Thermodynamics of the amalgam cell {LixHg1-x | Li2SO4(m) | Hg2SO4 | Hg} in water, (methanol + water), and (acetonitrile + water) solvent mixtures

The emf. E of the amalgam cell {LixH1-x | Li2SO4(m) | Hg2SO4 | Hg} was measured as a function of the mole fraction x of Li metal in amalgams, and of the molality m of Li2SO4 in (methanol + water) and (acetonitrile + water) solvent mixts. contg. up to 0.3 mass fraction of the org. component, at the temp. 298.15 K. The resp. std. electromotive forces Emo were detd. together with the relevant activity coeffs. γ± as a function of Li2SO4 molality. A new scheme is introduced here and implemented for verification of the internal consistency of the γ± results in terms of complementary pairs of concn. cells with transference. The Emo depends linearly on the mass fraction w of the org. component of the solvent mixt. within the range explored, according to: Emo/V = 2.80137 - 0.20325w(methanol), Emo/V = 2.80137 - 0.23139w(acetonitrile), which reproduce the obsd. Emo values to within ±0.2mV.