Physical Chemistry II Chem 402 Spring 2011

PS # 9: (Ch 9: 1, 5, 15, 20, 22, 27, 32)

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P9.1) Ratcliffe and Chao [Canadian Journal of Chemical Engineering 47, (1969), 148] obtained the
following tabulated results for the variation of the total pressure above a solution of isopropanol
( P1* = 1008 Torr) and n-decane ( P2* = 48.3 Torr) as a function of the mole fraction of the n-decane in

the solution and vapor phases. Using these data, calculate the activity coefficients for both components
using a Raoults law standard state.
(Torr) x2 y2
942.6 0.1312 0.0243
909.6 0.2040 0.0300
883.3 0.2714 0.0342
868.4 0.3360 0.0362
830.2 0.4425 0.0411
786.8 0.5578 0.0451
758.7 0.6036 0.0489

a) for isopropanol P1* 1008 Torr

for n-decane P2* 48.3 Torr

ai
Using the relations Pi yi Ptotal , ai Pi / Pi * , and i , the calculated activities and activity coefficients
xi
are shown below.
P (Torr) x2 y2 a1 a2 1 2
942.6 0.1312 0.0243 0.912 0.474 1.05 3.61
909.6 0.2040 0.0300 0.875 0.565 1.10 2.77
883.3 0.2714 0.0342 0.846 0.625 1.16 2.30
868.4 0.3360 0.0362 0.831 0.651 1.25 1.94
830.2 0.4425 0.0411 0.790 0.706 1.42 1.60
786.8 0.5578 0.0451 0.745 0.735 1.69 1.32
758.7 0.6036 0.0489 0.716 0.768 1.81 1.27

207
P9.5) The partial molar volumes of water and ethanol in a solution with xH 2O = 0.60 at 25C are 17.0

and 57.0 cm3 mol1, respectively. Calculate the volume change upon mixing sufficient ethanol with 2.00
mol of water to give this concentration. The densities of water and ethanol are 0.997 and 0.7893 g cm3,
respectively, at this temperature.

V nH 2O V H 2O nEt V Et
V H 2O 17.0 cm3 mol-1 and V Et 57.0 cm3 mol-1
nH 2 O
nH 2O 3.75 and xH 2O 0.450
nH 2O nEt
3.75 mol
0.450; nEt 4.58
3.75 mol nEt

V nH2O V H2O nEt V Et

The total mixed volume is given by 3.75 mol 17.0 cm3 mol-1 4.58 mol 57.0 cm3 mol-1
325 cm3
M H 2O M Et
Vunmixed nH2O nEt
H O
2
Et
1cm3
3.75 mol 18.02 g mol-1
0.997 g
1cm3
+ 4.58 mol 46.07 g mol-1
0.7893 g
335 cm3
V V Vunmixed 325 cm3 335 cm3 10. cm3

P9.15) At 39.9C, a solution of ethanol (x1 = 0.9006, P1* =130.4 Torr) and isooctane ( P2* = 43.9 Torr)
forms a vapor phase with y1 = 0.6667 at a total pressure of 185.9 Torr.
a. Calculate the activity and activity coefficient of each component.
b. Calculate the total pressure that the solution would have if it were ideal.
a) The activity and activity coefficient for ethanol are given by

208
 y1Ptotal 0.6667 185.9 Torr
a1 0.9504
P1* 130.4 Torr
a1 0.9504
1 1.055
x1 0.9006

Similarly, the activity and activity coefficient for isooctane are given by

a2
1 y1 Ptotal
0.3333 185.9 Torr
1.411
*
P 2 43.9 Torr
a2 1.411
2 14.20
x2 1 0.9006
b) If the solution were ideal, Raoults law would apply.
PTotal x1 P1* x2 P2*
0.9006 130.4 Torr 1 0.9006 43.9 Torr
121.8 Torr

P9.20) The partial pressures of Br2 above a solution containing CCl4 as the solvent at 25C are found to
have the values listed in the following table as a function of the mole fraction of Br2 in the solution [G.
N. Lewis and H. Storch, J. American Chemical Society 39 (1917), 2544]. Use these data and a graphical
method to determine the Henrys law constant for Br2 in CCl4 at 25C.
P (Torr) P (Torr)
0.00394 1.52 0.0130 5.43
0.00420 1.60 0.0236 9.57
0.00599 2.39 0.0238 9.83
0.0102 4.27 0.0250 10.27
The best fit line in the plot is PBr2 Torr 413 xBr2 0.063 . Therefore, the Henrys law constant in

terms of mole fraction is 413 Torr.

P9.22) The densities of pure water and ethanol are 997 and 789 kg m3, respectively. The partial molar
volumes of ethanol and water are 55.2 and 17.8 103 L mol1, respectively. Calculate the change in
volume relative to the pure components when 2.50 L of a solution with xethanol = 0.35 is prepared.
V nH 2OVH 2O nethanolVethanol
V
xH 2OVH 2O xethanolVethanol 0.65 17.8 103 L mol-1 0.35 55.2 10-3 L mol-1
ntotal
V
0.0309 L mol-1
ntotal
2.50 L
ntotal = 80.9 mol nH 2O nethanol
0.0309 L mol-1
xethanol n 0.350
ethanol ; nH 2O 52.6 mol nethanol 28.3 mol
xH 2O nH 2O 0.650
M ethanol M H 2O
Videal nethanol nH 2O
ethanol H O
2

46.07 10 kg mol-1 -3
18.02 10-3 kg mol-1
28.3 mol + 52.6 mol = 2.60 L
789 kg m -3 998 kg m -3
V V Videal 0.10 L

210
P9.27) A volume of 13.75 L of air is bubbled through liquid toluene at 298 K, thus reducing the mass of
toluene in the beaker by 5.95 g. Assuming that the air emerging from the beaker is saturated with
toluene, determine the vapor pressure of toluene at this temperature.
1 mol
5.95 g -1
0.08314 L bar K -1 298 K
nRT 92.14 g mol
P = 0.116 bar
V 13.75 L

P9.32) Calculate the activity and activity coefficient for CS2 at xCS2 = 0.573 using the data in Table 9.3

for both a Raoults law and a Henrys law standard state.

PCS2 420.3 Torr
R
aCS *
0.820
2
PCS2 512.3 Torr
R
aCS 0.820
R
CS2 2
1.43
xCS2 0.573

PCS2 420.3Torr
H
aCS 0.209
2
k H ,CS2 2010Torr
H
aCS 0.209
H
CS2 2
0.365
xCS2 0.573

mols A xc 0 mols Liquid xd xc .