University of San Carlos

Nasipit, Talamban, Cebu City 6000

Department of Chemical Engineering

CHE 411N

Assignment on Low Pressure Vapor-Liquid Equilibria in Non-ideal Mixtures

Submitted by:

Duterte, Jan Rommel T.

Submitted to:

Engr. Luis K. Cabatingan

Instructor

September 1, 2015

10.2-1
Given:
ethyl bromide (1) n-heptane (2) mixture at 303.15 K

vap

vap

P1 = 0.7569 bar , P2 = 0.0773 bar

regular solution parameters
VL (cm3/mol)
75
148

ethyl bromide
n-heptane

(cal/cm3)1/2
8.9
7.4

Required:
a) Composition of the vapor in equilibrium with a liquid containing 47.23 mol % ethyl bromide at
303.15 K and 0.4537 bar, assuming the solution is ideal
b) Vapor composition in part a assuming the solution is regular
c) Vapor composition in part a using the UNIFAC model
d) Vapor composition in part a given that a vapor of composition 81.5 mol % ethyl bromide is in
equilibrium with 28.43 mol % liquid ethyl bromide solution at a total pressure of 0.3197 bar at
303.15 K
Solution:
a) Using Raoults Law,

x1 P1vap
y1 =
= 0.7879
P
x2 P2vap
y2 =
= 0.0899
P
Assuming the solution is ideal, yi = 0.8778.
b) In order to use the regular solution model, the volume fraction i must first be determined.

1 =

x1 V 1
= 0.3120
x1 V 1 + x 2 V 2

2 =

x2 V 2
= 0.6880
x1 V 1 + x 2 V2

The activity coefficient i can now be calculated.

2

1 = e

V1 2 ( 1 - 2 )
RT

2 = e

V2 1 ( 1 - 2)
RT

= 0.8997
2

= 0.0949

Assuming the solution follows the regular solution model, y i = 0.9946. This value is much
closer to unity compared to the value obtained from the ideal solution model, and this is an
indication that the mixture is not ideal and is better described by the regular solution model.
c) Using the Modified UNIFAC program,

1 =1.1017

and

2 =1.0919 . The vapor

compositions can then be computed using the modified Raoults Law.

y1 =

x1 1 Pvap
1
= 0.8681
P

y2 =

x2 2 Pvap
2
= 0.0982
P

Assuming the solution follows the UNIFAC model, yi = 0.9663.

d) The van Laar model is to be used to calculate the vapor composition. The activity coefficient of
each component is first calculated (at x 1 = 0.2843, y1 = 0.815 and P = 0.3197 bar), then these
2

values are used to calculate the van Laar and parameters. These parameters are then used to
calculate the activity coefficients at the new composition (x 1 = 0.4723 and P = 0.4537 bar), and
the modified Raoults Law used to calculate the new vapor compositions.
First, the initial activity coefficients.
INI

1 =
INI
2 =

y1 P
x1 P

vap
1

y2 P
x2 P

vap
2

0.815(0.3197)
= 1.2108
0.2843(0.7569)

0.185(0.3197)
= 1.0691
0.7157(0.0773)

Using the van Laar equations for and ,

(
(

INI

= 1+

= 1+

x2 ln 2
x1 ln

INI
1

x 1 ln INI
1
x 2 ln

INI
2

)
)

ln 1INI = 0.6756

ln INI
2 = 0.3052

Calculating the final activity coefficients (for when x 1 = 0.4723 and P = 0.4537 bar)

FIN

=e

1+

x1
x2

) = 1.0790

x2
x1

) = 1.1443

FIN
2

(
=e

1+

The vapor compositions are then

vap
x1 FIN
1 P1
y1 =
= 0.8502
P
vap
x2 FIN
2 P2
y2 =
= 0.1029
P

Assuming that the solution follows the van Laar model, yi = 0.9531.
Answer/s:
The table below summarizes the calculated values.
Assuming the solution:
is ideal
is regular
follows the UNIFAC
model
follows the van Laar
model
The regular solution model describes
the closest to

y i=1

y1

y2

yi

0.7879
0.8997

0.0899
0.0949

0.8778
0.9946

0.8681

0.0982

0.9663

0.8502

0.1029

0.9531

the solution best because among all the models used, its results are

10.2-2
Given:
water (1) furfural (2) mixture at 109.5C and 1.013 bar
at equilibrium, x1 = 0.10 and y1 = 0.81
temperature of the mixture is changed to 100.6C, and some of the vapor condenses
3

vapor pressure data

Species

Pvap (bar)
1.4088
1.0352
0.1690
0.1193

Temperature (C)
109.5
100.6
109.5
100.6

Water
Furfural

Required:
Assuming that the vapor phase is ideal and the liquid-phase activity coefficients are independent of
temperature but dependent on concentration, compute the
a) equilibrium vapor composition
b) equilibrium liquid composition
at the new temperature.
Solution:
The van Laar model is to be used to calculate the vapor and liquid compositions. The activity coefficient
of each component is first calculated (at x 1 = 0.10, y1 = 0.81 and P = 1.013 bar), then these values are used
to calculate the van Laar and parameters. First, the initial activity coefficients.

