Chapter14 A

Chapter 14 - Section A - Mathcad Solutions
14.1
A12 := 0.59
A21 := 1.42
T := ( 55 + 273.15) K
Margules equations:
1 ( x1) := exp ( 1 x1) A12 + 2 ( A21 A12) x1
2
2 ( x1) := exp x1 A21 + 2 ( A12 A21) ( 1 x1)

2
Psat1 := 82.37 kPa

(a)
Psat2 := 37.31 kPa
BUBL P calculations based on Eq. (10.5):

Pbubl ( x1) := x1 1 ( x1) Psat1 + ( 1 x1) 2 ( x1) Psat2
y1 ( x1) :=
(b)
x1 1 ( x1) Psat1
Pbubl ( x1)
x1 := 0.25
Pbubl ( x1) = 64.533 kPa
y1 ( x1) = 0.562
x1 := 0.50
Pbubl ( x1) = 80.357 kPa
y1 ( x1) = 0.731
x1 := 0.75
Pbubl ( x1) = 85.701 kPa
y1 ( x1) = 0.808
BUBL P calculations with virial coefficients:

3
B11 := 963
cm
mol
B22 := 1523
cm
mol
12 := 2 B12 B11 B22
B11 ( P Psat1) + P y22 12
1 ( P , T , y1 , y2) := exp
R T
B22 ( P Psat2) + P y12 12
2 ( P , T , y1 , y2) := exp
R
539
B12 := 52
cm
mol
Guess:
x1 := 0.25
P :=
Psat1 + Psat2
y1 := 0.5
y2 := 1 y1
Given
y1 1 ( P , T , y1 , y2) P = x1 1 ( x1) Psat1

y2 2 ( P , T , y1 , y2) P = ( 1 x1) 2 ( x1) Psat2
y2 = 1 y1
y1
0.558
y
2 = 0.442
P
63.757
kPa
y1
y2 := Find ( y1 , y2 , P)
P
x1 := 0.50
Given
y1 1 ( P , T , y1 , y2) P = x1 1 ( x1) Psat1

y2 2 ( P , T , y1 , y2) P = ( 1 x1) 2 ( x1) Psat2
y2 = 1 y1
y1
0.733
y2 = 0.267
P
79.621
kPa
y1
y2 := Find ( y1 , y2 , P)
P
x1 := 0.75
Given
y1 1 ( P , T , y1 , y2) P = x1 1 ( x1) Psat1

y2 2 ( P , T , y1 , y2) P = ( 1 x1) 2 ( x1) Psat2
y2 = 1 y1
y1
0.812
y2 = 0.188
P
85.14
kPa
y1
y2 := Find ( y1 , y2 , P)
540
14.3
T := 200 K
P := 30 bar
H1 := 200 bar
B := 105
y1 := 0.95
3
cm
mol
Assume Henry's law applies to methane(1) in the liquid phase, and that the
Lewis/Randall rule applies to the methane in the vapor:
l
fhat1 = H1 x1
fhat1 = y1 1 P
By Eq. (11.36):
1 := exp
B P
R T
1 = 0.827
Equate the liquid- and vapor-phase fugacities and solve for x1:
x1 :=
14.4
y1 1 P
x1 = 0.118
H1
Ans.
Pressures in kPa
Data:
0.000
0.0895
0.1981
0.3193
x1 :=
0.4232
0.5119
0.6096
0.7135
i := 2 .. rows ( P)
(a)
12.30
15.51
18.61
21.63
P :=
24.01
25.92
27.96
30.12
x2 := 1 x1
0.000
0.2716
0.4565
0.5934
y1 :=
0.6815
0.7440
0.8050
0.8639
Psat2 := P1
It follows immediately from Eq. (12.10a) that:
ln 1 = A12
Combining this with Eq. (12.10a) yields the required expression
541
(b)
Henry's constant will be found as part of the solution to Part (c)
(c)
BARKER'S METHOD by non-linear least squares.

Margules equation.
The most satisfactory procedure for reduction of this set of data is to find
the value of Henry's constant by regression along with the Margules
parameters.
1 ( x1 , x2 , A12 , A21) := exp ( x2) A12 + 2 ( A21 A12) x1
2
2 ( x1 , x2 , A12 , A21) := exp ( x1) A21 + 2 ( A12 A21) x2

2
H1 := 50
Guesses:
A21 := 0.2
A12 := 0.4
Mininize the sums of the squared errors by

setting sums of derivatives equal to zero.
Given
0=
0=
0=
2
d
H1

Pi x1 1 x1 , x2 , A12 , A21
...
i
i
i
exp
A
dA12
(
)
12

+ x2i 2 x1i , x2i , A12 , A21 Psat2

2
d
H1

Pi x1 1 x1 , x2 , A12 , A21
...
i
i
i
exp
A
dA21
(
)
12

+ x2i 2 x1i , x2i , A12 , A21 Psat2

2
d
H1

Pi x1 1 x1 , x2 , A12 , A21
...
i
i
i
exp
A
dH1
(
)
12

+ x2i 2 x1i , x2i , A12 , A21 Psat2

A12
A21 := Find ( A12 , A21 , H1)

H
1
A12 0.348
A
=
21 0.178
H
1 51.337
542
Ans.
(d) 1 ( x1 , x2) := exp x22 A12 + 2 ( A21 A12) x1

2 ( x1 , x2) := exp x1 A21 + 2 ( A12 A21) x2
2
) exp( A12) + x2i 2 ( x1i , x2i) Psat2

H1
Pcalc := x1 1 x1 , x2
i
y1calc :=
H1
x1 1 x1 , x2
i
i
i exp ( A 12)
Pcalc
0.2
0
PiPcalc
(y1iy1calci) 100
0.2
0.4
0.6
0.2
0.4
x1
0.6
0.8
Pressure residuals
y1 residuals
Fit GE/RT data to Margules eqn. by least squares:

i := 2 .. rows ( P)
Given
0=
y2 := 1 y1
y1 Pi
i
d
x1 ln
H1
dA12 i
x
i exp ( A12)
y P
+ x ln 2i i
2i x2 Psat2
543
... A21 x1 ... x1 x2

i
i
i

+ A12 x2i
0=
0=
y1 Pi
i
d
x1 ln
H1
dA21 i
x
i exp ( A12)
y P
+ x ln 2i i
2i x2 Psat2
y1 Pi
i
d
x1 ln
H1
dH1 i
x
1
i exp ( A )
12
P
+ x ln 2i i
2i x2 Psat2
A12
A21 := Find ( A12 , A21 , H1)

