Critical evaluation of the solubility of ethene at a partial pressure not greater than 101.3 kPa in organic halides

In general mole fraction solubility in organic halides is lower than in alkanes but higher than in solvents containing oxygen or nitrogen. Consistent measurements in several organic halides have been obtained by more than one group. This enables a more reliable characterization of the solubility pattern in organic halides than in oxygen or nitrogen compounds.

Tetrachloromethane; CCl₄; [56-23-5]

Solubility in tetra chloromethane at a partial pressure of 101.3 kPa has been reported by Horiuti¹, Narasimhan and Nageshwar², Sahgal et al.³, Leites and Ivanovskii⁴, Hannaert et al.⁵, Briickl and Kim⁶, and by Jadot⁷. From the information available the single measurement by Narasimhan appears to be inconsistent with other measurements and must be ignored. The 19 data points from other sources can be fitted to the equation

ln x₁ = -20.598 + 1773.8/(T/K) + 1.8277 ln(T/K)
where is the mole fraction solubility at p₁ = 1.013 kPa standard deviation in values of x₁ = 3.1 × 10⁴.
This equation is recommended for the temperature range 253-323 K.

Trichloromethane; CHCl₃ [67-66-3]

Solubility in trichloromethane was measured by Leites and Ivanovskii⁴ at 243.15 K and by Camacho Rubio et al.⁸ at 293 K to 308 K. In each case data was presented in graphical form only. Data points from the two graphs fit the equation

ln x₁ = -9.4327 + 1525.5/(T/K)
where x₁ is the mole fraction solubility at p,sub>1 = 1.013 kPa standard deviation in values of x₁ = 3.1 × 10⁴.
This equation is based on 5 data points and corresponds to a solubility curve which differs from the pattern of curves shown by most of the other halocompounds for which corresponding data is available (see Fig 1). It should be accepted on a tentative basis for the temperature range 253 K to 323 K pending further measurements on the system.

Chloroethene; C₂H₃Cl; [75-01-4]

Solubility in chioroethene was measured by Hannaert et al⁵ over the temperature range of 213.15 K to 243.15 K. Results were published in the form of an equation for Henry's constant over this temperature range. Mole fraction solubility can be assumed to vary linearly with pressure to at least 101.3 kPa. Extrapolation of the mole fraction solubility to 298.15 K gives a value of 0.0183, close to the solubility in octane and appreciably greater than that in tetrachloro and trichioromethane. There is no reason to doubt Hannaert's measurements but they must be accepted on a tentative basis until they are confirmed by other measurements.

1 2-Dichloroethane; C₂H₄Cl₂; [107-06-2]

Hannaert et al.⁵ also measured solubility in 1,2-dichloroethane in the temperature range 273.15 K to 313.15 K. Choudhari and Doraiswami⁹ measured solubility in the range 280 K to 300.5 K. There is poor agreement between the two sets of measurements. The mole fraction solubility at 292.5 K from Hannaert's data is 0.00934 compared with Choudhari's value of 0.00804. The evaluator cannot determine which is likely to be the more reliable measurements. Data from the two sources can be fitted to the equation.

The evaluator cannot determine which is likely to be the more reliable measurements. Data from the two sources can be fitted to the equation
ln x₁ -279.08 + 12799/(T/K) + 40.604 ln x₁
where x₁ is the mole fraction solubility at p₁ = 1.013 kPa standard deviation in values of x₁ = 7.3 × 10^-4.

The variation in solubility with change in temperature as indicated by this equation is inconsistent with the variation in solubility in other halocompounds (see Fig.1). This equation should not be used outside the temperature range 273 K to 313 K. Further measurements are needed on this system.

1,1,2,2-Tetrachloroethane; C₂H₂Cl₄; [79-34-5]

Velichko et al.¹⁰ reported solubility in 1,1,2,2-tetrachloroethane over a partial pressure range to 101.3 kPa at three temperature from 273.15 K to 298.15 K. Mole fraction solubility at a partial pressure of 101.3 kPa fit the equation ln x₁ = -11.562 + 1977.3/(T/K)
where x₁ is the mole fraction solubility at p₁ = 1.013 kPa standard deviation in values of x₁ = 5.2 × 10^-4.

As can be seen in Fig. 1 the measurements indicate a much steeper change in mole fraction solubility with change in temperature as compared with most other chiorocompounds for which data are available. The change is similar to that apparent from the measurements on trichioromethane in the temperature range 293.15 K to 308.15 K but needs confirmation by further work.

