The Determination and Statistical Mechanical Interpretation of the Solubility of Water in Benzene, Carbon Tetrachloride, and Cyclohexane

Abstract

The solubility of water in each of benzene, carbon tetrachloride, and cyclohexane, was determined at 5" intervals over the range 10 to 40 " C . The solubilities were converted to Henry's law constants and these constants were interpreted by means of a statistical mechanical theory based on Zwanzig's perturbation theory of fluids. A fitting-parameter in the form of a correction factor to the water-solvent pairwise potential function was required. T h e values of this parameter for the benzene-water and cyclohexane-water systems could be rationalized on the basis of anisotropy of solvent polarizability. T h e values of the parameter for the carbon tetrachloride -water system were consistent with a hydrogen-bonding interaction between water and carbon tetrachloride.

Apparatus for the Determination of Water Solubility in Hydrocarbon: Toluene and Alkylcyclohexanes (C6 to C8) from 30 °C to 180 °C

“…For example, increasing the temperature from 34.0°C to 172.6°C raises the mole fraction solubility of water in ethylcyclohexane more than 34 times to (53.32 ( 0.07) × 10 -3 . (11) , 0.45 (13) , 0.96 (7) Figure 5 shows our experimental solubility values, previously reported experimental data, and those calculated by the correlation of Heidman et al 5 valid between (0 and 295)°C (expressed by eq 2). Our experimental solubility data are in good agreement with the experimental data of Heidman et al 5 but lie above the calculated data from the correlation of Heidman et al 5 The results obtained for the solubility of water in (Z + E)-1,2-dimethylcyclohexane are presented in Table 1.…”

The Dimerization Constant of Nitrobenzene in Benzene: A Critique of Partition as a Thermodynamic Method

“…The average sample standard deviation for the water analyses was about 1z. The solubility of water in pure benzene was in accord with previously determined values (10,13). The results of the calorimetric experiments are given in Table 3.…”

“…This was reagent grade benzene, further purified as described previously (10). The benzene used in the calorimetric experiments was dried by allowing it to be in contact with drierite for several weeks.…”

“…These analyses were performed with an Aquatest I1 automatic Karl Fischer Titrator (model 702, Photovolt). The techniques used for equilibration, sampling, and analysis of the benzene phase for water, have all been previously described (10).…”

π-hydrogen bonding between water and aromatic hydrocarbons at high temperatures and pressures

“…Some authors claimed that the rather large mutual solubility of water with aromatic hydrocarbons as compared with alkanes at ambient condition should be the result of a hydrogen-bondlike interaction between water and electrons of an aromatic ring. 17,18 This type of interaction involving electrons has been considered to be important in biological systems. 19 The common constituents of globular proteins such as phenylalanine, tryptophan, and tyrosine possess an aromatic side-chain.…”