IUPAC-NIST Solubilities Database

IUPAC-NIST Solubility Database
NIST Standard Reference Database 106

Solubility System: Ethene with Organic halides, pressures greater than 0.2 MPa (2 atm)

Components:
   (1) Ethene; C2H4; [74-85-1]  NIST Chemistry WebBook for detail
   (2) Organic halides, pressures greater than 0.2 PMa (2 atm); ; []  NIST Chemistry WebBook for detail

Evaluator:
   Walter Hayduk, Department of Chemical Engineering, University of Ottawa, Ottawa, ON, Canada, K1N 6N5
January, 1994

Critical Evaluation:

   Critical Evaluation of Ethene Solubility in Organic Halides (mainly Alkyl Halides) for Pressures greater than 0.20 MPa

Ethene solubility in organic halide solvents was reported by seven groups of researchers^1-7 for pressures ranging from 0.2 MPa to 11.7 MPa. For these data, in every case, only one research group reported their results for any one solvent; hence, a comparison of data from two or more sources was not possible. Instead, it was only possible to check the consistency of the data. For that purpose graphs of log x (mole fraction solubility) versus log p (gas partial pressure) were drawn with the solubility shown as a function of temperature as a parameter. For several of the solvents it was possible to express the data, especially for relatively low pressures, using an equation of the form shown below, with the constant C being nearly equal to one when Henry’s law applied:

log x_p = A + B/T + C log p

(1)

The solubility in the individual solvents will now be considered.

Bromochioromethane; CH₂BrCl; [74-97-5]

Lebedeva et al.¹ reported ethene solubility in bromochloromethane at 323.15 K, 373.15 K and 423.15 K at pressures ranging from 1.013 MPa to 11.73 MPa. At the lower pressures, up to 10 MPa, Henry’s law is approximately obeyed and the corresponding Henry’s constants have been tabulated on the data sheet. There are a number of apparently anomalous results.

These data are classified as tentative.

Trichloromethane (chloroform); CHCl₃ [67-66-3]

The solubility of ethene in trichloromethane were reported by Shim and Kohn² for pressures ranging from 1.013 MPa to the critical pressures and for five temperatures ranging from 273.15 K to 373.15 K. Except for one result at a temperature of 373.15 K and a pressure of 1.013 MPa, the data appear consistent. They are well represented by the following correlating equation that relates the mole fraction ethene at equilibrium, the temperature, and ethene partial pressure:

log x_p = 522.32 (T/K)^-1 + 0.9600 log (p/MPa) – 2.5371

(2)

Equation (2) is limited to pressures 0.6 MPa < p < 6.0 MPa. For the indicated pressure range it yields an average, and a maximum deviation from the data of 3.1%, and 9.2%, respectively. Equation (2) and the data on which it is based, are shown in (Fig.1).. It is noted that Eq. (2) yields a value about 35% too high when extrapolated to 0.1013 MPa pressure at 298.15 K; hence, it is evident that this equation cannot be used outside the range of the data on which it is based.

The results of Shim and Kohn² are classified as tentative.

Tetrachloromethane (carbon tetrachloride); CCl₄ [56-23-5]

Konobeev and Lyapin³ reported solubility data for ethene in tetrachloromethane at 293.15 K, 313.15 K and 333.15 K and pressures from 0.29 MPa to 3.18 MPa. For the purpose of estimating the partial pressure of ethene in the gas phase, Raoult’s law was assumed and the pure solvent vapor pressures of 0.0122, 0.0284 and 0.059 MPa were used for the temperatures of 293.15 K, 313.15 K and 333.15 K, respectively. The solubility over the temperature and pressure range of the data is then well represented by the following equation:

log x_p = 521.68 (T/K)^–1 + 1.047 log (p/MPa) – 2.6314

(3)

Equation (3) has average, and maximum deviations from the experimental results of 3.9%, and 9.9%, respectively. Here also, it is cautioned that equation (3) cannot be accurately extrapolated for solubility at 0.1013 MPa pressure; deviations of approximately 20% are observed.

The data of Konobeev and Lyapin for solubility in tetra chloromethane are classified as tentative.

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

Konobeev and Lyapin³ also provided ethene solubility in 1,2 dichloroethane for pressures ranging from 0.29 MPa to 3.11 MPa and for the temperatures 293.15 K, 313.15 K and 333.15 K. As for the solvent tetra chloromethane, the pure solvent vapor pressures were used along with Raoult’s law to estimate ethene partial pressures. The resu1ting relation between ethene partial pressure, (p), temperature, T, and the mole fraction, x_p, is entirely consistent and is well expressed by the following equation:

log x_p = 446.77(T/K)^–1 + 1.052 log (p/MPa) – 2.5285

(4)

The average, and maximum deviations of the data from the correlating equation are 2.1%, and 4.5%, respectively.

The data of Konobeev and Lyapin for solubility in 1,2-dichloroethane are classified as tentative.

