IUPAC-NIST Solubility Database
NIST Standard Reference Database 106


Glass Ball as Bullet Solubility System: Dichloromethane with Water

Components:
   (1) Water; H2O; [7732-18-5]  NIST Chemistry WebBook for detail
   (2) Dichloromethane; CH2Cl2; [75-09-2]  NIST Chemistry WebBook for detail

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

Critical Evaluation:

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

Part 1. The solubility of dichloromethane (1) in water (2) has been studied by at least 32 groups of workers. Most of the data reported have been considered for inclusion in the smoothing equation with the following exclusions. The experimental data of Salkowski (ref. 1) are markedly lower than the other results and are therefore rejected. The solubility data of Booth and Everson (ref. 2), Alexandrova et al. (ref. 3), and Sadovnikova et al. (refs. 4 and 5) are several per cent higher than the smoothed solubility values and are also rejected. The data of Sabinin et al. (ref. 6) between 293.15 and 303.15 K show a temperature dependence of solubility much too large and are therefore rejected. The data of Svetlanov et al. (ref. 7) also show a change in solubility far too large between 288.15 and 333.15 K and are rejected; however, the value at 303.15 K is retained. The solubilities calculated from the distribution coefficients of Prosyanov et al. (ref. 8) are in very poor agreement, providing no confidence in their values which are regarded as dubious. The solubility data of Howe et al. (ref. 9) between 283.15 and 303.15 K show a maximum which is inconsistent with the trend of temperature dependence of solubility and are rejected; however, the value at 293.15 K is retained.

The remaining data of 25 laboratories by Rex (ref. 10), van Arkel and Vles (ref. 11), Bakowski and Treszczanovicz (ref. 12), Niini (ref. 13), McGovern (ref. 14), Donahue and Bartell (ref. 15), Kudryavtseva and Krutikova (ref. 16), Maretic and Sirocic (ref. 17), du Pont (ref. 18), Svetlanov et al. (ref. 7), Karger et al. (ref. 19), Antropov et al. (ref. 20), McConnell et al. (ref. 21), Pearson and McConnell (ref. 22), Archor and Stevens (ref. 23), Sato and Nakijima (ref. 24), Coca et al. (ref. 25), Hutchinson et al. (ref. 26), Leighton and Calo (ref. 27), Lincoff and Gossett (ref. 28), Gossett (ref. 29), Warner et al. (ref. 30), Howe et al. (ref. 9), Vogel (ref. 31), and Wright et al. (ref. 32), were used to obtain the following smoothing equation for solubility in mass per cent (1):

Solubility [100 w1] = 58.838 – 0.38224 (T/K) + 6.3928 × 10–4 (T/K)2

This equation represents the combined data with a 0.37 standard deviation in the 273 to 310 K temperature range.

The curve obtained from the smoothing equation shows a distinct minimum at 299 K as seen in Figure 1. The appearance of the minimum for the solubility versus temperature behavior is discussed in the Preface.

The recommended mass percent solubility values at 5 K intervals for dichloromethane (1) in water (2) are presented in the Table 1.

Part 2. The solubility of water (2) in dichloromethane (1) has been reported from 19 laboratories. The solubility measurements cover the 253 to 313 K temperature range as represented in Figure 2.

The data reported have been considered for inclusion in the smoothing equation with the following exclusions. The data of Bakowski and Terszczanovicz (ref. 12), Niini (ref. 13), Donahue and Bartell (ref. 15), and Kudryavtseva and Krutikova (ref. 16) are markedly higher than other results and are therefore rejected. The measured solubility of Aleksandrova et al. (ref. 3), and Sadovnikova et al. (refs. 4 and 5) are several per cent lower than the smoothed solubility and are also rejected. The solubilities calculated from the distribution coefficients of Prosyanov et al. (ref. 33), are in very poor agreement, providing no confidence in their values which are regarded as dubious.

The remaining data of 11 laboratories by Staverman (Ref. 34), McGovern (ref. 14), Davies et al. (ref. 35), Maretic and Sirocic (ref. 17), Sabinin et al. (ref. 6}. Lees and Sarram (ref. 36), Antropov et al. (ref. 20), Archer and Stevens (ref. 23), Coca et al. (ref. 25), Wu (ref. 37), and Ohtsuka and Kazama (ref. 38) were compiled or used for the smoothing equation. The fitting equation used was:

log10 x2 = 1.8214 – 1164.63/(T/K)

The equation represents the combined data with a standard deviation of 5.8 × 10–2 in the 253 to 313 K temperature range.

The recommended solubility values at 5 K intervals for water (2) in dichloromethane (1) are presented in the Table 2.

The linear relation between the solubility expressed as log10 x2 versus the reciprocal of absolute temperature behavior is illustrated in Figure 2. The straight line behavior of such plots is characteristic of the solubility of water in halogenated hydrocarbons, as discussed in the Preface.