Chlorobenzene; C₆H₅Cl; [108-90-7]
Bromobenzene; C₆H₅Br; [108-86-11]

Solubility in chlorobenzene at a partial pressure of 101.3 kPa has been measured by Lopez et al.¹¹, Horiuti¹, and by Sahgal et al.³ Measurements cover the temperature range 263.15 K to 363.15 K and are consistent with one another. Data can be fitted to the equation.

ln x₁ = -26.1311 + 1950.0/(T/K) + 2.6600 ln(T/K)
where x₁ is the mole fraction solubility at p₁ = 1.013 kPa standard deviation in values of = 6.7 × 10^-5.
This equation is recommended by the evaluator for the temperature range 263.15 to 363.15 K.

Solubility in bromobenzene was also measured by Lopez et al.¹¹ in the temperature range 263.15 K to 303.15 K. Mole fraction solubility at a partial pressure of 101.3 kPa may be fitted to the equation
x₁= -25.783 + 1910.4/(T/K) + 2.5971 ln(T/K)
where x₁ is the mole fraction solubility at p₁ = 1.013 kPa standard deviation in values of x1 = 1.2 × 10^-5.
This equation fits the experimental data slightly better than the one given by the authors. There is no reason to doubt the validity of these measurements but they should be accepted on a tentative basis until confirmed by further measurements.

Chlorocyclohexane; C₆H₁₁Cl; [542-18-7]
Bromocyclohexane; C₆H₁₁Br; [108-85-0]

Lopez et al.¹², measured the solubility in chlorocyclohexane and in bromocyclohexane in the temperature range 263.15 K to 303.15 K. Mole fraction solubility in chlorocyclohexane is greater than in bromocyclohexane and also greater than in chlorobenzene. Mole fraction solubility in cyclohexylamine is similarly greater than that in benzenamine.

The evaluator has found that the data for solubility in chlorocyclohexane at a partial pressure of gas of 101.3 kPa fits the equation

ln x₁ = -9.8501 + 1275.4/(T/K) + 0.2262 ln(T/K)
where x₁ is the mole fraction solubility at p₁ = 1.013 kPa standard deviation in values of x₁ = 1.0 × 10^-5; temp. range 263 K to 303 K. This equation gives better fit than the one given by the authors.

Data for bromocyclohexane may be fitted to the equation
ln x₁ = -28.775 + 2045.2/(T/K) + 3.0748 ln(T/K)
where x₁ is the mole fraction solubility at p₁ = 1.013 kPa
standard deviation in values of x₁ = 2.2 × 10^-5 temp. range 263 K to 303 K this equation gives better fit than the one given by the authors.

There is no reason to doubt the measurements of solubility in these two solvents and they can be accepted on a tentative basis until confirmed by other workers.

Mixed solvents

Trichloromethane; CHCl₃ [ 67-66-3] + 2-propanone; C₃H₆O; [67-64-11 methylbenzene; C₇H₈ [108-88-3]

Leites and Ivanovskii⁴ measured solubility in mixtures of trichloromethane with 2-propanone and with methylbenzene at 243.15 K. No other data for these mixtures are available for comparison. The solubility in pure trichloromethane is consistent with measurements at higher temperatures. The value of the solubility in pure 2-propanone differs by about 8% from that calculated from Hannaert's data. Data for the mixture of trichloromethane and 2-propanone may be accepted on a tentative basis, bearing in mind the uncertainty in the data for pure 2-propanone. Leites and Ivanovskii also measured solubility in pure methylbenzene at 213.15 K, 223.15 K and 243.15 K. The value at 243.15 K differs by about 6% from the value calculated from an equation published by Hannaert et al.⁵. The solubility in mixtures of trichloromethane and methylbenzene may be accepted on a tentative basis.

Tetrachloromethane; CCl₄; [56-23-5] + heptane; C₇H₁₆ [142-82-5]

Leites and Ivanovskii measured solubility in mixtures of tetrachloromethane and heptane at 253.15 K. Their value for the solubility in pure tetra chloromethane chloromethane at 253.15 K is consistent with data at higher temperatures from other workers. In addition their measurements of solubility in pure heptane from 213.15 K to 253.15 K are consistent with measurements by other workers^3,7 at higher temperatures. The data for solubility in mixtures of tetrachloromethane and heptane may be accepted on a tentative basis.

Tetrachloromethane CCl₄; (56-23-5] + benzene; C₆H₆; (71-43-2]

Narasimham & Nageshwar² measured solubility in mixtures of tetrachloromethane and benzene at 293.15 K. Mole fraction solubility corrected to a partial pressure of 101.3 kPa vary linearly with mole fraction of benzene. There is some uncertainty concerning corrections for the partial pressure of solvent (see compilation sheet). The solubility in pure tetrachloromethane at a partial pressure of 101.3 kpa, as estimated by the compiler from data reported in the same paper, has been rejected by the evaluator in favor of measurements by other workers. The value of the solubility in pure benzene that they reported is about 4% greater than that reported by Horiuti¹.