Ethane, 1,1,2-trichloro- 1,2,2-trifluoro-(Freon 113); C₂Cl₃F₃ [76-13-1]

Sokolov and Konshin⁴ reported data for ethene solubility in Freon 113 at the temperatures, 300.15 K, 343.15 K and 363.15 K for pressures ranging from 0.20 MPa to 1.11 MPa. No gas phase compositions were available; hence, Raoult’s law was used to estimate the solvent partial pressure in the gas phase. It became apparent that the gas contained significant concentrations of solvent vapor especially at the two higher temperatures, estimated to be more than 50% for a number of the results. Thus, because highly accurate results are difficult to obtain with volatile solvents there are some inconsistencies in these results.

Omitting the data point corresponding to a total pressure of 0.31 MPa at 343.15 K, an equation for the remaining data was derived:

log x_p = 531.24 (T/K)^–1 + 1.070 log (p/MPa) – 2.4376

The average, and maximum deviations of the data from Eq. (5) are 3.4%, and 10%, respectively. It is cautioned that the application of Raoult’s law is unlikely to be accurate at high vapor concentrations, so that Eq. (5) is approximate only.

The data of Sokolov and Konshin for ethene solubility in Freon 113 are classified as tentative.

3,3,3-Trifluoro, 1-propene (trifluoropropylene); C₃H₃F₃[677-21-4]

Zernov et al.⁵ reported solubility in 3,3,3-trifluoro 1-propene at temperatures from 283.1 K to 363.1 K and pressures from 0.393 MPa to 5.88 MPa. Henry’s law is only approximately obeyed for the temperatures below 333.1 K. The data at the higher temperatures (at 353.1 K and 363.1 K) appear to be inconsistent with those at the lower temperature.

These data are classified as tentative.

Acetic acid, trichloro-ethyl ester (ethyltrichloroacetate); C₄H₅Cl₃0₂ [515-84-4]

The results of Kristesashvili et al.⁶ for solubility in acetic acid, trichloro-ethyl ester were shown for the temperatures 363.15 K and 373.15 K and pressures up to 8.1 MPa only in graphical form. Approximate Henry’s constants were obtained from the graphs.

These data for acetic acid, trichloro-ethyl ester are classified as tentative.

1-Propene, 1,1,2, 3,3-pentafluoro-3 trifluoroethenyloxy-(perfluoropropylene vinyl ether); C₅F₈0; [64080-43-9]

Sokolov and Konshin⁴ reported solubility of ethene in 1,1,2,3,3-pentafluoro-3 trifluoroethenyloxy-1-propene at temperatures ranging from 298.15 K to 353.15 K and pressures from 0.20 MPa to 1.11 MPa. These data were reported as distribution constants in the form of ratios of concentrations in the liquid phase to those in the gas phase. In addition, the solubility was expressed in moles per litre and as Henry’s constants. It was not possible to calculate mole fraction solubility because neither solution densities nor gas phase compositions could be estimated. Nor could the tabulated results be checked for consistency.

These data are classified as tentative.

Propane, 1,1,1,3- Tetrachloro-; C₃H₄Cl₄ [1070-78-6]
Pentane, 1,1,1,5- Tetrachloro-; C₅H₈Cl₄ [2467-10-9]
Heptane, 1,1,1,7- Tetrachloro-; C₇H₁₂Cl₄ [3922-36-9]
Nonane, 1,1,1,9- Tetrachloro-; C₉H₁₆Cl₄ [1561-48-4]

Efremova and Kovpakova⁷ reported ethene solubility in the four tetrachloroalkanes in graphical form only, for temperatures ranging from 273.35 K to 373.15 K and for pressures from about 1 MPa to the critical pressures. From these graphs approximate Henry’s constants were estimated because Henry’s law was obeyed for ethene concentrations of up to about 0.4 mole fraction. When tested for consistency with respect to temperature, it was noted that the ethene solubility in tetrachloropropane solvent was only marginally different than that in tetrachloropentane. It is not clear whether or not this is anomolous because no clear consistency test is available. One might have expected lower solubility in tetrachloropropane to be consistent with those of the other three solvents.

These approximate results for solubility in the tetrachloroalkanes are classified as tentative.

Experimental Data:   (Notes on the Nomenclature)

View Figure 1 for this Evaluation

References: (Click a link to see its experimental data associated with the reference)

   1  Lebedeva, E.S.; Kashirina, A.S.; Grokholskaya, V.P., Ref. Zh. Khim. Abstr. 1971, No.138777, 92-100.
   2  Shim, J.; Kohn, J.P., J. Chem. Eng. Data 1964, 9, 1-2.
   3  Konobeev, B.I.; Lyapin, V.V., Khim. Prom. 1967, 43, 114-6.
   4  Sokolov, Yu. P.; Konshin, A.I., Zh. Prikl. Khim. 1989, 62, 1395-1398.
   5  Zernov, V.S.; Kogan, V.B.; Lyubetskii, S.G.; Duntov, F.I., Zh. Prikl. Khim. 1971, 44, 683-686, (J. App. Chem. USSR 1971, 44, 693-696).
   6  Kristesashvili, L.V.; Chkhubianishvili, N.G.; Tatenashvili, M.Kh., Soobshch. Akad. Nauk. Gruz. SSR 1979, 93, 365-368.
   7  Efremova, G.D.; Kovpakova, P.F., Zhur. Fiz, Khim. 1958, 32, 1231-1240.