H
1
... A21 x1 ... x1 x2

i
i
i

+ A12 x2i
... A21 x1 ... x1 x2

i
i
i

+
A
12 2i
A12 0.375
A21 = 0.148
H
1 53.078
1 ( x1 , x2) := exp x2 A12 + 2 ( A21 A12) x1

2
2 ( x1 , x2) := exp x1 A21 + 2 ( A12 A21) x2

H1
Pcalc := x1 1 x1 , x2
+ x2 2 x1 , x2 Psat2
i
i
i
i exp ( A 12)
i
i
i
2
y1calc :=
i
H1
x1 1 x1 , x2
i
i
i exp ( A 12)
Pcalc
544
Ans.
0.2
PiPcalc
(y1iy1calci) 100
0.4
0.6
0.8
0.2
0.4
x1
0.6
0.8
Pressure residuals
y1 residuals
14.5
Pressures in kPa
Data:
i := 1 .. 7
0.3193
0.4232
0.5119
0.6096
x1 :=
0.7135
0.7934
0.9102
1.000
21.63
24.01
25.92
27.96
P :=
30.12
31.75
34.15
36.09
x2 := 1 x1
0.5934
0.6815
0.7440
0.8050
y1 :=
0.8639
0.9048
0.9590
1.000
Psat1 := P8
(a) It follows immediately from Eq. (12.10a) that:
ln 2 = A21
Combining this with Eq. (12.10a) yields the required expression.

(b) Henry's constant will be found as part of the solution to Part (c).
545
(c) BARKER'S METHOD by non-linear least squares.

Margules equation.
The most satisfactory procedure for reduction of this set of data is to find
the value of Henry's constant by regression along with the Margules
parameters.
1 ( x1 , x2 , A12 , A21) := exp ( x2) A12 + 2 ( A21 A12) x1
2
2 ( x1 , x2 , A12 , A21) := exp ( x1) A21 + 2 ( A12 A21) x2

2
H2 := 14
Guesses:
A21 := 0.148
A12 := 0.375

Given 0 =
0=
dA21 Pi x1 1 ( x1 , x2 , A12 , A21) Psat1 ...

i
0=
d
2

dA Pi x1i 1 x1i , x2i , A12 , A21 Psat1 ...
12
H2

+ x2i 2 x1i , x2i , A12 , A21 exp ( A21)

H2
+
x
x
,
x
,
A
,
A
2
1
2
12
21
2
i
i
i
exp ( A21)
d
2

dH Pi x1i 1 x1i , x2i , A12 , A21 Psat1 ...
2
H

2
+
x
x
,
x
,
A
,
A
2i 2 1i 2i 12 21 exp ( A21)

A12
A21 := Find ( A12 , A21 , H2)

H
2
A12 0.469
A
=
21 0.279
H
2 14.87
(d) 1 ( x1 , x2) := exp x22 A12 + 2 ( A21 A12) x1

2 ( x1 , x2) := exp x1 A21 + 2 ( A12 A21) x2
2
546
Ans.
H2
Pcalc := x1 1 x1 , x2 Psat1 + x2 2 x1 , x2
i
i
i
i
i
i
i exp ( A 21)
x1 1 x1 , x2 Psat1
i
i
i
y1calc :=
i
Pcalc
i
The plot of residuals below shows that the procedure used (Barker's
method with regression for H2) is not in this case very satisfactory, no
doubt because the data do not extend close enough to x1 = 0.
1
0
PiPcalc
(y1iy1calci) 100
2
3
4
0.2
0.4
0.6
x1
0.8
Pressure residuals
y1 residuals

i := 1 .. 7
y2 := 1 y1
Given
0=
y1 Pi
d
x1 ln i
...
dA12 i x1i Psat1
2 Pi
i
+ x ln
2i
H2
x
2
i exp ( A )
21
547
A21 x1 ... x1 x2
i
i
i

+ A12 x2i
0=
0=
y1 Pi
d
x1 ln i
...
dA21 i x1i Psat1
2 Pi
i
+ x ln
2i
H2
x2i exp ( A )
21
y1i Pi
d
x1 ln
...
dH2 i x1i Psat1
2 Pi
i
+ x ln
2i
H2
i exp ( A )
21
A12
A21 := Find ( A12 , A21 , H2)

H
2
A21 x1 ... x1 x2
i
i
i

+
x
A
12 2i
A21 x1 ... x1 x2
i
i
i

+ A12 x2i
A12 0.37
A
=
21 0.204
H
2 15.065
1 ( x1 , x2) := exp x2 A12 + 2 ( A21 A12) x1

2
2 ( x1 , x2) := exp x1 A21 + 2 ( A12 A21) x2

2
H2
i
i
i
i
i
i
i exp ( A 21)
y1calc :=
i
x1 1 x1 , x2 Psat1
i
Pcalc
548
Ans.
PiPcalc
0.2
i
(y1iy1calci) 100
0.4
0.6
0.3
0.4
0.5
0.6
0.7
x1
0.8
0.9
Pressure residuals
y1 residuals
This result is considerably improved over that obtained with Barker's method.
14.6
Pressures in kPa
Data:
15.79
17.51
18.15
19.30
19.89
P :=
21.37
24.95
29.82
34.80
42.10
i := 2 .. rows ( P)
(a)
0.0
0.0932
0.1248
0.1757
0.2000
x1 :=
0.2626
0.3615
0.4750
0.5555
0.6718
x2 := 1 x1
0.0
0.1794
0.2383
0.3302
0.3691
y1 :=
0.4628
0.6184
0.7552
0.8378
0.9137
Psat2 := P1
ln 1 = A12
Combining this with Eq. (12.10a) yields the required expression

549
(b) Henry's constant will be found as part of the solution to Part (c)
(c) BARKER'S METHOD by non-linear least squares.
Margules equation.
The most satisfactory procedure for reduction of this set of data is to
find the value of Henry's constant by regression along with the
Margules parameters.
1 ( x1 , x2 , A12 , A21) := exp ( x2) A12 + 2 ( A21 A12) x1
2
2 ( x1 , x2 , A12 , A21) := exp ( x1) A21 + 2 ( A12 A21) x2

