Thermodynamics of Transfer of Hydrogen Halides (HCI, HBr) in Giyceroi–Dimethylformamide Mixtures from Electromotive Force Measurements

The standard potentials of Ag-AgX (X = Cl-or Br-) electrodes In glycerol-dlmethylformamlde (Gly-DMF) mixtures In different solvent compositions (up to 60 wt % DMF for Ag-AgCI and 40 wt % DMF for Ag-AgBr electrodes) have been determined at three different temperatures from 25-35°C by emf measurements with the cell Pt,H2(g, 1 atm)|HCI (m),DMF(x)-Gly(y)|AgX-Ag. The primary medium effects and the mean molal activity coefficients in the concentration ranges 0.01-0.02 mol kg-1at 25°C have been evaluated. The standard molal potentials,8E°m, have been expressed as a function of temperature. The thermodynamic parameters for the transfer of HCI and HBr from glycerol to glycerol-DMF mixtures have been evaluated from emf data at 25°C on the mole fraction scale. The significance of the various thermodynamic quantities associated with the transfer process is discussed. © 1990, American Chemical Society. All rights reserved.