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Example 7.1: Experimental VLE data for the acetone (1) ethanol (2) system for T = 32C is
available. Check the thermodynamic consistency using the Redlick-Kister test. Assume that the
vapour is ideal, and that the infinite dilution activity coefficients are given by: An 1 = 0,810 and
An 2 =0,738.
P/mmHg x1 y1 An (1 /2 )
87.64 0 0 0.809921
102.7 0.025 0.1605 0.747447
116.2 0.05 0.27 0.688215
128.3 0.075 0.3505 0.633862
139.7 0.1 0.413 0.584046
159.5 0.15 0.502 0.480999
175.9 0.2000 0.569 0.402465
190.1 0.25 0.619 0.322316
202.4 0.3 0.66 0.24899
223.8 0.4 0.722 0.098267
242 0.5 0.773 -0.03627
257.4 0.6 0.817 -0.17091
271.9 0.7 0.859 -0.30189
285.3 0.8 0.902 -0.42825
297.9 0.9 0.95 -0.51439
309.47 1 1 -0.73781
xi Pi *
Solution: With an ideal vapour phase the equilibrium relationship reduces to: i =
yi P
From the given data we have P1* = 309,47 mmHg and P2* = 87,64 mmHg. Thus we can calculate
the activity coefficients using the above calculation. The plot is shown in the Figure below. The
areas were determined using the trapezoid rule (and the Excel spreadsheet programme). The
1
values are sufficiently close for the data to be accepted as consistent.
0.8
0.6
0.4
Area I = 0,171
ln ( 1/ 2)
0.2
0
0 0.2 0.4 0.6 0.8 1
-0.2
-0.8
x1
Example 7.2 n-Hexane (1) and ethanol (2) form an azeotrope at 1 atm and 58C with x1 = 0,67.
Calculate the equilibrium constant K1 = y1/ x1, at x1 = 0,5 and 58C.
Answer: Let hexane be component (1) and ethanol component (2)
Assume ideal vapour
y1 P = 1 x1 P1 At the azeotrope x1 = y1 = 0,67
P P
1 =
2 =
P1 P2
2
Solve A12 = 1,695 and A21 = 3,501
y P 1 P1 2 1 P1
K1 = 1 = 1 1 =
= = 1,391
x1 P x1 1 P1 + x 2 2 P2 1 P1 + 2 P2
Example 7.3 A vapour mixture of acetone (1) and methanol (2) with y1 = 0,45 is to be
condensed at a pressure of 1 atm. The following VLE datum is available: x1 = 0,295; y1 = 0,420;
T = 59,6C and P = 1 atm.
(a) Do a rough calculation to determine the maximum temperature that the liquid can leave
the condensor at.
(b) Explain how you would improve on your calculation
y1 P y2 P
1 =
y2 =
x1 P1 x 2 P2
0,42 0,58
= =
0,295(1,125) 0,705(0,820)
= 1,268 = 1,001
The activity coefficients are very close to unity so it is very close to an ideal system
First assume it is ideal
Guestimate temperature until: P = 1 = x1 P1 + x 2 P2 = 0,45 P1 + 0,55 P2
to obtain bubble point temperature.
T = 60,78C
Do better by incorporating activity coefficient model. Use Van Laar:
Van Laar A12 = 0,2426 A21 = 9,8339
P = 1 = 1 x1 P1 + 2 x 2 P2
3
Now T = 56.8 C
Another method: We need the bubble point (max temperature) where the mixture is still
completely in the liquid state:
i Pi D
Ki zi = 1,0 Ki =
P
1 P1D 2 P2 D
x1 + (1 x1 ) = 1
P P
Guess temperature until LHS equals 1 (Note only T is unknown)
65
Acetone (1) - methanol (2)
63 1 atm
61
o Bubble point
T/ C
59
57
55
0 0.2 0.4 0.6 0.8 1
x 1, y 1
Example 7.4 The VLE K-values at 343 K and 1 bar are K1 = 0,719, K2 = 1,31 for the completely
miscible binary system benzene (1)/chloroform (2). Calculate the equilibrium compositions of
the liquid and vapour phases and the fraction of the total system that is liquid for a total system
composition of (a) 40 mole % benzene, and (b) 50 mole % benzene.
Answer:
Note: Constant T and P. Gibbs phase rule: F = 2 - + C = 2 2 + 2 = 2
4
(F = degrees of freedom, = number of equilibrium phases and C = number of components)
As there are two equilibrium phases and 2 components, fixing T and P means that
composition is fixed.