INI
1 =
INI

2 =

y1 P
x1 P

vap
1

y2 P
x2 P

vap
2

0.815(0.3197)
= 5.8243
0.2843(0.7569)

0.185(0.3197)
= 1.2654
0.7157(0.0773)

Using the van Laar equations for and ,

(
(

= 1+

x2 ln INI
2
x1 ln

INI
1

)
)

ln 1INI = 8.5461

INI 2

= 1+

x 1 ln 1
x 2 ln

INI
2

ln INI
2 = 0.7898

Since the final liquid compositions are yet to be found and they are needed to calculate the final activity
coefficients (which are used to calculate the final vapor compositions), a trial-and-error solution is used.
The following equations must be satisfied in order to find the vapor and liquid compositions:

x 1 + x2 = 1; y 1 + y 2 = 1
1.0352 x 1 1 = 1.013 y 1 ; 0.1193 x 2 2 = 1.013 y 2

FIN
1

(
=e

x1
1+
x2

);

FIN
2

(
=e

1+

x2
x1

A trial value of x1 and x2 is used to calculate

FIN
1
and

FIN
2
. The activity coefficients are then used

to calculate the vapor compositions. The calculation is repeated until

x i= y i=1

. Using the

Microsoft Excel Solver function, the vapor and liquid compositions are found to be x 1 = 0.9111, x2 =
0.0889,
y1 = 0.1293 and y2 = 0.8661.
Answer/s:
When the mixture is at 100.6C, the water content of the liquid is 91.11 mol % and that of the vapor is
12.93 mol %. The calculations tell us that the water content of the liquid increased from 10 to 91 mol %
and in the vapor decreased from 81 to 13 mol %; this means that the vapor that condensed may have
primarily been water vapor.
10.2-4
Given:
4

ethanol (1) benzene (2) mixture at 45C

experimental data

x1

y1

P (bar)

0
0.0374
0.0972
0.2183
0.3141
0.4150
0.5199
0.5284
0.6155
0.7087
0.8102
0.9193
0.9591
1.00

0
0.1965
0.2895
0.3370
0.3625
0.3842
0.4065
0.4101
0.4343
0.4751
0.5456
0.7078
0.8201
1.00

0.2939
0.3613
0.3953
0.4088
0.4124
0.4128
0.4100
0.4093
0.4028
0.3891
0.3615
0.3036
0.2711
0.2321

Required:
Prepare an x-y and P-x diagram for the system assuming, separately,
a) the mixture is ideal
b) the mixture is regular
c) the mixture is described by the UNIFAC model
d) the activity coefficients for this system obey the van Laar equation and the datum point at

x EA =0.6155 is used to obtain the van Laar parameters

Compare the results obtained in parts (a)(d) with the experimental data. Also compare the computed
van Laar coefficients with those given in Table 7.5-1.
Solution:
a) The complete x y diagram at constant temperature can be constructed by using the vapour
pressure data to calculate the total pressure and value of y i for each value of x i. From Raoults
Law, the equilibrium pressure at each liquid propylamine composition x 1 is given as
vap

vap

vap

vap

P ( x1 ) = x 1 P1 + x 2 P 2 = x 1 P1 + (1-x 1 P2
where

P1vap=0.2321

bar and

P2vap=0.2939

bar. To calculate the vapour-phase mole

fraction,
vap

x P
y1 = 1 1
P( x 1 )

The following table summarizes the quantities calculated using the equations above.
Table 1. Values obtained using the ideal solution model

x1

x2

P ( x1 )

y1

0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00

1.00
0.90
0.80
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00

0.2939
0.2877
0.2815
0.2754
0.2692
0.2630
0.2568
0.2506
0.2445
0.2383
0.2321

0
0.0807
0.1649
0.2529
0.3449
0.4413
0.5422
0.6482
0.7596
0.8767
1
5

The diagrams can now be constructed, as shown in Figure 1 and 2.

