540.

203 Engineering Thermodynamics

Homework #10 – Due 5/6/2010
No coupon allowed.

1. The molar volume (cm3mol-1) of a binary liquid mixture at T and P is given by:
V = 120 X 1 + 70 X 2 + (15 X 1 + 8 X 2 ) X 1 X 2
a. Find expressions for the partial molar volumes of species 1 and 2 at T and P.
b. Show that when these expressions are combined in accord with M = �X i M i the
i
given equation for V is recovered.
c. Show that these expressions satisfy the Gibbs-Duhem equation ( �X i dM i = 0 ).
i

d. Show that (dV1 / dX 1 ) X1 =1 = ( dV2 / dX1 ) X1 =0 = 0 .

e. Plot, using a graphing software, the values of V, V1 , and V2 calculated by the
given equation for V and by the equations developed in (a) vs X 1. Label points
� �
V1, V2, V1 , and V2 , and show their value.
Note: example 11.3 in the textbook might be helpful for this problem.

Solution:

a) Substitute x2 = 1 - x1 in the given equation for V and reduce:

V = 70 + 58 x1 - x12 - 7 x13
Now we can apply Eqns (11.15 and (11.16) from SVA to find an expression for the partial molar
volumes ( V1 and V2 ). First we can calculate the slope:
dV
= 58 - 2 x1 - 21x12 then we get the expression for partial molar volumes:
dx1
V1 = 128 - 2 x1 - 20 x12 + 14 x13 and V2 = 70 + x12 + 14 x13

b) We use Eq. (11.11) from SVA: M = �xi M i and we obtain:

i

V = x1 (128 - 2 x1 - 20 x + 14 x ) + (1 - x1 )(70 + x12 + 14 x13 )

2
1
3
1

V = 70 + 58 x1 - x12 - 7 x13
Which is the first equation developed in part (a).

c) Write the Gibbs-Duhem relation at constant T and P (Eq. (11.14)) for a binary system and
dV1 dV
divide by dx1: x1 + x2 2 = 0
dx1 dx1
We can differentiate the expression for the partial molar volumes obtained in part (a):
dV1 dV2
= -2 - 40 x1 + 42 x12 and = 2 x1 + 42 x12
dx1 dx1
Multiply each derivative by the appropriate mole fraction and add:

x1 (-2 - 40 x1 + 42 x12 ) + (1 - x1 )(2 x1 + 42 x12 ) = 0

The validity of this equation is readily confirmed.

d) Subsitute x1=1 in the first derivative expression of part (c) and substitute x1=0 in the second
derivative expression of part (c). The results are:
�dV1 � �dV2 �
� � =� � =0
�dx1 �x =1
1
�dx1 �x =0 1

e) See plot on top of next page

2. Assuming Raoult’s law to be valid, prepare a P-x-y diagram for a temperature of 90 oC

and a T-x-y diagram for a pressure of 90kPa for a mixture of
Benzene(1)/Ethylbenzene(2).

Solution:

We will first need to use the Antoine equation for vapor pressures of pure species. Using Table
B.2 in Appendix B of your textbook we can get the Antoine equation constants for benzene and
ethylbenzene.

For benzene:
A1 = 13.7819 B1 = 2726.81 C1 = 217.572

For ethylbenzene:
 A2 = 13.9726 B2 = 3259.93 C2 = 212.300

Writing the Antoine equation for benzene:

B1
ln P1sat = A1 -
t1 + C1

Writing the Antoine equation for ethylbenzene:

B2
ln P2sat = A2 -
t 2 + C2

At t=90oC, P2 = 24.26 and P1 = 136.5

sat sat

We are given in the problem that our temperature is 90oC for our P-x-y diagram. We can also
rewrite Raoult’s law at this point for our 2 component system:

P = �xi Pi sat = x1P1sat + x2 P2sat = x1P1sat + ( 1 - x1 ) P2sat Equation (1)

i =2

Similarly, we can solve for y1, our vapor-phase mole fraction for benzene:
x P sat x1 P1sat
y1 P = x1 P1sat � y1 = 1 1 = Equation (2)
P x1 P1sat + ( 1 - x1 ) P2sat

In order to create our P-x-y diagram, we can select values of our liquid-phase mole fraction for
benzene, x1, since we know it will range from 0 (no liquid benzene) to 1 (all liquid benzene).
At any given value of x1 we can calculate our total pressure, P, from equation (1) above. Once
we have our value of the total pressure, P, at a given value of x1, we can use this value of P to
calculate y1 from equation 2. For example, calculations at x1=0.1 gives:

The following graph results where the red line denotes x1 and the black dashed line denotes y1:
 P (kPa)

x1, y1

When the temperature of our mixture is fixed, the pressure varies along with x1 and y1. The
curve for P-y represents states of saturated vapor; the superheated-vapor region lies below this
curve. Points lying between teh saturated-liquid and vapor lines are in the two phase region,
where saturated liquid and saturated vapor coexist in equilibrium. The P-x1 and P-y1 lines meet
at the edges of the diagram, where saturated liquid and saturated vapor of the pure species
sat sat
coexist at the vapor pressures P2 and P1 .