2
H1 := 35
Guesses:
A21 := 1.27
A12 := 0.70

Given
0=
0=
0=
2
d
H1

Pi x1 1 x1 , x2 , A12 , A21
...
i
i
i
exp
A
dA12
(
)
12

+ x2i 2 x1i , x2i , A12 , A21 Psat2

2
d
H1
Pi x1 1 x1 , x2 , A12 , A21
...
i
i
i
exp
A
dA21
( 12)
+ x2i 2 x1i , x2i , A12 , A21 Psat2

2
d
H1

Pi x1 1 x1 , x2 , A12 , A21
...
i
i
i
exp
A
dH1
(
)
12

+ x2i 2 x1i , x2i , A12 , A21 Psat2

A12
A21 := Find ( A12 , A21 , H1)

H
1
A12 0.731
A
=
21 1.187
H
1 32.065
550
Ans.
(d)
1 ( x1 , x2) := exp x2 A12 + 2 ( A21 A12) x1

2
2 ( x1 , x2) := exp x1 A21 + 2 ( A12 A21) x2

2
) exp( A12) + x2i 2 ( x1i , x2i) Psat2

H1
Pcalc := x1 1 x1 , x2
i
y1calc :=
H1
x1 1 x1 , x2
i
i
i exp ( A 12)
Pcalc
0.5
0
PiPcalc
0.5
(y1iy1calci) 100
1
1.5
2
0.1
0.2
0.3
0.4
x1
0.5
0.6
0.7
Pressure residuals
y1 residuals

i := 2 .. rows ( P)
Given
0=
y2 := 1 y1
y1 Pi
i
d
x1 ln
H1
dA12 i
x
1
i exp ( A )
12
P
+ x ln 2i i
2i x2 Psat2
551
... A21 x1 ... x1 x2

i
i
i

+
A
12 2i
0=
0=
y1 Pi
i
d
x1 ln
H1
dA21 i
x
1
i exp ( A )
12
P
+ x ln 2i i
2i x2 Psat2
y1 Pi
i
d
x1 ln
H1
dH1 i
x
i exp ( A12)
y P
+ x ln 2i i
2i x2 Psat2
A12
A21 := Find ( A12 , A21 , H1)

H
1
... A21 x1 ... x1 x2

i
i
i

+
x
A
12 2i
... A21 x1 ... x1 x2

i
i
i

+ A12 x2i
A12 0.707
A
=
21 1.192
H
1 33.356
1 ( x1 , x2) := exp x2 A12 + 2 ( A21 A12) x1

2
2 ( x1 , x2) := exp x1 A21 + 2 ( A12 A21) x2

2
H1
Pcalc := x1 1 x1 , x2
+ x2 2 x1 , x2 Psat2
i
i
i
i exp ( A 12)
i
i
i
) exp( A12)
x1 1 x1 , x2
y1calc :=
i
Pcalc
H1
552
Ans.
0
0.5
PiPcalc
(y1iy1calci) 100
1.5
2
2.5
0.1
0.2
0.3
0.4
x1
0.5
0.6
0.7
Pressure residuals
y1 residuals
14.7
Pressures in kPa
Data:
0.1757
0.2000
0.2626
0.3615
0.4750
x1 :=
0.5555
0.6718
0.8780
0.9398
1.0000
i := 1 .. 9
(a)
19.30
19.89
21.37
24.95
29.82
P :=
34.80
42.10
60.38
65.39
69.36
x2 := 1 x1
0.3302
0.3691
0.4628
0.6184
0.7552
y1 :=
0.8378
0.9137
0.9860
0.9945
1.0000
Psat1 := P10
ln 2 = A21
Combining this with Eq. (12.10a) yields the required expression.

(b)
Henry's constant will be found as part of the solution to Part (c).

553
(c)
BARKER'S METHOD by non-linear least squares.

Margules equation.
The most satisfactory procedure for reduction of this set of data is to
find the value of Henry's constant by regression along with the
Margules parameters.
1 ( x1 , x2 , A12 , A21) := exp ( x2) A12 + 2 ( A21 A12) x1

2
2 ( x1 , x2 , A12 , A21) := exp ( x1) A21 + 2 ( A12 A21) x2

2
H2 := 4
Guesses:
A21 := 1.37
A12 := 0.68

Given
0=
dA12 Pi x1 1 ( x1 , x2 , A12 , A21) Psat1 ...

i
0=
0=
H2
+
x
x
,
x
,
A
,
A
2
1
2
12
21
2
i
i
i
exp ( A21)
d
2

dA Pi x1i 1 x1i , x2i , A12 , A21 Psat1 ...
21
H2

+ x2i 2 x1i , x2i , A12 , A21 exp ( A21)

dH2 Pi x1 1 ( x1 , x2 , A12 , A21) Psat1 ...

i
H2
+
x
x
,
x
,
A
,
A
2
1
2
12
21
2
i
i
i
exp ( A21)
A12
A21 := Find ( A12 , A21 , H2)

H
2
A12 0.679
A
=
21 1.367
H
2 3.969
554
Ans.
(d) 1 ( x1 , x2) := exp x22 A12 + 2 ( A21 A12) x1

2 ( x1 , x2) := exp x1 A21 + 2 ( A12 A21) x2
2
H2
i
i
i
i
i
i
i exp ( A 21)
y1calc :=
x1 1 x1 , x2 Psat1
i
Pcalc
PiPcalc
0
i
(y1iy1calci) 100
1
0.2
0.4
0.6
x1
0.8
Pressure residuals
y1 residuals

i := 1 .. 9
Given
0=
y2 := 1 y1
y1 Pi
d
x1 ln i
...
dA12 i x1i Psat1
2 Pi
i
+ x ln
2i
H2
x
2
i exp ( A )
21
555
A21 x1 ... x1 x2
i
i
i

+ A12 x2i
0=
0=
y1 Pi
d
x1 ln i
...
dA21 i x1i Psat1
2 Pi
i
+ x ln
2i
H2
i exp ( A )
21
A21 x1 ... x1 x2
i
i
i

+ A12 x2i
y1i Pi
d
x1 ln
...
dH2 i x1i Psat1
2 Pi
i
+ x ln
2i
H2
x2i exp ( A )
21
A12
A21 := Find ( A12 , A21 , H2)

H
2
A21 x1 ... x1 x2
i
i
i

+
A
12 2i
A12 0.845
A21 = 1.229
H
2 4.703
1 ( x1 , x2) := exp x2 A12 + 2 ( A21 A12) x1

