Thermodynamic properties of solutions of alcohols and carbon tetrachloride. Part 2.—Heats and entropies of mixing

Application of Quasi-Lattice Theory to Alcohol – Carbon Tetrachloride Systems

“…Values of HpE read from the curves a t concentration intervals of 0.05 are collected in Table 111. Heats of mixing for some of the same systems have been reported by several previous investigators (6,8,11,12,13 appears that a reliable interpolation can be made only in the case of the data of Otterstedt and l\?issen (6). Using the cubic form suggested by these authors, values of HPE a t -25' C were calulated for systems I and V a t the 19 concentrations given in Table 111; the standard deviation from the values in Table I11 was 2.4 cal mole-l for system I and 1.5 cal mole-' for system V. This agreement is quite satisfactory since the standard deviations are of the same magnitude as those quoted in reference 6.…”

On the Origin of Excess Thermodynamic Quantities in Liquid Mixtures

“…2b) and refractive index behave linear with CCl 4 volume fraction. The pure components have similar molar volumes (96.5 cm 3 /mole for CCl 4 and 80.0 cm 3 /mole for CHCl 3 ) and densities (1.59 g/cm 3 for CCl 4 and 1.49 g/cm 3 for CHCl 3 ) and the two molecules are similar, differing just for the substitution of a chlorine atom with an hydrogen. In addition, we do not expect that the weak dipole of CHCl 3 molecule is able to drive local configurations stable on the time scale of a Brillouin scattering experiment (~10 -9 s).…”

“…In such a way, the distances of closer approach are d a and d b for collisions between like molecules and (d a + d b )/2 for collisions between unlike molecules. The total number density of the system is written as ρ = ρ a + ρ b (ρ a and ρ b being the number densities of the species a and b, respectively) and depends on the packing fraction η through the relation: (3) being x the mole fraction of the specie b. The virial equation of state (whose second and third coefficient are known analytically while the first one is identically equal to 1) is immediately written as [14]: (4) where p is the pressure, T is the absolute temperature, k B is the Boltzmann constant.…”

“…The investigation of the excess thermodynamic properties in liquid mixtures is a commonly adopted approach to infer information about the nature of the inter-specie interaction [1][2][3][4][5][6][7][8][9][10][11]. In particular, the concentration dependence of the compressibility of a binary mixture is a quantity whose deviations from ideality are assumed able to give direct indications about the attractive or repulsive nature of the inter-specie potential.…”

Molecular Reorientation of Methanol in Mixtures with Carbon Tetrachloride

“…Otterstedt and Missen [8] noticed that at high alcohol concentration the enthalpy of mixing is negative for mixtures of alcohols and carbon tetrachloride, but not for mixtures of alcohols and hydrocarbons, such as hexane [9]. Wolff and Hoeppel found the solvation enthalpy of methanol in carbon tetrachloride to be by 0.5 to 1 kcal/mol greater than that for the mixture of methanol with hexane [10].…”