Evaluator
Ari L. Horvath Imperial Chemical Industries (ICI) LimitedEvaluation
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):
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:
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.
Table 1. Recommended Solubility of Dichloromethane (1) in Water (2)
| C $T$ (°C) | C $T$ ($\pu{K}$) | D 100w1 | D $x_{1}$ |
|---|---|---|---|
| 0.0 | 273.15 | 2.126 | 4.587 x 10-3 |
| 5.0 | 278.15 | 1.977 | 4.260 x 10-3 |
| 10.0 | 283.15 | 1.86 | 4.004 x 10-3 |
| 15.0 | 288.15 | 1.766 | 3.799 x 10-3 |
| 20.0 | 293.15 | 1.722 | 3.703 x 10-3 |
| 25.0 | 298.15 | 1.701 | 3.657 x 10-3 |
| 30.0 | 303.15 | 1.712 | 3.681 x 10-3 |
| 35.0 | 308.15 | 1.754 | 3.773 x 10-3 |
Table 2. Recommended Solubility of Water (2) in Dichloromethane (1)
| C $T$ (°C) | C $T$ ($\pu{K}$) | D 100w2 | D $x_{2}$ |
|---|---|---|---|
| -20.0 | 253.15 | 3.53 x 10-2 | 1.663 x 10-3 |
| -15.0 | 258.15 | 4.34 x 10-2 | 2.042 x 10-3 |
| -10.0 | 263.15 | 5.22 x 10-2 | 2.487 x 10-3 |
| -5.0 | 268.15 | 6.40 x 10-2 | 3.008 x 10-3 |
| 0.0 | 273.15 | 7.68 x 10-2 | 3.612 x 10-3 |
| 5.0 | 278.15 | 9.17 x 10-2 | 4.308 x 10-3 |
| 10.0 | 283.15 | 1.09 x 10-1 | 5.109 x 10-3 |
| 15.0 | 288.15 | 1.28 x 10-1 | 6.021 x 10-3 |
| 20.0 | 293.15 | 1.51 x 10-1 | 7.057 x 10-3 |
| 25.0 | 298.15 | 1.76 x 10-1 | 8.226 x 10-3 |
| 30.0 | 303.15 | 2.04 x 10-1 | 9.541 x 10-3 |
| 35.0 | 308.15 | 2.36 x 10-1 | 1.1015 x 10-2 |
| 40.0 | 313.15 | 2.71 x 10-1 | 1.2656 x 10-2 |
Figures
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