b) In order to use the regular solution model, the volume fraction and solubility parameter must be
known. Table 9.6-1 lists the molar volume and solubility parameter for some compounds
(including benzene), but the values for ethanol are not given and must be calculated. The molar
volume is given by
L

V =

MW

For ethanol, MW = 46.07 g/mol and = 0.789 g/cm3 [reference: Green, D. & Perry, R. (2008)
Perrys Chemical Engineers Handbook. 8th edition. McGraw Hill: USA] so

VL =

58.39

cm3/mol. The solubility parameter can be estimated from

vap U
V

vap H -RT
VL

The heat of vaporization can be estimated using the approximate integrated Clausius-Clapeyron
equation, which is valid over small temperature ranges:

P vap ( T2 )
H 1 1
ln vap
= - vap
R
T2 T1
P ( T1 )

Using the constants found in the 8 th edition of Perrys Chemical Engineers Handbook to calculate
the ethanol vapor pressure at T1 = 45C and T2 = 46C,

vap H = 41.845 kJ/mol. This is used

to calculate the solubility parameter for ethanol, which is calculated to be 12.667 (cal/cm 3)1/2. In
summary,
VL (cm3/mol)
Ethanol
58.39
Benzene
89
The volume fractions can then be calculated from

i =

(cal/cm3)1/2
12.667
9.2

xi Vi
x 1 V1 + x2 V 2

The activity coefficients are calculated from

1 = e

2 = e

V1 2 ( 1 - 2 )
RT

V2 1 ( 1 - 2)
RT

The equilibrium pressure and vapor composition is calculated using the modified Raoults Law:

Peq = x 1 1 Pvap
+ x2 2 Pvap
1
2
yi =

x i i P vap
i
Peq

The following table summarizes the calculated values.

Table 2. Values obtained using the regular solution model

1
0

2
1

1
3.0353

2
1

x1
0.00

Peq
0.2939

y1
0
6

0.0679
0.9321
2.6237
1.0078
0.10
0.1409
0.8591
2.2693
1.0342
0.20
0.2195
0.7805
1.9669
1.0849
0.30
0.3043
0.6957
1.7116
1.1696
0.40
0.3962
0.6038
1.4991
1.3042
0.50
0.4960
0.5040
1.3258
1.5164
0.60
0.6049
0.3951
1.1893
1.8574
0.70
0.7241
0.2759
1.0882
2.4286
0.80
0.8552
0.1448
1.0236
3.4476
0.90
1
0
1
5.4324
1.00
The diagrams can now be constructed, as shown in Figure 1 and 2.

0.3275
0.3485
0.3602
0.3652
0.3656
0.3629
0.3570
0.3448
0.3151
0.2321

0.1860
0.3023
0.3803
0.4352
0.4758
0.5088
0.5413
0.5860
0.6785
1

c) Using the Modified UNIFAC program, the activity coefficients of benzene and ethanol were
determined at various compositions. The following table summarizes the obtained values.
Table 3. Values obtained using the UNIFAC model

1
2
x2
x1
Peq
12.0387
1
1.00
0.00
0.2939
4.8244
1.0431
0.90
0.10
0.3879
2.9856
1.1329
0.80
0.20
0.4050
2.1796
1.2569
0.70
0.30
0.4103
1.7353
1.4202
0.60
0.40
0.4115
1.4589
1.6362
0.50
0.50
0.4097
1.2753
1.9281
0.40
0.60
0.4043
1.1503
2.3357
0.30
0.70
0.3928
1.0668
2.9292
0.20
0.80
0.3703
1.0172
3.8409
0.10
0.90
0.3254
1
5.3405
0.00
1.00
0.2321
The diagrams can now be constructed, as shown in Figure 1 and 2.

y1
0
0.2887
0.3422
0.3698
0.3915
0.4132
0.4393
0.4758
0.5350
0.6531
1

d) The van Laar model is to be used to calculate the vapor composition. The activity coefficient of
each component is first calculated (at x 1 = 0.6155, y1 = 0.4343 and P = 0.4028 bar), then these
values are used to calculate the van Laar and parameters. These parameters are then used to
calculate the activity coefficients at the new compositions, and the modified Raoults Law used to
calculate the new vapor compositions.
First, the initial activity coefficients.
INI

1 =
INI
2 =

y1 P
x1 P

vap
1

y2 P

0.4343(0.4028)
= 1.22455
0.6155(0.2321)

= 2.0164

vap

x 2 P2

Using the van Laar equations for and ,

(
(

= 1+

x2 ln INI
2
x1 ln

INI
1

)
)

ln 1INI = 2.0263

INI 2

= 1+

x 1 ln 1
x 2 ln

INI
2

ln INI
2 = 1.4998

The final activity coefficients are calculated using

FIN
1

(
=e

1+

x1
x2


FIN
2

(
=e

1+

x2
x1

And the vapor composition is then

vap
x1 FIN
1 P1
y1 =
P

The following table summarizes the calculated values.