2
2 ( x1 , x2) := exp x1 A21 + 2 ( A12 A21) x2

2
H2
i
i
i
i
i
i
i exp ( A 21)
y1calc :=
i
x1 1 x1 , x2 Psat1
i
Pcalc
556
Ans.
PiPcalc
0
i
(y1iy1calci) 100
1
0.2
0.4
0.6
x1
0.8
Pressure residuals
y1 residuals
14.8 (a)
Data from Table 12.1
15.51
18.61
21.63
24.01
P := 25.92 kPa x1 :=
27.96
30.12
31.75
34.15
n := rows ( P)
Psat1 := 36.09kPa
0.0895
0.1981
0.3193
0.4232
0.5119
y1 :=
0.6096
0.7135
0.7934
0.9102
n=9
0.2716
0.4565
0.5934
0.6815
0.7440
1 :=
0.8050
0.8639
0.9048
0.9590
i := 1 .. n
Psat2 := 12.30kPa
1.304
1.188
1.114
1.071
1.044
2 :=
1.023
1.010
1.003
0.997
x2 := 1 x1
i
1 :=
i
y1 Pi
i
x1 Psat1
i
2 :=
i
y2 Pi
i
x2 Psat2
i
557
y2 := 1 y1
T := ( 50 + 273.15)K
Data reduction with the Margules equation and Eq. (10.5):
1.009
1.026
1.050
1.078
1.105
1.135
1.163
1.189
1.268
( )
( )
i := 1 .. n
GERTi := x1 ln 1 + x2 ln 2
i
i
i
i
Guess:
A12 := 0.1
f ( A12 , A21) :=
A21 := 0.3
i=1
2
GERTi A21 x1i + A12 x2i x1i x2i
A12
:= Minimize ( f , A12 , A21)
A
21
A12 = 0.374
A21 = 0.197
RMS Error: RMS :=

RMS = 1.033 10
i=1
Ans.
2
n
x1 := 0 , 0.01 .. 1
0.1
GERT i
A21 x1+A12 ( 1x1) x1 ( 1x1)
0.05
0.2
0.4
0.6
0.8
x1 , x1
i
Data reduction with the Margules equation and Eq. (14.1):

3
cm
B11 := 1840
mol
cm
B22 := 1800
mol
cm
B12 := 1150
mol
12 := 2 B12 B11 B22
( )
B11 ( Pi Psat1) + Pi y2 2 12
1 := exp
i
R T
558
1 :=
i
y1 1 Pi
i
x1 Psat1
i
( )
B22 ( Pi Psat2) + Pi y1 2 12
2 := exp
i
R T
i := 1 .. n
( )
x2 Psat2
i
( )
GERTi := x1 ln 1 + x2 ln 2
i
i
i
i
Guess:
f ( A12 , A21) :=
A12 := 0.1
A21 := 0.3
i=1
2
A12
:= Minimize ( f , A12 , A21)
A
21
RMS :=
A12 = 0.379
Ans.
i=1
RMS = 9.187 10
A21 = 0.216
2
RMS Error:
2 :=
y2 2 Pi
x1 := 0 , 0.01 .. 1
0.1
GERT i
A21 x1+A12 ( 1x1) x1 ( 1x1)
0.05
0.5
x1 , x1
i
The RMS error with Eqn. (14.1) is about 11% lower than the RMS error
with Eqn. (10.5).
Note: The following problem was solved with the temperature (T) set at
the normal boiling point. To solve for another temperature, simply change
T to the approriate value.
559
14.9
(a) Acetylene:
Tc := 308.3K
T := Tn
Tr :=
T
Tc
Pc := 61.39bar
Tn := 189.4K
Tr = 0.614
For Redlich/Kwong EOS:

:= 1
:= 0
:= 0.08664
:= 0.42748
( Tr) := Tr
q ( Tr) :=
( Tr )
Tr
Table 3.1
a ( Tr) :=
Eq. (3.54)
( Tr , Pr) :=
Define Z for the vapor (Zv)

Given
Table 3.1
( Tr ) R Tc
Guess:
Eq. (3.45)
Pc
Pr
Eq. (3.53)
Tr
zv := 0.9
Eq. (3.52)
zv = 1 + ( Tr , Pr) q ( Tr) ( Tr , Pr)
zv ( Tr , Pr)
( zv + ( Tr , Pr) ) ( zv + ( Tr , Pr) )
Zv ( Tr , Pr) := Find ( zv)

Define Z for the liquid (Zl)
Guess:
zl := 0.01
Given Eq. (3.56)
)(
1 + ( Tr , Pr) zl
zl = ( Tr , Pr) + zl + ( Tr , Pr) zl + ( Tr , Pr)
q ( T r ) ( T r , Pr )
To find liquid root, restrict search for zl to values less than 0.2, zl < 0.2
Zl ( Tr , Pr) := Find ( zl)
Define I for liquid (Il) and vapor (Iv)
Il ( Tr , Pr) :=
Iv ( Tr , Pr) :=
Zl ( Tr , Pr) + ( Tr , Pr)
ln
Zl ( Tr , Pr) + ( Tr , Pr)
Zv ( Tr , Pr) + ( Tr , Pr)
ln
Zv ( Tr , Pr) + ( Tr , Pr)
560
Eq. (6.65b)
lnl ( Tr , Pr) := Zl ( Tr , Pr) 1 ln Zl ( Tr , Pr) ( Tr , Pr) q ( Tr) Il ( Tr , Pr)

Eq. (11.37)
lnv ( Tr , Pr) := Zv ( Tr , Pr) 1 ln Zv ( Tr , Pr) ( Tr , Pr) q ( Tr) Iv ( Tr , Pr)

Guess Psat: Psatr :=
Given
1bar
Pc
lnl ( Tr , Psatr) = lnv ( Tr , Psatr)
Psatr = 0.026
Zl ( Tr , Psatr) = 4.742 10
Psat := Psatr Pc
Psat = 1.6 bar
Psatr := Find ( Psatr)