Benzene (1) chloroform (2)
y1 = K1x1
y2 = K2x2
1 - y1 = K2(1 - x1)
1 - K1y1 = K2 K2x1
(K1 - K2)x1 = 1 K2
1 K2
x1 =
K1 K 2
K1 (1 K 2 )
y1 =
K1 K 2
Note that x1 and y1 are independent of z1
x1 = 0,5245 x2 = 0,4755
y1 = 0,3771 y2 = 0,6229
Basis: 1 mol mixture
V + L =1 (Mole balance)
y1V + x2 L = z1 (component balance)
K1x1 (1 L )+ x1 L = z1
K1x1 K1x1L + x1 L = z1
L1x1 (1 K1 ) = z1 - K1x1 = z1 - y1
z1 y1 z (K K 2 ) K1 (1 K 2 )
L = = 1 1
x1 (1 K1 ) (1 K 2 ) (1 K1 )
for z1 = 0,4 L = 0,1554
for z1 = 0,5 L = 0,8338
Example 7.5 In the system PQ, activity coefficients can be expressed as:
An P = 0,5 xQ and An Q = 0,5 x P
2 2
* *
The vapour pressures of P and Q at 80C are PP = 900 mmHg and PQ = 600 mmHg. Is there
an azeotrope in this system at 80C, and if so, what is the azeotrope pressure and composition?
Answer:
At azeotrope xP = yP xQ = yQ
y P P = x P P PP* equilibrium relationship
5
P
P = at azeotrope
PP*
P
An( P ) = An * = 0,5 xQ = 0,5 (1 x P )
2 2
(1)
PP
P
similarly An Q = An * = 0,5 x P
2
(2)
P
Q
(1) (2) :
PQ*
An * = 0,5(1 x P ) 0,5 x P
2
P
P
[
= 0,5 1 2 x P + x P x P
2 2
]
= 0,5[1 - 2 xP]
= 0,5 - xP
= -0,40547
xP = 0,90547 xQ = 0,09453
Also (
P = PQ* exp 0,5 x P
2
)
= 904,03 mmHg
Example 7.6 n
A = B + C KP = 16
Component A decomposes to form B & C in the gas phase. Liquid B is immiscible with either A
or C. Assume that the vapour behaves ideally and that A & C form an ideal solution in the liquid
phase. Find the pressure below which only a gas phase exists when initially only A was present
and the system is at chemical equilibrium. PA = 5 atm PB = 20 atm PC = 2 atm
Answer:
Basis: 1 mol mixture
nA = 1 - nB =
B nC = nT = 1 +
1
yA = y B = yC =
1+ 1+
6
2
P 2
p B pC 1 + 2
KP = = = P
pA 1 12
P
1+
Since PB* >> PA* , PC* assume that the first drop of liquid at the dew point will consist of a
mixture of A and C.
yAP 1 P
p A = x A PB = yAP xA = =
PA
1 + PA
P
pC = xC PB = yC P xC =
1 + PC
At the dew point xA + xC = 1
1 P P
+ = 1
1 + A
P 1 + PC
1
P =
1 1 1
+
1 + PA (1 + ) PC
From equation 1:
2 P = (1 2 ) K p
Kp
or = (2)
P + Kp
10(1 + )
P = (3)
2 + 3
7
0.8881 4.0480 0.8934
0.8934 4.0456 0.8934
0.8934 4.0455 0.8934
0.8934 4.0455 0.8934
0.8934 4.0455 0.8934
0.8934 4.0455 0.8934
0.8934 4.0455 0.8934
P = P(a)
4.8 a = a(P)
4.6
Intersection
P, atm
defines solution
4.4
4.2
4
0 0.2 0.4 0.6 0.8 1
a
Now check that pure B liquid was not present. If it were present it would contribute its vapour
pressure to the total pressure, i.e. 20 atm. This is higher than the system pressure. Therefore there
is no liquid B present.
Example 7.7. The binary system, pentane (1) acetone (2), forms an azeotrope at 566,65 mmHg
pressure and 25C that contains 24,5 % (mole basis) acetone. At this temperature the vapour
pressures of the two components are: P sat pen tan e = 226,3 mmHg and P sat acetone = 502,4 mmHg.
