CAB 2023 CHEMICAL THERMODYNAMIC

Tutorial Nine

Real Liquid Mixtures – Part 2

6. The liquid mixture (1) + (2) at 70oC has the following activity coefficients:

x1 γ1 γ2
0.1 4.90 1.05
0.2 2.90 1.20
0.3 1.95 1.30
0.4 1.52 1.50
0.5 1.30 1.70
0.6 1.20 2.00
0.7 1.10 2.25
0.8 1.04 2.60
0.9 1.01 2.95

The pure-component vapor pressures are 0.03107 and 0.03116 MPa,

respectively, at this temperature.
a. Find the van Laar constants that fit these data.
b. What are the infinite-dilution activity coefficients?
c. Is there an azeotrope?

[Ans : a. A = 2.433 , B = 1.189, b. γ1 = 11.39, γ2 = 3.28 c. Yes ]

7. Ethyl acetate and ethanol form an azeotrope at 1 atm, 344.9 K. The mole fraction
of ethanol is 0.461. Calculate the van Laar constants for this mixture at this
temperature, based only on this datum and vapor pressures calculated from the
Antoine constants in Appendix III.
[ Ans : A  1.495 B  1.486 ]

8. The binary mixture: chloroform (1)- ethanol (2) at 55 oC is well represented with
the Margules equation in the form:
ln  1  x 22  A12  2 A21  A12  x1 
ln  2  x12  A21  2 A12  A21  x 2 

a. Find the coefficients in these equations from the azeotrope composition and
pressure: x1 = 0.84 and P=0.08667 MPa

The pure-component vapor pressures at this temperature are:

P10  0.0824 MPa P20  0.03731 MPa

1
 b. Plot the entire activity coefficient-mole fraction diagram using these
parameters.

A21  1.32
[ Ans : , Activity Coefficient Plot
A12  0.97

Activity coefficient for Chloroform(1)/Ethanol(2)

2.5 7

6
2
5
1.5 4 γ1
γ1

γ2
3 γ2
1
2
0.5
1

0 0
0 0.2 0.4 0.6 0.8 1
Mole Fraction chloroform

9. The measured freezing point of a 0.0107 molar NaCl-water solution is 28.6 oF.
Take the melting point of pure water as 32oF and calculate the activity coefficient
of the water at 0.0107 molar NaCl. The NaCl is completely dissociated (see
example 11.6)
[Ans :  H 2O  1.021 ]

10. The following are data for the solubility of hydrogen in water at 23oc:

PH2, [mmHg] xH2 ×105

1100 1.861
2000 3.382
3000 5.067
4000 6.729
6000 9.841
8000 12.56

Find the Henry’s constant and the best value for A in the one-parameter equation
for the asymmetric activity coefficient?
K CO , H 2O  5.76  10 7 mmHg
[Ans : ]
A  336