Table 4. Values obtained using the van Laar model

1
2
x1
x2
Peq
7.5860
1
0.00
1.00
0.2939
4.6268
1.0259
0.10
0.90
0.3787
3.1027
1.1003
0.20
0.80
0.4027
2.2540
1.2234
0.30
0.70
0.4086
1.7522
1.4005
0.40
0.60
0.4096
1.4428
1.6410
0.50
0.50
0.4086
1.2476
1.9590
0.60
0.40
0.4040
1.1247
2.3736
0.70
0.30
0.3920
1.0506
2.9095
0.80
0.20
0.3661
1.0118
3.5985
0.90
0.10
0.3171
1
4.4808
1.00
0.00
0.2321
The diagrams can now be constructed, as shown in Figure 1 and 2.

y1
0
0.2835
0.3576
0.3841
0.3971
0.4098
0.4300
0.4661
0.5329
0.6665
1

0.8

Ideal mixture model

UNIFAC mixture model

0.6

van Laar model

yEtOH
0.4

0.2
Regular mixture model

0
0.00

0.10

0.20

Experimental data

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

xEtOH

Figure 1. x-y diagram of the ethanol-benzene system at 45C using different solution models

0.42
0.4
0.38
0.36
Ideal mixture model
0.34

UNIFAC mixture model

van Laar model

0.32
P, bar

0.3
0.28
0.26
Regular mixture model
0.24

Experimental data

0.22
0.2
0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

xEtOH

Figure 2. P-x diagram for the ethanol-benzene system at 45C using different solution models

Answer/s:
The P-x and x-y diagrams are given in Figure 1 and 2. These figures show that the experimental
data are most closely matched by the predictions of the UNIFAC and van Laar models. The calculated
values of the van Laar and parameters are about 4% larger and 7% smaller, respectively, than the
tabulated values for this system ( = 1.946, = 1.61), although the tabulated values were valid for the
temperature range 67C 80.1C and the system in the problem is at 45C.
10.2-8
Given:
N-pentane (1) acetone (2) system at 1.013 bar
Vapor-liquid equilibrium data
(bar)
x1

y1

T (C)

0.021
0.108
49.15
0.061
0.307
45.76
0.134
0.475
39.58
0.210
0.550
36.67
0.292
0.614
34.35
0.405
0.664
32.85
0.503
0.678
32.35
0.611
0.711
31.97
0.728
0.739
31.93
0.869
0.810
32.27
0.953
0.906
33.89
Required: Are these data thermodynamically consistent?
Solution: The thermodynamic consistency relation is
1

vap
1

1.560
1.397
1.146
1.036
0.960
0.913
0.903
0.887
0.880
0.896
0.954

P2vap
0.803
0.703
0.551
0.493
0.453
0.425
0.421
0.413
0.410
0.419
0.445

ln 2 dx 1 =0
0

2
ln
Figure 3 is a plot of
1

versus mole fraction.

2
1.5
1

II

0.5
ln 2/1

0
-0.5

-1
-1.5
0

0.2

0.4

0.6

0.8

x1

Figure 3. Thermodynamic consistency test for the n-pentane - acetone system

The two areas, I and II, between the curve and the

ln

2
=0 line are equal in size but opposite in sign
1

so that the consistency relation can be considered satisfied, although the value of

ln

2
1

at x1 = 0.021

appears to be an outlier as all the other data points are linear.

Answer: Yes, the data are thermodynamically consistent.
10.2-14
Given:
20 mol % ethanol (1) solution in water (2) at 78.15C

At 78.15C,

P1vap=1.006 bar
vap

P2 =0.439 bar
lim 1 = 1 = 1.6931

x1 0

lim 2 = 2 = 1.9523

x2 0

Required:
Estimate the
a) total pressure and
b) composition
of the vapor in equilibrium with the system.
Solution:
The van Laar model uses the following two equations to predict activity coefficients:

10

ln 1=

ln 2=

x
1+ 1
x2

x
1+ 2
x1

For

x 1 0 and

1 ,

2 ,

x 2 0 . These allow the above equations to be simplified

to

ln 1 =

ln 2 =

(0)
1+
x2

(0)
1+
x1

which gives = 0.52656 and = 0.66901. These values are then used to calculate the activity
coefficients and, subsequently, the total pressure and equilibrium vapor composition.

