1

Problems for the Lecture Activity Coefficient Models

Problem 1. Henrys law constants and infinite dilution activity
coefficients

At 300 K, some experimental data are available for dilute liquid mixtures
of components 1 and 2. When 1 is dilute in an excess of 2, the Henrys
law constant is H
1,2
=2 bar. When 2 is dilute in an excess of 1, the Henrys
law constant is H
2,1
=1.60 bar. Estimate the vapour composition, which is
in equilibrium with an equimolar liquid mixture of 1 and 2 at 300 K.
Assume that the vapour is an ideal gas. At 300 K, the pure-component
vapour pressures are 1.07 bar for pure liquid 1 and 1.33 for pure liquid 2.

Hint. Assume the validity of a simple two-parameter activity coefficient
model e.g. van Laar or Margules two-parameter. Why cant we use the
one-parameter Margules equation ?

Problem 2. Comparison with experimental data

The vapour-liquid equilibrium data reported in the table below (Gmehling
et al., 1979) are for the system acetone (1)/cyclohexane (2) at 25
o
C.
Assume for simplicity that, at the low pressures involved, we have ideal
vapour behaviour.

Pressure
(mmHg)
x
1
y
1
Activity
Coefficient of
compound (1)
Activity
Coefficient of
compound (2)
97.45 0.0 0.0
118.05 0.0115 0.1810
172.90 0.0575 0.4580
253.90 0.4235 0.6800
259.40 0.5760 0.7050
252.00 0.9250 0.8580
243.80 0.9625 0.9160
230.40 1.0000 1.0000

i. Calculate the experimental activity coefficients of the two
compounds and complete the table above. Do we have positive
or negative deviations from Raoults law ?
ii. Use a single experimental data point (at P=253.9 mm Hg) to
estimate the parameters of an activity coefficient model and
then calculate the equilibrium pressure and vapour compositions
at liquid acetone concentrations: 0.0115, 0.5760 and 0.9625.
Prepare a table showing for these three compositions the
2

percentage deviations between calculated and experimental
activity coefficients (for both components), equilibrium
pressures and vapour phase mole fractions. Compare the results
to the experimental data and comment on the results.

Problem 3. K-factors for distillations using the Regular Solution
Theory

For distillation-column design, we need K factors (K
i
=y
i
/x
i
). A liquid
mixture at 50
o
C contains 30 mol% n-hexane and 70 mol% benzene.
At 50
o
C, the pure component vapour pressure of n-hexane is 0.533 bar
and of benzene is equal to 0.380 bar.

1. Calculate the K factors of n-hexane and benzene in this mixture.
Assume that the pressure is sufficiently low to neglect gas-phase
corrections and Poynting factors. Then calculate the relative
volatility of hexane/benzene.
2. What would be the relative volatility assuming an ideal liquid
solution ?

The molar volumes and solubility parameters are (all values at 25
o
C):

Compound Volume (cm
3
/mol) Solubility parameter
(J cm
-3
)
1/2
n-hexane 132 14.9
Benzene 89 18.8

Problem 4. Azeotropes with the Regular Solution Theory

A binary liquid mixture contains the non-polar components 1 and 2. The
mixture is to be separated by ordinary distillation. To determine if this is
feasible, it is necessary to know whether or not the mixture has an
azeotrope. The pure component vapour pressures at 300 K and the
solubility parameters are given for the two compounds in the table below.
The pure-component molar volumes are both 160 cm
3
/mol.

At 300 K, does this mixture have an azeotrope ? If so, what is its
composition ? Assume that the vapour phase is ideal.





3

Compound Vapor Pressure (kPa) Solubility parameter
(J cm
-3
)
1/2
(1) 53.3 14.3
(2) 80 17.4



Problem 5. Using azeotropic data to predict VLE for a binary
mixture

Benzene and cyclohexane form an azeotrope at 0.525 mole fraction
benzene at temperature of 77.6 C and a total pressure of 1.013 bar. At this
temperature the vapour pressure of pure benzene is 0.993 bar and that or
pure cyclohexane is 0.980 bar.

i. Using the van Laar model, estimate the activity coefficients of
benzene and cyclohexane at liquid mole fractions (benzene) 0.0,
0.2, 0.5, 0.8 and 1.0. Use this activity coefficient information to
compute the equilibrium pressure versus liquid and vapour
composition at the same temperature.
ii. Make predictions for the activity coefficients of benzene and
cyclohexane using the regular solution theory and compare
these with the results obtained in question i. Volume and
solubility parameters of benzene are given in problem 3, while
for cyclohexane they are 109 cm /mol and 16.8 (J/cm
3
)
1/2


Problem 6. Interrelations between models Derivations


1. Slide 22 presents the expression of the RST for multicomponent
systems using l
ij
=0. Starting from this expression, derive the
expression for binary systems which is shown on the top of the
same slide.

2. The excess Gibbs energy equation of the van Laar equation is prior
to the assumption of any mixing rules is:

b
a
x g
i
i i
E
=
|
.
|

\
|
=

c
c c


4

Consider a binary mixture. Derive the expression for the activity
coefficient of compound (1) in the following cases / types of mixing
rules:

i.

=
i
i i
x c c

ii.

=
i j
ij j i
x x c c
j i ij
c c c =

iii. the classical van der Waals one fluid parameters for the energy
and co-volume parameters (a,b) using also the well-known geometric
mean combining rule for the cross energy parameter and the arithmetic
mean rule for the cross co-volume parameter. Assume that all
interaction parameters (k
ij
and l
ij
) are equal to zero.


Comment on the results and discuss especially to what type of
solutions your three models can be potentially applied. Give some
examples.