IUPAC-NIST Solubility Database
NIST Standard Reference Database 106

Glass Ball as Bullet Solubility System: Trichlorofluoromethane with Water

   (1) Water; H2O; [7732-18-5]  NIST Chemistry WebBook for detail
   (2) Trichlorofluoromethane; CCl3F; [75-69-4]  NIST Chemistry WebBook for detail

   A. L. Horvath, Imperial Chemical Industries Limited, Runcorn, U.K.

Critical Evaluation:


The trichlorofluoromethane (1) and water (2) binary system is discussed in two parts; part 1 is trichlorofluoromethane (1) in water (2) and part 2 is water (2) in trichlorofluoromethane (1).

Part 1. The solubility of trichlorofluoromethane (1) in water (2) has been studied by at least eleven different work groups with only partial agreement of results. The data of Howe et al. (ref. 1) are substantially lower than other measurements and are therefore rejected. The solubility data reported by du Pont (refs. 2 and 3), Rauws et al. (ref. 4), McConnell et al. (ref. 5), Pearson and McConnell (ref. 6), and Sukornick (ref. 7) show some consistency, while the measurements reported by Park et al. (ref. 8), Warner and Weiss (ref. 9), Wisegarver and Cline (ref. 10), Warner et al. (ref. 11), Balls (ref. 14), and Zeininger (ref. 15) are relatively high in value.

It may be assumed that the solubility data reported in the du Pont bulletins were produced in the same laboratories with similar methods and accuracy at 298.15 and 304.15 K, respectively. There appears to be no significant difference between the two data points despite the 6 K difference in temperature. Similarly, the two measurements reported by McConnell et al. and Pearson and McConnell in 1975 most likely were made in the same laboratories under much the same conditions.

There is no obvious reason to explain the difference between the lower (refs. 2, 3, 5, 6, and 7) and higher (refs. 8, 9, 10, 11, 14, and 15) sets of data. In the opinion of the evaluator, there is not enough evidence to justify rejection of measurements from either of the two data sets. Although both data sets are classified as tentative, the smoothed solubility values in mass per cent (1) for the 273 through 313 K temperature interval (Table 1) are based upon a regression equation for all data shown in Figure 1:

Solubility [100 w1] = 25.0094 – 0.16263 (T/K) + 2.6547 × 10–4 (T/K)2

with a standard error of 5.0 × 10–2 about the regression line.

A minimum solubility occurs for most halogenated hydrocarbons in water systems between 270 and 310 K (refs. 12 and 13). A minimum solubility temperature can be calculated from an enthalpy of solution at infinite dilution and a change in solute heat capacity in going from a pure liquid to an infinitely dilute aqueous solution. However, such thermodynamic data are rarely available in the literature.

Part 2. The solubility of water (2) in trichlorofluoromethane (1) has been measured by three research groups (refs. 2, 3, and 7) with only partially consistent results with the exception of the measurements of Sukornick (ref. 7). Generally, the solubility behavior of water in halogenated hydrocarbons shows a definite increase with increasing temperature. This trend has been demonstrated in a comprehensive compilation of solubility data (ref. 12). The two measurements at 294.15 and 298.15 K from the du Pont laboratories compare favorably with the recommended values, whereas the reported value of Sukornick (ref. 7) at 304.15 K is low and classified as doubtful. More accurate solubility measurements are required for more reliable values.

Experimental Data:   (Notes on the Nomenclature)

Table 1. Tentative Solubility of Trichlorofluoromethane (1) in Water (2)
t/°CT/K102 * Mass Fraction w1104 * Mole Fraction x1
View Figure 1 for this Evaluation

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

   1  Howe, G.B.; Mullins, M.E.; Rogers, T.N., AFESC Tyndall Air Force Base, Report ESL-TR-86-66, Vol. 1, Florida, Sept. 1987, 86 pp. (AD-A188 571).
   2  du Pont de Nemours & Company, Solubility Relationship of the Freon Fluorocarbon Compounds, Tech. Bull. B-7, Wilmington, Del., 16 pp. (1966).
   3  du Pont de Nemours & Company, Solubility Relationship of the Freon Fluorocarbon Compounds, Tech. Bull. B-7, Wilmington, Del., 16 pp. (1966).
   4  Rauws, A.G.; Olling, M.; Wibowo, A.E., J. Pharm. Pharmac. 1973, 25, 718-22.
   5  McConnell, G.; Ferguson, D.M.; Pearson, C.R., Endeavour 1975, 34, 13-8.
   6  Pearson, C.R.; McConnell, G., Proc. Roy. Soc. B. 1975, 189, 305-32.
   7  Sukornick, B., Inter. J. Thermophys. 1989, 10, 553-61.
   8  Park, T.; Rettich, T.R.; Battino, R.; Peterson, D.; Wilhelm, E., J. Chem. Eng. Data 1982, 27, 324-6.
   9  Warner, M.J.; Weiss, R.F., Deep-Sea Res. 1985, 32, 1485-97.
   10  Wisegarver, D.P.; Cline, J.D., Deep-Sea Res. 1985, 32, 97-106.
   11  Warner, H.P.; Cohen, J.M.; Ireland, J.C., Determination of Henry's Law Constants of Selected Priority Pollutants, U. S. EPA Technical Report, PB87-212684, Cincinnati, OH., July 1987.
   12  Horvath, A.L., Halogenated Hydrocarbons: Solubility-Miscibility with Water. Marcel Dekker, Inc., New York, 1982, 889 pp.
   13  Sabinin, V.E.; Kiya-Oglu, N.V.; Gorichnina, V.P., J. Appl. Chem. USSR. 1970, 43, 1788-90.
   14  Balls, P.W., Ph. D. Thesis, Univ. of East Anglia, Norwich, U. K., July 1980, 375 pp.
   15  Zeininger, H.; Hoechst A.G., Internat Report, 1975.