(
=e

1+

x1
x2

) = 1.44433

x2
x1

) = 1.01825

(
=e

1+

The total pressure is

P= x 1 1 P1vap + x2 2 Pvap
2 =0.6482
bar

And the vapor composition is

x1 1 Pvap
1
y1 =
= 0.4483
P
vap

x P
y2 = 2 2 2
P

= 0.5517

Answer/s:
At 78.15C, the vapor in equilibrium with the system is at 0.65 bar and contains 44.83 mol %
ethanol and 55.17 mol % water.
10.2-16
Given:
benzene (1) cyclohexane (2) mixture
based on vapor-liquid equilibrium data, some authors have claimed that the system is described
by

ex
G = A x 1 x 2 where A ( J /mol ) = 3750-8T for T in Kelvin.

Required:
a) Derive expressions for the activity coefficients of benzene and cyclohexane

11

b) Determine the enthalpy and entropy changes on mixing when 1 mole of benzene and 2 moles of
cyclohexane are mixed at T = 300 K and constant pressure
c) Given the following vapor pressure data at T = 320 K,

vap

P1 =

vap

P2 =

0.3203 bar and

0.3218 bar, determine the bubble point pressure of the liquid in part (b) at T = 320 K, and the
composition of the vapor in equilibrium with that liquid
Solution:
a)

ex
Gex = x 1 Gex
1 + x 2 G 2 = x1 RT ln 1 + x2 RT ln 2
ex

G 1 = RT ln 1 and

Gex = A x 1 x 2 =A

Gex
2 = RT ln 2

N1
N1 + N 2

)(

N2
=A N1 N2 ( N1 + N2 )-2
N 1 + N2

N G ex = A N1 N 2 ( N1 + N 2 )-1
ex

G1 =

ex
N2
N1 N2
NG
-2
-1
2
=A N 1 N 2 ( N 1 + N 2 ) +A N 2 ( N1 + N 2 ) =A

=A x 2
N1
N 1 + N 2 ( N 1 + N 2 )2

Gex
2 =

ex
N1
N1 N2
NG
= A N 1 N 2 ( N 1 + N 2 )2 + A N 1 ( N 1 + N 2 )1= A

= A x 21
2
N2
N 1+ N 2 ( N 1 + N 2 )

Gex
1 = RT ln 1 ,

Since

ex

1 =e

G1
RT

A x2
RT

=e

A (1- x1)
RT

A (1- x2)
RT

=e

Similarly,
ex

2 =e
b)

x1=

G2
RT

1
3

A x1
RT

=e

=e

2
x
=
2
and
3

Recall,
ex
ex
Smix = SIM
mix + S =R x i ln x i +S
,
ex
ex
Gmix = GIM
mix + G =RT x i ln x i + G
, and

Hmix = Gmix +TSmix .

Gmix =N[RT ( x 1 ln x 1 + x 2 ln x 2 ) + x1 x 2 (37508T ) ] =3862.77 J
From the Maxwell relation between Gibbs energy and temperature,

Gex
=Sex =8x1 x 2
T
Smix =N[R ( x1 ln x 1 + x2 ln x 2 ) +8 x 1 x2 ] =21.21

J
K

Hmix = Gmix +TSmix =2500.23 J

c) Using the expressions for the activity coefficients derived in part (a),
12

vap

vap

P= x 1 1 P1 + x2 2 P2 =0.3557 bar
x1 1 Pvap
1
y1 =
= 0.3662
P bubble
y2 =
Answer/s:
a) The

x2 2 Pvap
2
= 0.6338
P bubble

activity coefficients
A ( 1- x1 )

1 = e RT

of

A ( 1-x2 )

the

benzene

and

cyclohexane

can

be

described

by

and 2 = e RT

, respectively.

b) When 1 mole of benzene and 2 moles of cyclohexane are mixed at T = 300 K and constant

Smix = 21.21 J K-1 and Hmix = 2500.23 J.

