Glycerol water-rich mixtures

Below 40 mol% of glycerol-water, domains appear. This critical concentration is related to the numbers of H-bonds of glycerol and of water respectively. DSC studies also confirm the same critical concentration. In water-rich mixtures, some water is frozen as a result, three relaxation processes where observed. These were related to ice-like structures, interfacial bound-water, and glycerol-water mixtures in the mesoscopic domains, where the concentration remains at 40 mol%. 

Table 6.2 shows values of the standard molar enthalpy and entropy for the transfer of ions from water into equimolar aqueous mixtures with cosolvents at 25°C, A, /f or A j5 "(I, W 0.5W-i-0.5S), taken from the compilation by Hefter et al. [13]. Further values for the solvents shown there are available at 0.1 mole fraction steps over the entire composition range. The ionic data were selected from data on electrolytes hsted in these references on the basis of their conformation to the TATB or TPTB assumptions (Section 4.3.1). Data are available in this reference also for many other aqueous solvents (n- and i-PrOH, f-BuOH, glycerol, tetrahydrofuran, 1,4-dioxane, acetone, A,A-dimethylacetamide, and sulfolane) for at least a part (the water-rich part) of the composition range, as well as for some other ions that were not measured atX3=0.5 in the solvents shown in Table 6.2 or that could not be traced to the TATB or TPTB assumptions. This table also includes data for these functions for the transfer of ions into aqueous urea, which, though urea is not a solvenf it behaves in aqueous solutions as if it were a liquid amide. 

To illustrate the application of the film model for nonideal fluid mixtures we consider steady-state diffusion in the system glycerol(l)-water(2)-acetone(3). This system is partially miscible (see Krishna et al., 1985). Determine the fluxes Ap A2, and A3 in the glycerol-rich phase if the bulk liquid composition is... 

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