Zv ( Tr , Psatr) = 0.965
Ans.
The following table lists answers for all parts. Literature values are interpolated
from tables in Perry's Chemical Engineers' Handbook, 6th ed. The last column
shows the percent difference between calculated and literature values at 0.85Tc.
These range from 0.1 to 27%. For the normal boiling point (Tn), Psat should be
1.013 bar. Tabulated results for Psat do not agree well with this value.
Differences range from 3 to > 100%.
Tn (K) Psat (bar) 0.85 Tc (K) Psat (bar) Psat (bar) % Difference
@ Tn
@ 0.85 Tc Lit. Values
189.4
1.60
262.1
20.27
19.78
2.5%
Acetylene
87.3
0.68
128.3
20.23
18.70
8.2%
Argon
353.2
1.60
477.9
16.028
15.52
3.2%
Benzene
272.7
1.52
361.3
14.35
12.07
18.9%
n-Butane
0.92
113.0
15.2
12.91
17.7%
Carbon Monoxide 81.7
447.3
2.44
525.0
6.633
5.21
27.3%
n-Decane
169.4
1.03
240.0
17.71
17.69
0.1%
Ethylene
371.6
2.06
459.2
7.691
7.59
1.3%
n-Heptane
111.4
0.71
162.0
19.39
17.33
11.9%
Methane
77.3
0.86
107.3
14.67
12.57
16.7%
Nitrogen
14.10 (a) Acetylene: := 0.187

T := Tn
Tc := 308.3K
Pc := 61.39bar
Note: For solution at 0.85T c, set T := 0.85Tc.
:= 0
Tr :=
T
Tc
Tr = 0.614
For SRK EOS:

:= 1
Tn := 189.4K
:= 0.08664
561
:= 0.42748
Table 3.1
2
2
( Tr , ) := 1 + ( 0.480 + 1.574 0.176 ) 1 Tr
Tr ,

Given
Eq. (3.45)
Eq. (3.54)
Tr
Table 3.1
Tr , R Tc
a ( Tr) :=
Pc
q ( Tr) :=
( Tr , Pr) :=
Guess:
Pr
Tr
Eq. (3.53)
zv := 0.9
Eq. (3.52)
zv = 1 + ( Tr , Pr) q ( Tr) ( Tr , Pr)
zv ( Tr , Pr)
( zv + ( Tr , Pr) ) ( zv + ( Tr , Pr) )

Given
Guess:
zl := 0.01
Eq. (3.56)
)(
1 + ( Tr , Pr) zl
q ( T r ) ( T r , Pr )
To find liquid root, restrict search for zl to values less than 0.2, zl < 0.2
Il ( Tr , Pr) :=
Iv ( Tr , Pr) :=
Zl ( Tr , Pr) + ( Tr , Pr)
ln
Zl ( Tr , Pr) + ( Tr , Pr)
Zv ( Tr , Pr) + ( Tr , Pr)
ln
Zv ( Tr , Pr) + ( Tr , Pr)
562
Eq. (6.65b)

Eq. (11.37)

Guess Psat: Psatr :=
Given
2bar
Pc
Psatr = 0.017
Psat := Psatr Pc
Zl ( Tr , Psatr) = 3.108 10

Zv ( Tr , Psatr) = 0.975
Psat = 1.073 bar Ans.
These range from less than 0.1 to 2.5%. For the normal boiling point (Tn), Psat
should be 1.013 bar. Tabulated results for Psat agree well with this value.
Differences range from near 0 to 6%.
Acetylene
Argon
Benzene
n-Butane
Carbon Monoxide
n-Decane
Ethylene
n-Heptane
Methane
Nitrogen
14.10
@ Tn
189.4
1.073
262.1
20.016
19.78
1.2%
87.3
0.976
128.3
18.79
18.70
0.5%
353.2
1.007
477.9
15.658
15.52
0.9%
272.7
1.008
361.3
12.239
12.07
1.4%
81.7
1.019
113.0
12.871
12.91
-0.3%
447.3
1.014
525.0
5.324
5.21
2.1%
169.4
1.004
240.0
17.918
17.69
1.3%
371.6
1.011
459.2
7.779
7.59
2.5%
111.4
0.959
162.0
17.46
17.33
0.8%
77.3
0.992
107.3
12.617
12.57
0.3%
(b) Acetylene: := 0.187

T := Tn
Tc := 308.3K
Pc := 61.39bar
Note: For solution at 0.85T c, set T := 0.85Tc.
For PR EOS:
:= 1 +
2 := 1
Tn := 189.4K
Tr :=
T
Tc
Tr = 0.614
2 := 0.07779
563
:= 0.45724
Table 3.1
2
2 Table 3.1
( Tr , ) := 1 + ( 0.37464 + 1.54226 0.26992 ) 1 Tr
a ( Tr) :=
q ( Tr) :=
Pc
Tr ,
Tr

Given
Tr , R Tc
Eq. (3.45)
Eq. (3.54)
( Tr , Pr) :=
Guess:
Pr
Tr
Eq. (3.53)
zv := 0.9
Eq. (3.52)
zv = 1 + ( Tr , Pr) q ( Tr) ( Tr , Pr)
zv ( Tr , Pr)
( zv + ( Tr , Pr) ) ( zv + ( Tr , Pr) )

Guess:
zl := 0.01
Given Eq. (3.56)
)(
1 + ( Tr , Pr) zl
q ( T r ) ( T r , Pr )
To find liquid root, restrict search for zl to values less than 0.2,zl < 0.2
Il ( Tr , Pr) :=
Iv ( Tr , Pr) :=
Zl ( Tr , Pr) + ( Tr , Pr)
ln
Zl ( Tr , Pr) + ( Tr , Pr)
Zv ( Tr , Pr) + ( Tr , Pr)
ln
Zv ( Tr , Pr) + ( Tr , Pr)
564
Eq. (6.65b)

Eq. (11.37)

2bar
Pc
Guess Psat:
Psatr :=
Given
Psatr = 0.018
Zl ( Tr , Psatr) = 2.795 10
Psat := Psatr Pc
Psat = 1.09 bar

