Department of Chemical Engineering

University of San Carlos

Nasipit, Talamban, Cebu City

CHE 411N
Phase & Chemical Equilibria of Mixtures
Problem Set on Liquid-Liquid Equilibrium and Vapour-Liquid-Liquid Equilibrium

Date Submitted
September 15, 2015

Submitted to
Engr. Luis K. Cabatingan

Submitted by
Jan Rommel T. Duterte

11.2-14
Given:
Alcohol (1) water mixture containing 2 mol% alcohol
Bubble point is 90C and 1.013 bar
Vapor pressure data
PH2O (T = 90C) = 0.7733 bar
PROH (T = 90C) = 0.4 bar
Required:
Assuming that H2O = 1, find the composition of the vapor in equilibrium with the solution. Also
find the activity coefficient of alcohol in the solution.
When more than 2 mol% alcohol is present, a second liquid phase forms that contains 65 mol%
alcohol. Find the activity coefficients of alcohol and water in the second liquid phase.
Solution:
Using the modified Raoults Law,

x2 2 P2vap 0.98 ( 0.7733 )

y 2=
=
=0.75
P
1.013
1=

( 1 y 2 ) P
vap

x 1 P1

=31.66

When the second liquid phase is formed, the liquid-liquid equilibrium relation is used.

II1 =

x 1I I1 0.02 ( 31.66 )
=
=0.9742
0.65
x II1

x 2I I2 0. 98
= II =
=2.8
0.3 5
x2
II
2

Answer:
The vapor in equilibrium with the 2 mol% alcohol solution contains 75 mol% water and 25 mol%
alcohol, and the activity coefficient of alcohol is 31.66. Once the second liquid phase forms, the activity
coefficients of water and alcohol are 2.8 and 0.9742, respectively.
11.2-15
Given:
For a binary liquid mixture, activity coefficients are given by

RT ln i= i ( 1xi ) 2+ i ( 1x i )3 for i=1, 2

ln 1 =2, ln 2 =3

Required:
Determine whether a mixture containing 30 mol% of component 1 forms a single stable liquid
phase or two liquid phases at 245 K
Solution:
Refer to next page.
Answer:
The mixture is not stable and phase separation will occur.

11.3-2
Given:
50 mol % isobutane (1) 50 mol % furfural (2) mixture at 37.8C
At 37.8C, the two coexisting liquid phases contain 11.8 and 92.5 mol% isobutane, ISO (xISO =
0.925) = 1.019, FUR (xFUR = 0.882) = 1.033
Vapor pressure data
PISO (T = 37.8C) = 4.909 bar
PFUR (T = 37.8C) = 0.00493 bar
Required:
Estimate the pressure and vapor-phase composition in equilibrium with the liquid
Solution:
As given,

II

x 1 =0.118 and

x 1=0.925 . For liquid-liquid equilibrium,

II

II

x i i =xi i

so

II II vap
Pbubble = x Ii Ii Pvap
i = x i i Pi

Additionally,

x2II II2
= I =12.1481
x2
I
2

So the bubble point pressure is

Pbubble =( 0.9251.0194.909 )+ ( 0.07512.14810.00493 )=4.63

The vapor phase composition is then

x1 1 Pvap
1
y 1=
=0.9994
P
Answer:
The vapor in equilibrium with the liquid has a composition of 99.94 mol% isobutane and is at 4.63 bar.
11.3-4
Given:

Glycerol (1) acetophenone (2) at 140C

One liquid phase contains 9.7 mol% acetophenone, the other 90.3 mol%
Assume the one-constant Margules equation is obeyed for the activity coefficients
Vapor pressure data
PGLY (T = 140C) = 0.00313 bar
PAC (T = 140C) = 0.167 bar
Required:
P-x diagram for the system
Solution:
Since

x Ii Ii =xiII IIi ,
2

0.097 e

A ( 10.097 )
RT

=0.903 e

A ( 10.903 )
RT

[ (10.097) ( 10.903) ]
0.097
=e RT
0.903

ln

0.097 0.806 A
=
0.903
RT

A
=2.77
RT
Therefore,
2

1=2.77 ( 1x1I ) 2=2.77 ( 1x2I )

The equilibrium pressure is then computed as

P= x i i Pvap
i

The values and graph are shown below.

