The solubility of bromobenzene in water has been reported in eight published sets of data (1-6,14,15). The solubility behavior as a function of temperature is illustrated in Figure 1. Some rather serious discrepancies between the various solubility measurements are evident in the figure.
The solubility of water in bromobenzene has been measured by several investigators between 1932 and 1963 and reported in five published sets of data (7-10,14). As shown in Figure 2, which gives the solubility behavior relative to Absolute temperature, the agreement among experimental values is reasonable.
Of the more recent works, that of Nelson and Smit (4) reported the solubility data for temperatures in the range between 278 and 318 K. However, despite the equilibration period of 24 hours (which might not have been long enough), the solubility values obtained are substantially lower than those found by the earlier investigators. It is not possible to establish any shortcomings of their experimental procedure from the very brief description. No information was provided on the source and purity of materials used. Also, it was not indicated whether or not a water stripper had been employed for the analysis of the very dilute aqueous solutions by gas chromatography, or whether or not an internal standard had been used for the calibration of the gas chromatograph which employed a flame ionization detector. However, the authors agreed to re-examine their raw data in order to verify the reported values (13). Consequently, for the present evaluation, their results have not been considered for inclusion in the selected solubility values.
The reported solubility value of Yalkowsky et al. is too low. This could be due to an insufficient time allowed for saturation equilibrium. According to the authors, the accuracy of the experimental determination was ± 10 percent (11). The remaining reported data, that of Andrews and Keefer (1), Gross and Saylor (2), Hine et al. (3), and Vesala (5,15), have been correlated against Absolute temperature using a normal polynomial equation of second degree. In the regression, twice as much weight was assigned to the data of Vesala as was assigned to the remaining data. The equation below represents the solubility of bromobenzene in water between 283 and 308 K:
S1(g(l)/kg) = 1.8293 - 1.35675 x l0-2 T
+ 2.99322 x 10-5 T2 [1]
The values calculated from equation [1] for the saturation of bromobenzene in
water in the range of tmeperatures between 283 and 313 K together with corresponding molarities and mole fractions are given in Table 1. Also, the solubility values calculated from equation [1] are shown in Figure 1 as a solid line along with the measured values.
The solubility of water in bromobenzene has been reported in the temperatures range between 288 and 308 K in five investigations. The original report from Columbia University by Hutchinson and Lyon (8) has been lost, and all details reported here in that work have been taken from a secondary source (12). The single value from Hutchinson and Lyon is too high in relation to other reported determinations at the same temperature so it was not included in the correlation of the data against temperature. On the other hand, the solubility reported by Donahue and Bartell (14) appears too low and this value also was not used in the correlation. The reported values of Bell (7), Jones and Monk (9), and Wing and Johnston (10) are represented by the equation:
log10x(2) = 2.43149 - 1514.54/T [2]
In this equation, x(2) is the mole fraction solubility of water in the water-bromobenzene system and I is the Absolute temperature. The calculated solubility values in the 283 to 308 K range are shown in Figure 2 as a solid line along with the reported values.
The calculated mole fraction values for the solubility of water in bromobenzene from equation [2] are included in Table 2 together with the corresponding molarities and g(2)/kg values in the temperature range between 283 and 313 K.