google Scholar 

  51. Gritzner, G., Single-ion transfer properties: a measure of ion-solvation in solvents and solvent mixtures, Electrochim. Acta, 1998, vol. 44, p. 73.

    Article  CAS  Google Scholar 

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  1. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, 119071, Russia

    V. V. Emets & A. A. Mel’nikov

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  1. V. V. Emets
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Original Russian Text © V.V. Emets, A.A. Mel’nikov, 2018, published in Elektrokhimiya, 2018, Vol. 54, No. 12, pp. 1032–1043.

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Emets, V.V., Mel’nikov, A.A. Electric Double Layer on a Renewable Liquid (Cd–Ga) Electrode in Acetonitrile Solutions. Russ J Electrochem 54, 1012–1021 (2018). https://doi.org/10.1134/S1023193518130128

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  • DOI: https://doi.org/10.1134/S1023193518130128

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