Experimental Data:   (Notes on the Nomenclature)

Table 1. Recommended Solubility of Dichloromethane (1) in Water (2)
t/°CT/K102 * Mass Fraction w1103 * Mole Fraction x1
0273.152.1264.587
5278.151.9774.260
10283.151.8604.004
15288.151.7663.799
20293.151.7223.703
25298.151.7013.657
30303.151.7123.681
35308.151.7543.773
Table 2. Recommended Solubility of Water (2) in Dichloromethane (1)
t/°CT/K102 * Mass Fraction w2103 * Mole Fraction x2
-20253.150.03531.663
-15258.150.04342.042
-10263.150.05222.487
-5268.150.06403.008
0273.150.07683.612
5278.150.09174.308
10283.150.1095.109
15288.150.1286.021
20293.150.1517.057
25298.150.1768.226
30303.150.2049.541
35308.150.23611.015
40313.150.27112.656
View Figure 1 for this Evaluation

View Figure 2 for this Evaluation

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

   1  Salkowski, E., Biochem. Z. 1920, 107, 191-201.
   2  Booth, H.S.; Everson, H.E., Ind. Eng. Chem. 1948, 40, 1491-3.
   3  Alexandrova, M.V.; Sadovnikova, L.V.; Martinov, W.W., Sb. Nauch. Tr., Ivanov. Energ. Inst. 1972, 14, 146-54.
   4  Sadovnikova, L.V.; Komarova, V.P.; Alexandrova, M.V., Sb. Nauch. Tr., Ivanov. Energ. Inst. 1972, 14, 205-9.
   5  Sadovnikova, L.V.; Komarova, V.P.; Alexandrova, M.V.; Serafimov, L.A., Izv. Vyssh. Ucheb. Zaved., Khim. Khim. Tekhnol. 1972, 15, 1891-4.
   6  Sabinin, V.E.; Kiya-Oglu, N.V.; Gorichnina, V.P., J. Appl. Chem. USSR. 1970, 43, 1788-90.
   7  Svetlanov, E.B.; Velichko, S.M.; Levinskii, M.I.; Treger, Yu.A.; Flid, R.M., Russ. J. Phys. Chem. 1971, 45, 488-90.
   8  Prosyanov, N.N.; Shalygin, V.A.; Zel'venskii, Ya.D., Tr. Mosk. Khim. Tekhnol. Inst. 1974, 81, 55-6.
   9  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).
   10  Rex, A., Z. Phys. Chem. 1906, 55, 355-70.
   11  van Arkel, A.E.; Vles, S.E., Recl. Trav. Chim. Pays-Bas 1936, 55, 407-11.
   12  Bakowski, S.; Treszczanowicz, E., Przemysl Chemiczny 1937, 21, 204-6.
   13  Niini, A., Suomen Kemistilehti A 1938, 11, 19-20.
   14  McGovern, E.W., Ind. Eng. Chem. 1943, 35, 1230-9.
   15  Donahue, D.J.; Bartell, F.E., J. Phys. Chem. 1952, 56, 480-4.
   16  Kudryavtseva, G.I.; Krutikova, A.D., J. Appl. Chem. USSR. 1953, 26, 1129-33.
   17  Maretic, M.; Sirocic, V., Nafta (Zagreb) 1962, 13, 126-31.
   18  du Pont de Nemours & Company, Solubility Relationship of the Freon Fluorocarbon Compounds, Tech. Bull. B-7, Wilmington, Del., 16 pp. (1966).
   19  Karger, B.L.; Chatterjee, A.K.; King, J.W., Tech. Rept. No. 3, Dept. of Chemistry, Northeastern Univ., Boston, Mass., May 10, 1971.
   20  Antropov, L.I.; Populyai, V.E.; Simonov, V.D.; Shamsutdinov, T.M., Russ. J. Phys. Chem. 1972, 46, 311-2 (VINITI No. 3739-71).
   21  McConnell, G.; Ferguson, D.M.; Pearson, C.R., Endeavour 1975, 34, 13-8.
   22  Pearson, C.R.; McConnell, G., Proc. Roy. Soc. B. 1975, 189, 305-32.
   23  Archer, W.L.; Stevens, V.L., Ind. Eng. Chem. Prod. Res. Dev. 1977, 16, 319-25.
   24  Sato, A.; Nakijima, T., Arch. Envir. Health 1979, 34, 69-75.
   25  Coca, J.; Diaz, R.M.; Pazos, C., Fluid Phase Equilibr. 1980, 4, 125-36.
   27  Leighton, D.T.; Calo, J.M., J. Chem. Eng. Data 1981, 26, 382-5.
   28  Lincoff, A.H.; Gossett, J.M., in Gas Transfer at Water Surfaces by Brutsaert, W. and Jirka, G.H., Eds., D. Reidel Publ. Co., Dordrecht, 1984, p. 17-25.
   29  Gossett, J.M., Environ. Sci. Technol. 1987, 21, 202-8.
   30  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.
   31  Vogel, A.I., rev. by Furniss, B.S., et al. Vogel's Textbook of Practical Organic Chemistry, 5th ed., Longman, London, 1989, p. 1442.
   32  Wright, D.A.; Sandler, S.I.; DeVoll, D., Environ. Sci. Technol. 1992, 26, 1828-31.
   33  Prosyanov, N.N.; Shalygin, V.A.; Zel'venskii, Ya.D., Tr. Mosk. Khim. Tekhnol. Inst. 1974, 81, 55-6.
   34  Staverman, A.J., Recl. Trav. Chim. Pays-Bas 1941, 60, 836-41.
   35  Davies, W.; Jagger, J.B.; Whalley, H.K., J. Soc. Chem. Ind. (London) 1949, 68, 26-31.
   36  Lees, F.P.; Sarram, P., J. Chem. Eng. Data 1971, 16, 41-4.
   37  Wu, X., Huaxue Shiji 1981, 221-4.
   38  Ohtsuka, K.; Kazama, K., Sen't Seihin Shohi Kagaku Kaishi 22, 197-201 (1982).