pressure,

c) At T = 320 K, the bubble point pressure of the liquid is 0.3557 bar and the vapor in equilibrium
with the liquid contains 36.62 mol % benzene and 63.38% cyclohexane.
10.2-21
Given:
At 20C, the methyl acetate (1) methanol (2) system forms an azeotrope with the following
properties:

x 1 = y1 =0.754 , x 2 = y2 =0.246 , and P = 183.54 mm Hg

The azeotrope is to be fed into a second distillation column operating at 50C

Pure-component vapor pressures
vap

log 10 PMA ( mm Hg ) =7.06524

1157.63
T ( K ) -53.424

vap

log 10 PMeOH ( mm Hg ) =8.08097

1582.271
T ( K ) -33.424

Required:
a) To determine whether the proposed process is possible, compute the azeotropic composition of a
methyl acetate methanol mixture at 50C. Assume that the parameters in the activity coefficient
you use are independent of temperature.
Solution:
The van Laar model is to be used to calculate the final azeotropic vapor and liquid compositions. The
activity coefficient of each component is first calculated at the initial azeotropic conditions (at x 1 = y1 =
0.754, x2 = y2 = 0.246 and P = 183.54 mm Hg), then these values are used to calculate the van Laar and
parameters. First, the initial activity coefficients.

1AZ,i =

P
183.54
=
= 1.0653
vap
172.2934
P1

2AZ,i =

P
183.54
=
= 1.8829
vap
97.475
P2

Using the van Laar equations for and ,

= 1+

x2 ln 2AZ,i
x1 ln

AZ,i
1

ln 1AZ,i = 1.150046

13

AZ,i 2

= 1+

x 1 ln 1
x 2 ln

AZ,i
2

ln AZ,i
= 1.0800
2

Since the final liquid compositions are yet to be found and they are needed to calculate the final activity
coefficients (which are used to calculate the final vapor compositions), a trial-and-error solution is used.
The following equations must be satisfied in order to find the vapor and liquid compositions:

x 1 + x2 = 1; y 1 + y 2 = 1

AZ,f

(
=e

1+

x1
x2

);

AZ,f
2

(
=e

1+

x2
x1

593.425 x 1 1 = y 1 P; 416.5845 x 2 2 = y 2 P
vap

vap

P= x 1 1 P1 + x2 2 P2

A trial value of x1 and x2 is used to calculate

1AZ,f and

2AZ,f . The activity coefficients are used to

calculate the total equilibrium pressure, then the vapor compositions. The calculation is repeated until

x i= y i=1

and

x i =y i . Using the Microsoft Excel Solver function, the azeotropic vapor and

liquid compositions are found to be x1 = y1 = 0.6533 and x2 = y2 = 0.3467 at 50C and 673.94 mm Hg.
Answer/s: The azeotropic composition of a methyl acetate methanol mixture at 50C is x MA = yMA =
0.6533 and xMeOH = yMeOH = 0.3467 at a pressure of 673.94 mm Hg.
10.2-23
Given:
Benzene (1) polyisobutylene (2) mixture at 10C
Data on physical properties
benzene
Molecular weight, g/mol

polyisobutylene
40 000
104 (monomeric)
131.9 (monomeric)

78

Molar volume, cm3/mol

88.26
0.1266 (at 298.15 K)
Vapour pressure, bar
Assumed to be negligible
0.2392 (at 312.75 K)
Data for the activity of benzene in PIB as a function of the mass ratio of benzene to PIB

m B /m PIB

a B = x B B

0.8331
0.5543
0.291

0.9811
0.9595
0.8388

Required:
a) Using the data in Illustration 10.2-7, compare the predictions of the Flory-Huggins theory using
= 1.0 with the data above
b) Compute the equilibrium partial pressure of benzene over benzene-PIB mixtures
Solution:
a) The average number of monomer units in PIB is

n=

M W2
= 384.6 units
M W 2, m

Assuming that mPIB = 1.0, the benzene weight fractions are given by

wB =

mB
m B + m PIB
14

and are 0.4545, 0.3566 and 0.2254, respectively. The benzene mole fractions (in terms of the
weight fraction) are then calculated as

wB
78
xB =
w B w PIB
+
78 40000
and are 0.9977, 0.9965 and 0.9933, respectively. The Flory-Huggins equations use the volume
fraction as a parameter, which is given by

B =

x B VB
x B VB + nx PIB VPIB

The benzene volume fractions are 0.4301, 0.3313 and 0.2050, respectively. Knowing this, and
calculating the parameter m as

m=

V PIB
=574.8
VB

allows us to calculate the activity coefficients using the Flory-Huggins equations.

For benzene at the three compositions given,

B = e

ln

B
1
2
+ 1(1- B) + (1- B)
xB
m

( )

The activities are calculated by multiplying the activity coefficients with the corresponding mole
fractions. The following table summarizes the calculated values.
Table 5. Results from the calculation of activities

REPORTED

m B / m PIB

CALCULATED

a B = x B B

% difference

0.8331
0.9811
1.0512
6.7
0.5543
0.9595
1.0101
5.0
0.291
0.8388
0.8529
1.7
b) As the vapour pressure of benzene at 10C is not given, it will be calculated using the constants
found in the 8th edition of Perrys Chemical Engineers Handbook.

