Problem sheet 5

1. An ideal binary solution is formed from liquids A and B. The pure component vapor
pressures at 75 C are 300 and 800 mmHg for A and B, respectively. Determine the
composition of a mixture which normal boiling point is 75C and the composition of the
equilibrium vapor. Sol. xl(A)=0.080, xv(A)=0.032

2. An ideal binary solution is formed from liquids A and B and is observed to have PA=PB. The
pure component vapor pressures at 50 C are 300 and 100 mmHg for A and B, respectively.
Compute the composition of the solution and the total vapor pressure. Sol. 25%A, 150 mm Hg.

3. Forty grams of Ba(NO3)2 are dissolved in 1 kilogram of water.

a. If no ionization of the Ba(NO3)2 takes place, compute the vapor pressure of the solution at
313.15 K, where the equilibrium vapor pressure of pure water is 55.324 torr. Assume that the
solution is ideal. Sol. 55.172 torr

b. If the vapor pressure of the solution is found to be 54.909 torr, compute the fraction of the
Ba(NO3)2 that is ionized in the solution. Sol. 87.2%

c. What would the equilibrium H2O vapor pressure be if we had 100% ionization of Ba(NO3)2?
Sol. 54.871 torr

4. Fifteen grams of NaCl are dissolved in one kg of H2O at 363.15K. The equilibrium H2O vapor
pressure over the solution is found to be 521.00 torr. Pure H2O at 363.15K has an equilibrium
vapor pressure of 525.76 torr. Determine the ionization percentage of NaCl in this solution. Sol
97.95%

5. At 293K, the vapor pressure of pure liquid A and B are 68.8 and 82.1 kPa, respectively. A
certain liquid mixture of these two components has an vapor-phase A mole fraction of 0.612.
Find the mole fractions in the liquid mixture and the vapor pressure. Sol. 73.4 kPa, xA=0.653

6. A solution of ethanol (et) and chloroform (cl) at 45C with xet=0.9900 has a vapor pressure of
177.95 torr. At this high dilution of chloroform, the solution can be assumed to be essentially
ideally dilute. The vapor pressure of pure ethanol at 45C is 172.76 torr.

a. Find the partial pressures of the gases in equilibrium with the solution. Sol. 171, 6.92 torr

b. Find the mole fractions in the vapor phase. Sol. 0.9611, 0.0389

c. Find the Henry´s law constant for chloroform in ethanol at 45C. Sol. 692

d. Predict the vapor pressure and vapor-phase mole fractions at 45C for a chloroform-ethanol
solution with xet=0.9800. Sol. 183.1 torr, 0.9244, 0.0756
7. The attached figure shows the vapor pressures as a function of the composition for the
benzene-toluene system at 25C, which are ideal solutions.
a) Using the data in this figure, determine the composition of vapor in equilibrium with a
solution of 18.4 g of toluene and 62.4 g of benzene. Sol. B 92.9%
b) Calculate the mixing functions ( G,  S,  V,  H) for the solution of a. Sol.
-1239.8 J, 4.16 J/K, 0, 0

8. Using the vapor pressure data shown in the attached figure,

calculate:

a. Henry´s constant for component A

b. The activity coefficient of A when xA=0.6 assuming that the

reference state is the pure liquid A.

c. the activity coefficient of A when xA=0.6 using the

convention II, being B the solvent.

Sol. a) 0.5, b) 0.67, c) 1.66

9. Given the following data on alcohol+water solutions at 20C

w% Ethanol Pethanol/torr Pwater/torr

0 0 17.5

20.0 12.6 15.9

40.0 20.7 14.7

60.0 25.6 14.1

80.0 31.2 11.3

100.0 43.6 0

Compute the activity coefficients of ethanol and water in a 40% solution. Sol. et=2.29,
agua=1.06

10. Semiempirical equation proposed by Margules expresses vapor pressure (p1) of one of the
 x 22
components of a solution by: p1  p1* x 1e
where p1 * is the vapor pressure of pure component 1, x1 and x2 are the mole fractions and 
 x12
is a constant. Demonstrate that component 2 obeys the equation p 2  p *2 x 2 e

 
11. In a dilute binary solution, the activity coefficient of the solute is given by  2  exp Ax 22 ,
where A is a constant. Derive an expression for the activity coefficient of the solvent. Sol.

ln 1  2A x 2  x 22 / 2  ln 1  x 2 
12. At 35C, the vapor pressure of chloroform is 295.1 torr, and that of ethanol (Et) is 102.8
torr. A chloroform-ethanol solution at 35C with xl(et)=0.200 has a vapor pressure of 304.2 torr
and a vapor composition xv(et)=0.138.

a. Calculate 1 and a1 for chloroform and for ethanol in this solution applying convention I. Sol.
et=2.042, Cl=1.111

b. Calculate G for the mixing of 0.200 mol of liquid ethanol and 0.800 mol of liquid
chloroform at 35C. Sol. -700.5 J

13. One liter of a simple synthetic sea water, which has approximately the same major ionic
components, can be made by adding water to 29.31 g of NaCl, 3.99 g of MgCl2, 1.83 g of MgSO4,
1,34 g of CaSO4 and 0.85 g of K2SO4. What is the ionic strength of this synthetic sea water?
What is the mean activity coefficient of MgCl2 at 25 C in this solution, estimated using Debye-
Hückel’s theory? (Atomic weight: Na 23, Cl 35.5, Mg 24.3, Ca 40, K 39.1, S 32, O 16). Sol. 0.7418
molL-1, 0.338
14. Mean molal activity coefficients for HBr as a function of HBr composition are given in the
following table:

m(HBr) 0.001 0.005 0.01 0.02 0.05 0.1 0.2 0.5 1

 0.966 0.930 0.906 0.879 0.838 0.805 0.782 0.790 0.871

Calculate and plot the activity coefficients according to the following equations, compare the
dependence of the activity coefficients on ionic strength with the experimental data:

a. The limiting law of Debye-Hückel

b. The Debye-Hückel equation

c. The Davies equation.