EXAMPLE 10.

2 Convention II activity coefficients

Find the Convention II activity coefficients at 35.2C for acetonechloroform solutions, taking acetone as the solvent. Use Table 10.1. Ordinarily, one would use Convention I for acetonechloroform solutions, but for illustrative purposes we use Convention II. Equation (10.16) for the solvent Convention II activity coefficient gII,A is the same as the Convention I equation (10.14), so gII,A _ gI,A. Since acetone has been designated as the solvent, we have gII,ac _ gI,ac. The gI,ac values were found in Example 10.1. For the solute chloroform, Eq. (10.15) gives gII,chl _ Pchl /Kchlxl chl. We need the Henrys law constant Kchl. In Fig. 9.21a, the Henrys law dotted line for chloroform intersects the right-hand axis at 145 torr, and this is Kchl in acetone. (A more accurate value of Kchl can be found by plotting Pchl /xl chl versus xl chl and extrapolating to xl chl _ 0. See also Prob. 10.11.) The Table 10.1 data and Kchl _ 145 torr then allow calculation of gII,chl . Time can be saved by noting that gI, i _ Pi /xi lP*i , so gII, i /gI, i _ (Pi /Ki xi l ) _ (Pi /xi lP*i ) _ P*i /Ki _ (293 torr)/(145 torr) _ 2.02. Thus gII,chl _ 2.02gI,chl. Using the gI,chl values from Example 10.1 and (10.10), we find:
xac 0 0.082 0.200 0.336 0.506 0.709 0.815 0.940 1 gII,chl 2.02 1.99 1.93 1.77 1.56 1.31 1.19 1.08 1 gII,ac 0.494 0.544 0.682 0.824 0.943 0.981 0.997 1

The gIIs are plotted in Fig. 10.4. Both gIIs go to 1 as the solvent mole fraction xac1, whereas gI,chl1 as xchl1 and gI,ac1 as xac1 (Fig. 10.3a).

Exercise
Use Table 10.1 to find gII,ac and gII,chl in a 35.2C acetonechloroform solution with xl ac _ 0.4188 if acetone is considered to be the solvent. (Answer: 0.751,