PBvap ( 10) = e

83.107

6486.2
-6
2
-9.2194 ln283.15+6.9844 10 ( 283.15 )
283.15

=0.0605 bar

The benzene partial pressures are given by

PB = xB B P vap
B
The calculated partial pressures are shown in the following table.
Table 6. Calculation of the benzene partial pressure at different weight fractions

wB
xB
B
PB, bar
0.0
0.0
0.0
0
0.1
0.9828
0.5208
0.0310
0.2
0.9923
0.8112
0.0487
0.3
0.9955
0.9654
0.0581
0.4
0.9971
1.0364
0.0625
0.5
0.9981
1.0587
0.0639
0.6
0.9987
1.0545
0.0637
0.7
0.9992
1.0385
0.0628
0.8
0.9995
1.0201
0.0617
0.9
0.9998
1.0057
0.0608
1.0
1.0
1
0.0605
Answer:
a) The predictions of the Flory-Huggins theory when = 1.0 are in reasonably close agreement with
the experimental data.
15

b) The partial pressures of benzene are shown in table 6.

10.2-35
Given:
Component 1 and 2 mixture in vapour-liquid equilibrium
At 90C and 1.8505 bar, a vapour of composition y 1 = 0.3767 coexists with a liquid of
composition x1 = 0.4
Vapour pressures are given by

log 10 Pvap
i = A i

Bi
T

for pressure in bar and T in K, where A1 = 4.125, B1 = 1500, A2 = 5.000 and B2 = 1750
Required:
a) Determine the van Laar parameters of the system using the given data
b) Determine whether the mixture has an azeotrope at 90C and, if so, determine its composition and
identify whether it is a maximum- or minimum-pressure azeotrope
c) Obtain P-x-y and x-y diagrams for the system at 90C
d) An equimolar mixture of species 1 and 2 initially at very low pressure is compressed at a constant
90C. At what pressure does the first drop of liquid form, and what is its composition? At what
pressure does the last bubble of vapour disappear, and what was its composition?

Solution:
a) First, the initial activity coefficients.

INI
1 =
INI
2 =

y1 P
x1 P

vap
1

y2 P

0.3767(1.8505)
= 1.7649
0.4(0.9874)

= 1.2670

vap

x 2 P2

Using the van Laar equations for and ,

(
(

= 1+

= 1+

x2 ln INI
2
INI
1

x1 ln

x 1 ln INI
1
x 2 ln

INI
2

)
)

ln 1INI = 1.4999

ln INI
2 = 1.6004

b) The mixture has an azeotrope if xi = yi at any point within the composition range. Table 7 shows
the calculated values for species 1 using the van Laar model.
Table 7. Calculating the vapor composition using the van Laar model

x1
0.00
0.10
0.20
0.30
0.32
0.34
0.36
0.37
0.38
0.40
0.50
0.60

1
4.4812
3.4223
2.6765
2.1457
2.0591
1.9782
1.9024
1.8663
1.8314
1.7650
1.4913
1.2958

2
1
1.0143
1.0594
1.1404
1.1617
1.1849
1.2101
1.2235
1.2374
1.2670
1.4544
1.7271

Peq
1.5172
1.7230
1.8144
1.8468
1.8492
1.8507
1.8513
1.8513
1.8512
1.8505
1.8396
1.8159

y1
0
0.1961
0.2913
0.3442
0.3518
0.3589
0.3653
0.3683
0.3712
0.3767
0.4002
0.4228
16

0.70
1.1592
2.1246
1.7683
0.4531
0.80
1.0688
2.7111
1.6669
0.5065
0.90
1.0170
3.5935
1.4490
0.6237
1.00
1
4.9550
0.9874
1
The highlighted row is the azeotropic point; the mixture forms an azeotrope at approximately
0.37 mole fraction of species 1 at 90C and a pressure of 1.8513 bar. The mixture is a maximum
pressure azeotrope since the activity coefficients of both species are greater than 1.0, and there
are positive deviations from Raoults Law.
c) Using the values summarized in the previous table, the x-y and P-x-y diagrams can be
constructed.
1
0.8
0.6
y1
0.4
0.2
0
0.00