Zv ( Tr , Psatr) = 0.974
Ans.
These range from less than 0.1 to 1.2%. For the normal boiling point (Tn), Psat
should be 1.013 bar. Tabulated results for Psat agree well with this value.
Differences range from near 0 to 7.6%.
Acetylene
Argon
Benzene
n-Butane
Carbon Monoxide
n-Decane
Ethylene
n-Heptane
Methane
Nitrogen
14.12
(a)
van der Waals Eqn.
:= 0
q ( Tr) :=
Given
@ Tn
189.4
1.090
262.1
19.768
19.78
-0.1%
87.3
1.015
128.3
18.676
18.70
-0.1%
353.2
1.019
477.9
15.457
15.52
-0.4%
272.7
1.016
361.3
12.084
12.07
0.1%
81.7
1.041
113.0
12.764
12.91
-1.2%
447.3
1.016
525.0
5.259
5.21
0.9%
169.4
1.028
240.0
17.744
17.69
0.3%
371.6
1.012
459.2
7.671
7.59
1.1%
111.4
0.994
162.0
17.342
17.33
0.1%
77.3
1.016
107.3
12.517
12.57
-0.4%
:= 0
( Tr)
Tr
:=
Tr := 0.7
1
8
:=
( Tr , Pr) :=
Pr
Tr
zv = 1 + ( Tr , Pr) q ( Tr) ( Tr , Pr)
( Tr) := 1
27
64
zv := 0.9 (guess)
zv ( Tr , Pr)
( zv)
565
Eq. (3.52)

zl := .01
(guess)
2 1 + ( Tr , Pr) zl
zl = ( Tr , Pr) + ( zl)
Given
q ( Tr) ( Tr , Pr)
Eq. (3.56)
zl < 0.2

Iv ( Tr , Pr) :=
( Tr , Pr)
Zv ( Tr , Pr)
Il ( Tr , Pr) :=
( Tr , Pr)
Zl ( Tr , Pr)
Case II, pg. 218.
By Eq. (11.39):
lnv ( Tr , Pr) := Zv ( Tr , Pr) 1 ln ( Zv ( Tr , Pr) ( Tr , Pr) ) q ( Tr) Iv ( Tr , Pr)
lnl ( Tr , Pr) := Zl ( Tr , Pr) 1 ln ( Zl ( Tr , Pr) ( Tr , Pr) ) q ( Tr) Il ( Tr , Pr)
Psatr := .1
Given
lnl ( Tr , Psatr) lnv ( Tr , Psatr) = 0
Zv ( Tr , Psatr) = 0.839
Zl ( Tr , Psatr) = 0.05
lnl ( Tr , Psatr) = 0.148
lnv ( Tr , Psatr) = 0.148 ( Tr , Psatr) = 0.036
:= 1 log ( Psatr)
= 0.302
(b)
Psatr = 0.2
Ans.
Redlich/Kwong Eqn.Tr := 0.7
:= 1
:= 0
:= 0.08664
:= 0.42748
.5
( Tr) := Tr
q ( Tr) :=
( Tr)
( Tr , Pr) :=
Tr
Pr
Tr
Given zv = 1 + ( Tr , Pr) q ( Tr) ( Tr , Pr)

Guess:
zl := .01
566
Guess:
zv := 0.9
zv ( Tr , Pr)
zv ( zv + ( Tr , Pr) )
Eq. (3.52)
Given
zl = ( Tr , Pr) + zl ( zl + ( Tr , Pr) )
zl < 0.2
1 + ( Tr , Pr) zl
q ( Tr) ( Tr , Pr)
Eq. (3.55)
Zv ( Tr , Pr) + ( Tr , Pr) Il ( Tr , Pr) := ln Zl ( Tr , Pr) + ( Tr , Pr)
Zv ( Tr , Pr)
Zl ( Tr , Pr)
Iv ( Tr , Pr) := ln
By Eq. (11.39):
lnv ( Tr , Pr) := Zv ( Tr , Pr) 1 ln ( Zv ( Tr , Pr) ( Tr , Pr) ) q ( Tr) Iv ( Tr , Pr)
lnl ( Tr , Pr) := Zl ( Tr , Pr) 1 ln ( Zl ( Tr , Pr) ( Tr , Pr) ) q ( Tr) Il ( Tr , Pr)
Psatr := .1
Given
Zv ( Tr , Psatr) = 0.913
Zl ( Tr , Psatr) = 0.015
lnv ( Tr , Psatr) = 0.083 lnl ( Tr , Psatr) = 0.083

:= 1 log ( Psatr)
14.15 (a) x1 := 0.1

Guess:
= 0.058
x2 := 1 x1
A12 := 2
Psatr = 0.087
( Tr , Psatr) = 0.011
Ans.
x1 := 0.9
x2 := 1 x1
A21 := 2
1 ( A21 , A12) := exp x2 A12 + 2 ( A21 A12) x1

2
1( A21 , A12) := exp x2 A12 + 2 ( A21 A12) x1

2
2 ( A21 , A12) := exp x1 A21 + 2 ( A12 A21) x2

2
2( A21 , A12) := exp x1 A21 + 2 ( A12 A21) x2

2
567
Given
x1 1 ( A21 , A12) = x1 1( A21 , A12)

x2 2 ( A21 , A12) = x2 2( A21 , A12)
A12
:= Find ( A12 , A21)
A
21
(b) x1 := 0.2
Guess:
A21 = 2.747
A12 = 2.747
x2 := 1 x1
x1 := 0.9
A12 := 2
A21 := 2
Ans.
x2 := 1 x1
1 ( A21 , A12) := exp x2 A12 + 2 ( A21 A12) x1

2
1( A21 , A12) := exp x2 A12 + 2 ( A21 A12) x1

2
2 ( A21 , A12) := exp x1 A21 + 2 ( A12 A21) x2

2
2( A21 , A12) := exp x1 A21 + 2 ( A12 A21) x2

2
Given
x1 1 ( A21 , A12) = x1 1( A21 , A12)

x2 2 ( A21 , A12) = x2 2( A21 , A12)
A12
:= Find ( A12 , A21)
A
21
(c) x1 := 0.1
Guess:
A12 = 2.148
A21 = 2.781
x2 := 1 x1
x1 := 0.8
A12 := 2
A21 := 2
x2 := 1 x1
1 ( A21 , A12) := exp x2 A12 + 2 ( A21 A12) x1

2
1( A21 , A12) := exp x2 A12 + 2 ( A21 A12) x1

2
2 ( A21 , A12) := exp x1 A21 + 2 ( A12 A21) x2

2
2( A21 , A12) := exp x1 A21 + 2 ( A12 A21) x2

2
568
Ans.
Given
x1 1 ( A21 , A12) = x1 1( A21 , A12)

x2 2 ( A21 , A12) = x2 2( A21 , A12)
A12
:= Find ( A12 , A21)
A
21
14.16 (a) x1 := 0.1