We are now ready to prepare our t-x-y diagram at our fixed pressure of 90kPa. When the
pressure of our mixture is fixed, the temperature varies along with x1 and y1. For a given
sat sat
pressure of 90kPa, the pressure range is bounded by t2 and t1 --the temperatures at which the
pure species exert vapor pressures equal to P. We can rearrange the Antoine equation and solve
sat
for ti to get the following equations for benzene and ethlybenzene, respectively:
B1 B2
t1sat = - C1 and t2sat = - C2
A1 - ln P A2 - ln P

Calculating at 90kPa gives t2 = 131.8 C and t1 = 76.20 C :

sat o sat o

sat sat sat sat

We can select values of t between t1 and t2 and then calculate P2 and P1 using the Antoine
equation at these temperatures.

Again, the Antoine equation for benzene is:

B1
ln P1sat = A1 -
t1 + C1

Again, the Antoine equation for ethylbenzene is:

B2
ln P2sat = A2 -
t 2 + C2
 sat sat
Once we calculate a value of P1 and P2 , we can rearrange equation 1 to solve for x1:
P - P2sat
x1 = sat Equation (3)
P1 - P2sat

We can then use equation (2) to calculate y1:

x1 P1sat
y1 =
P

For example, calculations at t=100oC gives:

t (˚C) P1sat (kPa) P2sat (kPa) x1 y1

100 180.45 34.27 0.381 0.764

The following graph results where the red line denotes x1 and the black dashed line denotes y1:

T (˚C)

3. A binary mixture of benzene (1) and toluene (2) is flashed to 75 kPa and 90 oC. Analysis
of the effluent liquid and vapor streams from the separator yields x1 = 0.1604 and
y1 = 0.2919 . An operator remarks that the products are “off-specs”, and you are asked
to diagnose the problem.
a. Verify that the exiting streams are not in binary equilibrium.
b. Verify that an air leak into the separator could be the cause
You can assume that the mixture is well-represented by Raoult’s law and that the vapor
pressure can be described by Antoine’s equation.
Solution:
First we will calculate the vapor pressure of the pure components using Antoine equation, then
combine it with Raoult’s law using the measured composition to see it is possible.
Part a)
Vapor pressure calculations for Benzene (1) and Toluene (1):
2726.81
Benzene: ln P1sat / kPa = 13.7819 - o � P1sat = 136.5kPa
T / C + 217.572
3056.96
Toluene: ln P2sat / kPa = 13.9320 - o � P2sat = 54.31kPa
T / C + 217.625
Raoult’s Law: i y P = x P
i i
sat

x1 P1 = y1 P
sat

(1 - x1 ) P2sat = (1 - y1 ) P
If we combine both equations we can extract the equilibrium composition:
( P - P sat ) (75 - 54.31)kPa
x1 = sat 2 sat = = 0.252
P1 - P2 (136.5 - 54.31)kPa
x1 P1sat 0.252*136.5kPa
y1 = = = 0.458
P 75kPa
We see that they are not the same as the measured values.
Part b). We can recalculate the equilibrium compositions with air as a third component. Air most
likely will not be present in a large amount in the liquid phase, so we will assume that the liquid
consist solely of benzene and toluene.
Liquid phase: x1 = 0.1604 and x2 = 1 - 0.1604 = 0.8396 (measured)
Vapor phase: y3 corresponds to the mole fraction of air in the vapor phase.
We have: 1 = y1 + y2 + y3 .
We employ Raoult’s law for the toluene:
y2 P = x2 P2sat
(1 - y1 - y3 ) P = x2 P2sat
x2 P2sat 0.8396*54kPa
y3 = 1 - y1 + P = 0.7081 +
75kPa
y3 = 0.100
Then we find what would be the Toluene mole fraction in the vapor phase to see if it
corresponds to the measured value: y2 = 1 - y1 - y3
We get y2 = 0.608 which corresponds to the measured value