0.20

0.40

0.60

0.80

1.00

x1

Figure 4. x-y diagram of the species 1-2 mixture at 90C

1.88
1.78
1.68
1.58
1.48
P, bar

1.38

P-x

P-y

1.28
1.18
1.08
0.98
0.00

0.20

0.40

0.60

0.80

1.00

x1, y1

Figure 5. P-x-y diagram of the species 1-2 mixture at 90C

d) The pressures can be read from the P-x-y diagram of the system. The pressure at which the first
drop of liquid forms is approximately 1.67 bar, and this drop has a composition x 1 = 0.80. The last
bubble of vapor disappears at 1.84 bar, and the bubble had a composition of y 1 = 0.40.
Answer:
a) The van Laar parameters for the mixture are = 1.4999 and = 1.6004.
17

b) The mixture forms an azeotrope at approximately 0.37 mole fraction of species 1 at 90C and a
pressure of 1.8513 bar. The mixture is a maximum pressure azeotrope since the activity
coefficients of both species are greater than 1.0, and there are positive deviations from Raoults
Law.
c) See figures 4 and 5.
d) The pressure at which the first drop of liquid forms is approximately 1.67 bar, and this drop has a
composition x1 = 0.80. The last bubble of vapor disappears at 1.84 bar, and the bubble had a
composition of y1 = 0.40.
10.2-39
Given:
Water (1) 1,4-dioxane (2) mixture at 323.15 K
Vapor-liquid equilibrium data
P (mm Hg)
x1
120.49
0.0000
140.85
0.0560
151.16
0.0970
159.17
0.1700
164.57
0.2160
165.65
0.2980
167.89
0.3660
167.74
0.4400
167.79
0.4460
167.95
0.4840
166.84
0.5390
165.48
0.6290
160.82
0.7490
155.14
0.8110
142.64
0.8900
114.76
0.9670
92.51
1.0000
Required:
a) Activity coefficients at each of the reported compositions
b) Are these data thermodynamically consistent?
c) Plot of excess Gibbs energy as a function of composition
Solution:
a) The van Laar model will be used to calculate the activity coefficients.
coefficients at the azeotropic composition are calculated.

1AZ =

P
167.79
=
= 1.8138
vap
92.51
P1

2AZ =

P
= 1.3926
vap
P2

y1
0.0000
0.1920
0.2680
0.3450
0.3830
0.4030
0.4250
0.4430
0.4460
0.4510
0.4550
0.4660
0.4950
0.5430
0.6040
0.7950
1.0000

First, the activity

Using the van Laar equations for and ,

= 1+

(1x 1)ln 2AZ

x1 ln

AZ
1

ln 1AZ = 1.7022

(1-x1
x 1 ln 1AZ
1+
ln AZ
2

2
AZ
= ( ) ln 2 = 1.9836
The activity coefficients at every other composition are calculated using

18

 (1-x1
x
1+ 1

FIN
= e ()
1

(1- x 1
1+

FIN
2

=e

2
( x1)

The results are summarized in the following table.

Table 8. Activity coefficients of the water-dioxane system

x1
1
2
0.0000
5.4862
1
0.0560
4.6707
1.0047
0.0970
4.1663
1.0142
0.1700
3.4258
1.0453
0.2160
3.0449
1.0752
0.2980
2.4957
1.1519
0.3660
2.1409
1.2432
0.4400
1.8354
1.3795
0.4460
1.8138
1.3926
0.4840
1.6863
1.4837
0.5390
1.5283
1.6447
0.6290
1.3264
2.0072
0.7490
1.1437
2.7896
0.8110
1.0807
3.4103
0.8900
1.0273
4.5522
0.9670
1.0025
6.2638
1.0000
1
7.2690
b) For a system at constant temperature, the thermodynamic consistency relation is
1

ln 2 dx 1 =0
0

2
ln
Figure 6 is a plot of
1

versus mole fraction.

19

2.5
2
1.5
1
0.5
ln 2/1

0
-0.5
-1

-1.5
-2
0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

x1

Figure 6. Thermodynamic consistency test for the activity coefficients of the water-dioxane system

The two areas, I and II, between the curve and the

ln

2
=0 line are equal in size but opposite
1

in sign, so that the consistency relation can be considered satisfied.

c) Values of

Gex are computed from

ex
Gex = x 1 Gex
1 + x 2 G 2 = x1 RT ln 1 + (1-x 1 )RT ln 2

Figure 7 is a plot of the excess Gibbs energy as a function of composition.

1250
1000
750
Gex, J/mol
500
250
0
0.00

0.20

0.40

0.60

0.80

1.00

x1

Figure 7. Excess Gibbs energy as a function of mole fraction for the water-dioxane system

Answer:
a) See table 8.
b) Based on figure 5, the data are thermodynamically consistent.
c) See figure 6.

20