Guess:
Given
A12 = 2.781
A21 = 2.148
x2 := 1 x1
x1 := 0.9
a12 := 2
a21 := 2
Ans.
x2 := 1 x1
2
2
a12 x1
a12 x1
exp a12 1 +
x1 = exp a12 1 + a21 x2

x1
a
x2
21

2
2
a21 x2
a21 x2
exp a21 1 +
x2 = exp a21 1 + a12 x1

x2
a
x1
12
a12
:= Find ( a12 , a21)
a
21

(b) x1 := 0.2
Guess:
Given
a12 = 2.747
x2 := 1 x1
a12 := 2
a21 = 2.747
x1 := 0.9
Ans.
x2 := 1 x1
a21 := 2
2
2
a12 x1
a12 x1
exp a12 1 +
x1 = exp a12 1 + a21 x2

x1
a
x2
21

2
2
a21 x2
a21 x2
exp a21 1 +
x2 = exp a21 1 + a12 x1

x2
a
x1
12
a12
:= Find ( a12 , a21)
a
21

a12 = 2.199
569
a21 = 2.81
Ans.
x1 := 0.1
x2 := 1 x1
x1 := 0.8
Guess:
a12 := 2
a21 := 2
(c)
Given
x2 := 1 x1
2
2
a12 x1
a12 x1
exp a12 1 +
x1 = exp a12 1 + a21 x2

x1
a
x2
21

2
2
a21 x2
a21 x2
exp a21 1 +
x2 = exp a21 1 + a12 x1

x2
a
x1
12
a12
:= Find ( a12 , a21)
a
21

14.18
(a) a := 975
a12 = 2.81
b := 18.4
T := 250 .. 450
A ( T) :=
a21 = 2.199
Ans.
c := 3
a
+ b c ln ( T)
T
2.1
A ( T)
1.9
250
300
350
400
450
Parameter A = 2 at two temperatures. The lower one is an UCST,

because A decreases to 2 as T increases. The higher one is a LCST,
because A decreases to 2 as T decreases.
Guess:
Given
x0
x := 0.25
1 x
x
A ( T) ( 1 2 x) = ln
x 0.5
x1 ( T) := Find ( x)
570
Eq. (E), Ex. 14.5

x2 ( T) := 1 x1 ( T)
UCST := 300 (guess)

Given
A ( UCST) = 2
UCST := Find ( UCST)
UCST = 272.93
LCST := Find ( LCST)
LCST = 391.21
LCST := 400 (guess)

Given
A ( LCST) = 2
Plot phase diagram as a function of T

T1 := 225 , 225.1 .. UCST
T2 := LCST .. 450
500
T1
400
T1
T2
T2
300
200
0.2
0.3
0.4
0.5
0.6
x1 ( T1 ) , x2 ( T1 ) , x1 ( T2 ) , x2 ( T2 )
(b) a := 540
b := 17.1
T := 250 .. 450
A ( T) :=
c := 3
a
+ b c ln ( T)
T
2.5
A ( T)
1.5
250
300
350
400
450
Parameter A = 2 at a single temperature. It is

a LCST, because A decreases to 2 as T decreases.
571
0.7
0.8
Guess:
x := 0.25
Given
A ( T) ( 1 2 x) = ln
1 x
x
x0
x 0.5
Eq. (E), Ex. 14.5
x1 ( T) := Find ( x)
LCST := 350 (guess)

LCST := Find ( LCST)
A ( LCST) = 2
Given
LCST = 346
T := LCST .. 450
450
400
T
T
350
300
0.1
0.2
0.3
0.4
0.5
0.6
x1 ( T ) , 1x1 ( T)
(c)
a := 1500
b := 19.9
T := 250 .. 450
A ( T) :=
c := 3
a
+ b c ln ( T)
T
3
2.5
A ( T)
2
1.5
250
300
350
400
450
Parameter A = 2 at a single temperature. It is

an UCST, because A decreases to 2 as T increases.
572
0.7
0.8
Guess:
x := 0.25
Given
A ( T) ( 1 2 x) = ln
1 x
x
x0
x 0.5
Eq. (E), Ex. 14.5
x1 ( T) := Find ( x)
UCST := 350 (guess)

A ( UCST) = 2
Given
UCST := Find ( UCST)
UCST = 339.66
T := UCST .. 250
350
T
300
250
0.2
0.4
0.6
0.8
x1 ( T ) , 1x1 ( T)
x1 := 0.5
14.20 Guess:
x1 := 0.5
Write Eq. (14.74) for species 1:
Given
2
2
x1 exp 0.4 ( 1 x1) = x1 exp 0.8 ( 1 x1)
x1
1 x1
x1
1 x1
= 1
x1
:= Find ( x1 , x1)
x1
(Material balance)
x1 = 0.371
573
x1 = 0.291
Ans.
14.22 Temperatures in kelvins; pressures in kPa.

P1sat ( T) := exp 19.1478
P2sat ( T) := exp 14.6511
5363.7
T
water
2048.97
T
SF6
P := 1600
Find 3-phase equilibrium temperature and vapor-phase composition (pp.

594-5 of text):
Guess:
Given
T := 300
P = P1sat ( T) + P2sat ( T)
Tstar := Find ( T)
Tstar = 281.68
P1sat ( Tstar)
6
y1star 10 = 695
P
Find saturation temperatures of pure species 2:
y1star :=
Guess:
Given
T := 300
P2sat ( T) = P
T2 := Find ( T)
T2 = 281.71
P2sat ( T)
P
P1sat ( T)
TI := Tstar , Tstar + 0.01 .. Tstar + 6
y1I ( T) :=
P
Because of the very large difference in scales appropriate to regions I and
II [Fig. 14.21(a)], the txy diagram is presented on the following page in two
parts, showing regions I and II separately.
TII := Tstar , Tstar + 0.0001 .. T2
y1II ( T) := 1
281.7
TII
Tstar
281.69
281.68
100
200
300
400
6
500
6
y1II ( TII) 10 , y1II ( TII) 10

574
600
700
288
286
TI
Tstar
284
282
280
650
700
750
800
850
900
950
y1I ( TI) 10 , y1I ( TI) 10
1000
1050
14.24 Temperatures in deg. C; pressures in kPa

P1sat ( T) := exp 13.9320
3056.96
T + 217.625
3885.70
P2sat ( T) := exp 16.3872
T + 230.170
Toluene
P := 101.33
Water
Find the three-phase equilibrium T and y:

T := 25
Guess:
Given
y1star :=
P1sat ( Tstar)
P
Tstar := Find ( T)
y1star = 0.444
For z1 < y1*, first liquid is pure species 2.

y1 := 0.2
Given
Guess:
y1 = 1
Tdew := Tstar
P2sat ( Tdew)
P
Tdew := Find ( Tdew)

Tdew = 93.855
For z1 > y1*, first liquid is pure species 1.
575
Ans.
Tstar = 84.3
y1 := 0.7
Guess:
y1 =
Given
Tdew := Tstar
P1sat ( Tdew)
P

Tdew = 98.494
Ans.
In both cases the bubblepoint temperature is T*, and the mole fraction of
the last vapor is y1*.
14.25 Temperatures in deg. C; pressures in kPa.
P1sat ( T) := exp 13.8622
P2sat ( T) := exp 16.3872
2910.26
T + 216.432
n-heptane
3885.70
T + 230.170
water
P := 101.33
Find the three-phase equilibrium T and y:

Guess:
T := 50
Given
y1star :=
P1sat ( Tstar)
P
Tstar := Find ( T)
Tstar = 79.15
y1star = 0.548
Since 0.35<y1*, first liquid is pure species 2.

y1 ( T) := 1
P2sat ( T)
P
Find temperature of initial condensation at y1=0.35:

y10 := 0.35
Given
Guess:
y1 ( Tdew) = y10
Tdew := Tstar
Tdew = 88.34
Define the path of vapor mole fraction above and below the dew point.
y1path ( T) := if ( T > Tdew , y10 , y1 ( T) )
T := 100 , 99.9 .. Tstar
Path of mole fraction heptane in residual vapor as temperature is

decreased. No vapor exists below Tstar.
576
100
95
Tdew
90
T
85
Tstar
80
75
0.3
0.35
0.4
0.45
0.5
0.55
y1path ( T )
P1sat := 75
14.26 Pressures in kPa.
P2sat := 110
A := 2.25
2
1 ( x1) := exp A ( 1 x1)
2 ( x1) := exp A x1
Find the solubility limits:

Guess:
x1 := 0.1
Given
A ( 1 2 x1) = ln
1 x1
x1
x1 = 0.224
x1 := 1 x1
x1 := Find ( x1)
x1 = 0.776
Find the conditions for VLLE:

Guess:
Given
Pstar := P1sat
y1star := 0.5
Pstar = x1 1 ( x1) P1sat + ( 1 x1) 2 ( x1) P2sat

y1star Pstar = x1 1 ( x1) P1sat
Pstar
:= Find ( Pstar , y1star)
y1star
Pstar = 160.699
Calculate VLE in two-phase region.

Modified Raoult's law; vapor an ideal gas.
Guess:
x1 := 0.1
P := 50
577
y1star = 0.405
P = x1 1 ( x1) P1sat + ( 1 x1) 2 ( x1) P2sat
Given
P ( x1) := Find ( P)
y1 ( x1) :=
x1 1 ( x1) P1sat
P ( x1)
Plot the phase diagram.

Define liquid equilibrium line:
PL ( x1) := if ( P ( x1) < Pstar , P ( x1) , Pstar)
Define vapor equilibrium line:
PV ( x1) := if ( P ( x1) < Pstar , P ( x1) , Pstar)
Define pressures for liquid phases above Pstar:
Pliq := Pstar .. Pstar + 10
x1 := 0 , 0.01 .. 1
200
175
Pstar
PL ( x1) 150
PV ( x1)
125
Pliq
Pliq
100
75
50
0.2
0.4
0.6
x1 , y1 ( x1) , x1 , x1
x1 := 0 , 0.05 .. 0.2
x1 =
PL ( x1) =
y1 ( x1) =
110
0.05
133.66
0.214
0.1
147.658
0.314
0.15
155.523
0.368
0.2
159.598
0.397
578
0.8
x1 := 1 , 0.95 .. 0.8
x1 =
PL ( x1) =
y1 ( x1) =
75
0.95
113.556
0.631
0.9
137.096
0.504
0.85
150.907
0.444
0.8
158.506
0.414
x1 = 0.224
x1 = 0.776
y1star = 0.405

Water:
P1sat ( T) := exp 16.3872
3885.70
T + 230.170
n-Pentane:
P2sat ( T) := exp 13.7667
2451.88
T + 232.014
n-Heptane:
P3sat ( T) := exp 13.8622
2910.26
T + 216.432
P := 101.33
z1 := 0.45
(a)
z2 := 0.30
z3 := 1 z1 z2
Calculate dew point T and liquid composition

assuming the hydrocarbon layer forms first:
Guess:
Tdew1 := 100
x2 := z2
x3 := 1 x2
Given
P = x2 P2sat ( Tdew1) + x3 P3sat ( Tdew1)

z3 P = x3 P3sat ( Tdew1)
x2 + x3 = 1
x2
x3 := Find ( x2 , x3 , Tdew1)
Tdew1
Tdew1 = 66.602
x3 = 0.706
579
x2 = 0.294
Calculate dew point temperature assuming the water layer forms first:
x1 := 1
Tdew2 := 100
Guess:
x1 P1sat ( Tdew2) = z1 P
Given
Tdew2 := Find ( Tdew2)

Tdew2 = 79.021
Since Tdew2 > Tdew1, the water layer forms first

(b) Calculate the temperature at which the second layer forms:
Guess:
Given
Tdew3 := 100
x2 := z2
x3 := 1 x2
y1 := z1
y2 := z2
y3 := z3
P = P1sat ( Tdew3) + x2 P2sat ( Tdew3) + x3 P3sat ( Tdew3)

y1 P = P1sat ( Tdew3)
y2
z2
=
y3
z3
y1 + y2 + y3 = 1
y2 P = x2 P2sat ( Tdew3)
x2 + x3 = 1
y1
y2
y3
:= Find ( y1 , y2 , y3 , Tdew3 , x2 , x3)
Tdew3
x2
x3
y1 = 0.288
y2 = 0.388
y3 = 0.324
Tdew3 = 68.437
x2 = 0.1446
x3 = 0.8554
(c)
Calculate the bubble point given the total molar composition of the
two phases
Tbubble := Tdew3
x2 :=
z2
z2 + z3
x2 = 0.545
580
x3 :=
z3
z2 + z3
x3 = 0.455
Given
P = P1sat ( Tbubble) + x2 P2sat ( Tbubble) + x3 P3sat ( