화학공학소재연구정보센터
Journal of Chemical Thermodynamics, Vol.33, No.5, 499-512, 2001
Thermodynamics of the cell Pt vertical bar H-2(p)vertical bar HCl (m)vertical bar AgCl vertical bar Ag and primary medium effects upon HCl in (glycerol plus water) solvents
The electromotive force (e.m.f.) E of the cell Pt \H-2(p)\ HCl(m) in Z \ AgCl \ Ag in {glycerol (G) + water (W)} solvents, Z = (G + W), up to glycerol mass fraction w(G) = 0.7 has been measured within the temperature range from 273.15 K to 313.15 K at HCl molalities up to 0.1 mol/kg(-1). On this basis, the standard molar e.m.f. E-m(o) values pertaining to such solvent mixtures have been obtained, and have been combined with sparse literature data for optimization. At glycerol mass fractions up to w(G)approximate to0.5, at constant temperature, E-m(o) shows a linear dependence on the glycerol mole fraction X-G and, in parallel, E-c(o) (on the amount-of-substance concentration scale) shows linear dependence on the glycerol volume fraction phi (G). The primary medium effect upon HCl, defined as the difference (E-c(o))w - (E-c(o))Z, has been considered as a function of the water volume fraction phi (W) in terms of Feakins and French's theory: this would lead to a primary hydration number n(hydr) = 2.4 for HCl, in good agreement with previous results obtained with solvents other than (glycerol + water). In this connection, some basic methodological aspects are discussed. Ancillary values of the densities rho (Z) of the relevant solvent mixtures, which were hitherto unavailable and are necessary for the data processing leading to E-m(o), have also been measured.