x1
x2
1
0
1
15.95863
0.02
0.98
14.30069
0.04
0.96
12.84342
0.06
0.94
11.56024
0.08
0.92
10.42835
0.1
0.9
9.428151
0.2
0.8
5.887315
0.3
0.7
3.885688
0.4
0.6
2.710681
0.5
0.5
1.998706
0.6
0.4
1.557684
0.7
0.3
1.283127
0.8
0.2
1.117171
0.9
0.1
1.028087
0.91
0.09
1.022691
0.92
0.08
1.017886
0.93
0.07
1.013666
0.94
0.06
1.010022
0.95
0.05
1.006949
0.96
0.04
1.004442
1
0
1

2
1
1.001109
1.004442
1.010022
1.017886
1.028087
1.117171
1.283127
1.557684
1.998706
2.710681
3.885688
5.887315
9.428151
9.912901
10.42835
10.97668
11.56024
12.18158
12.84342
15.95863

Peq
0.00313
0.050835
0.088812
0.118805
0.142254
0.160346
0.199434
0.197484
0.183999
0.17002
0.159474
0.153646
0.15294
0.157473
0.158211
0.158999
0.159837
0.160724
0.161659
0.16264
0.167

0.25

0.2

0.15
P, bar
0.1

0.05

0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

xAC

11.3-5
Given:
Methyl ethyl ketone (1) water (2) at 73.4C
LLE data
T = 20C
xMEK
0.0850
0.6363

Liquid phase 1
Liquid phase 2
Vapor pressure data
PMEK (T = 73.4C) = 0.8337 bar
PH2O (T = 73.4C) = 0.3603 bar
Required:
Make a P-x-y diagram
Determine whether an azeotrope occurs, and at what composition
Solution:
The two-constant Margules equations are to be used.

xH2O
0.9150
0.3637

RT ln 1= 1 x 22+ 1 x 32
2

RT ln 2= 2 x 1+ 2 x 1
Where
i +1

i=A +3 (1 )

i=4 (1 )i B
Using the general LLE relation,

[
[

I2

I3

]
]

[
[

II 2

II 3

x + 1 x2
x + 1 x2
x exp 1 2
=x1II exp 1 2
RT
RT
I
1

x 2 exp

2 x I12 + 2 x 1I 3
2 x II1 2 + 2 x 1II 3
II
=x2 exp
RT
RT

]
]

Solving for A and B requires two equations. These are derived from the general LLE relation.

x I1
II

x1

=exp

1 x II2 2 + 1 x 2II 3( 1 x2I 2+ 1 x I23 )

RT

x1
= 1 x II2 2 + 1 x 2II 3( 1 x2I 2 + 1 x I23 )
II
x1
RT ln
0.705 1 +0.718 1=4906.23
0.705 A0.757 B=4906.23

x I2
2 x II1 2 + 2 x 1II 3( 2 x I12 + 2 x I13 )
=exp
RT
x 2II

x I2
= 2 x II1 2 + 2 x 1II 3( 2 x I12 + 2 x I13 )
II
x2
RT ln
0. 398 2 +0. 257 2 =2248.593
0. 398 A0. 166 B=2248.593
Solving these equations simultaneously gives A = 4818.03 J/mol and B = -1994.08 J/mol. The activity
coefficients are calculated using the two-constant Margules equations with these constants.
xMEK
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0

xH2O
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

1
10.63677
5.42413
3.186138
2.120311
1.572248
1.277661
1.119101
1.039126
1.006002
0.998729
1

2
1
1.035326
1.136318
1.300332
1.525901
1.805936
2.120162
2.428354
2.66881
2.768041
2.664787

Peq
0.3603
0.787935
0.858789
0.858268
0.854183
0.857932
0.865354
0.868904
0.863278
0.849108
0.8337

yMEK
0
0.573918
0.618611
0.617885
0.613819
0.620787
0.646899
0.697918
0.777228
0.882544
1

0.9
0.8
0.7
P, bar

0.6
P-x
0.5

P-y

0.4
0.3
0

0.1

0.2

0.3

0.4

0.5

x, y of MEK

0.6

0.7

0.8

0.9

1
0.9
0.8
0.7
0.6
yMEK

0.5
0.4
0.3
0.2
0.1
0
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

xMEK

Answer:
The mixture has an azeotrope that occurs when the liquid composition is approx. 70 mol% methyl ethyl
ketone at a pressure of approx. 0.87 bar at 73.4C.