Assume that this system is well described by the following modified Wilson activity coefficient
model:
8
E
Answer:
nG E
An 1 =
n1 RT
T , P , n2
n1 + n 2 A12 n 2 + n1 A21
= n1 An n 2 An
n1 n1 + n 2 n1 + n 2
n +n A (n + n ) (n 2 + n1 A21 )
n 2 1 2 21 1 2
n1 + n 2 A21 (n1 + n2 )2
n1 n 2 (1 A12 ) n 2 n 2 ( A21 1)
= An( x1 + x 2 A12 )
n1 + n2 n1 + n 2 A12 n1 + n 2 n 2 + n1 A21
x x 2 A12 x ( A 1)
= An( x1 + x 2 A12 ) x1 2 x 2 2 21
x1 + x 2 A12 x 2 + x1 A21
1 x1 x 2 A12
= An( x1 + x 2 A12 ) x1 x 2 x 2 A21 x 2 x1 A21 + x1 A21
x1 + x 2 A12 x 2 + x1 A21
A21
= An( x1 + x 2 A12 ) + x1 1
1
x2 1
x1 + x 2 A12 x 2 + x1 A21
x1 x 2 A21
= 1 An( x1 + x 2 A12 )
x1 + x 2 A12 x 2 + x1 A21
x1 + x 2 A12 x1 x 2 A21
= An( x1 + x1 A21 )
x1 + x 2 A12 x1 + x 2 A12 x 2 + x1 A21
A12 A21
= An( x1 + x 2 A12 ) + x 2
x1 + x 2 A12 x 2 + x1 A21
Similarly
A21 A12
An 2 = An(x1 + x 2 A12 ) + x1 (2)
x 2 + x1 A21 x1 + x 2 A12
9
(B) Azeotrope Assume vapour behaves ideal at azeotrope since x1 = y1 and x2 = y2 and
P
y1 P = 1 x1 P1 1 =
sat
sat
(1)
P1
P
2 = sat
(2)
P2
we can solve for A12 and A21 using these two equations.
(c) Heat of mixing (Use Gibbs-Helmholtz)
d GE HE
=
dT RT RT 2
d GE
=
d
[ x1An(x1 + x2 A21 ) x2 An(x2 + x1 A12 )]
dT RT dT
dA21 dA12
x 2 dT x1 dT
= x1 x2
x1 + x 2 A21 x 2 + x1 A12
dA21 dA12
= + 212 = 122
dT RT dT RT
d GE 21 12
H E
= RT 2
= x1 x 2 +
dT RT x1 + x 2 A21 x 2 + x1 A12
Example 7.8 Consider a binary mixture of aniline and methylcyclohexane (MCH) having
infinite dilution activity coefficients at 25C and 1 atm of 16,1 and 11,4 respectively. Using Van
Laar activity coefficient model shown below, determine their mutual solubilities. (Hint: Use a
graphical solution technique!)
2 2
A12 x A21 x
An 1 = A21 and An 2 = A12
A21 x1 + A12 x 2 A21 x1 + A12 x 2
Answer:
Aniline (1) MCH (2)
10
An 1 = A21 = 2,7788 An 21 = A12 = 2,434
The activity coefficients can now be calculated over the whole concentration range. The
equilibrium conditions are:
( 1 x1 ) = ( 1 x1 ) (I)
and ( 2 x 2 ) = ( 2 x 2 ) (II)
[ 2 (1 x1 )] = [ 2 (1 x1 )]
Conditions I and II must be satisfied simultaneously for two different x1 and x1 . A graphical
solution procedure is as follows:
x1 1 2 1 x1 2 x2
0,01 15,12 1,0003 0,1512 0,9903
0,08 9,937 1,0202 0,7949 0,9386
0,10 8,884 1,0316 0,8884 0,9284
0,12 7,9697 1,0455 0,9564 0,9201
0,20 5,3376 1,1283 1,0675 0,9027
0,40 2,4311 1,5769 0,9724 0,9461
0,80 1,0922 5,0932 0,8738 1,0186
0,90 1,0217 7,427 0,9195 0,7427
1.1
0.9
2x 2
Two values:
0.8
x 1 = 0,105 and
x 1 = 0,848
0.7
0.6
0 0.4 0.8 1.2
1x 1
11
Aniline in methylcyclohexane: x1 = 0,105
Methylcyclohexane in aniline: x1 = 0,152
Example 7.9 The activity coefficient, for component A, in the system A + B is given by:
RT An A = 3367 x 2
Answer:
1. Gibbs-Duhen x A dAn A + x B dAn B = 0
An A = Ax B
2
dAn A = 2 Ax B dx B = 2 Ax B dx A
dAn B 2 Ax A dx A
2 xA
An B xA x
D
dA n B = 2 A D
x A dx A = 2A A
2 0
3367 2
or An B = Ax A = xA
2
RT
2. Yes! (See below!)
3. y A P = x A A PA y B P = x B B PB
D D
If azeotrope x A = y A and x B = y B P = A PA = B PB
D D
A P
D
= BD = 2 =
exp Ax B
2
( )
B PA exp Ax A
2
( ) = 1
12
or An A An B = AxB Ax A = A( x A + xB )( xB x A ) = A(1 2 x A ) = An 2
2 2
A An 2 1,5 An 2
xA = = = 0,269 xB = 0,7310
2A 3
D D
(
P = B PB = PB exp 1,5 x A
2
) = 73,56 kPa
13