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Two-dimensional pressure of chemisorbed dimethylformamide and N-methylformamide molecules at Ga-, (In-Ga)-, and (Tl-Ga)-electrodes

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Abstract

By using differential capacitance curves taken in solutions of surface-inactive electrolyte, charge dependences of two-dimensional pressure of chemisorbed solvent molecules Δ HgM ξchem are obtained at renewable liquid electrodes [Ga, (In—Ga) (14.2 at % In), and (Tl—Ga) (0.02 at % Tl)] in dimethylformamide and N-methylformamide. Analysis of the obtained data showed that at a fixed charge density in both solvents Δ HgM values, hence, values of the metal—solvent chemisorption interaction energy ΔG chem increase in the sequence Hg < (Tl-Ga) < (In-Ga) < Ga. The values of Δ HgM ξchem increase when passing from N-methylformamide to dimethylformamide. The data are confirmed with the corresponding dependences for the haloid ions’ twodimensional pressure. The two-dimensional pressure of the dimethylformamide and N-methylformamide chemisorbed molecules was shown to approach that of the haloid ions (ξads) concerning the charge interval and the pressure magnitude; therefore it affects significantly the ions’ specific adsorption parameters. The simultaneous increase in Δ HgM ξchem and ξads during the passing from (Tl-Ga) to (In-Ga) and Ga, both in dimethylformamide and N-methylformamide, is an unambiguous evidence of the increase in the metal-ion interaction energy ΔG M-A in the sequence (Tl-Ga) < (In-Ga) < Ga. The analysis reveals the reason of the change of the haloid ion specific adsorption parameters in the series of solvents. It was shown that the increase in the energy ΔG ads of the haloid ion adsorption at Ga-, (In-Ga)-, and (Tl-Ga)-electrodes, which is observed when passing from N-methylformamide to dimethylformamide, cannot be attributed to the solvent chemisorption. The unambiguous reason thereof is the decrease in the haloid ions’ solvation energy in aprotic dimethylformamide as compared with proton N-methylformamide.

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Authors and Affiliations

  1. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 119071, Russia

    V. V. Emets

  2. Moscow State University, Vorob’evy Gory 1, Moscow, 119991, Russia

    B. B. Damaskin

Authors
  1. V. V. Emets
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  2. B. B. Damaskin
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Correspondence to V. V. Emets.

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Original Russian Text © V.V. Emets, B.B. Damaskin, 2015, published in Elektrokhimiya, 2015, Vol. 51, No. 8, pp. 891-897.

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Emets, V.V., Damaskin, B.B. Two-dimensional pressure of chemisorbed dimethylformamide and N-methylformamide molecules at Ga-, (In-Ga)-, and (Tl-Ga)-electrodes. Russ J Electrochem 51, 789–795 (2015). https://doi.org/10.1134/S1023193515080054

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  • DOI: https://doi.org/10.1134/S1023193515080054

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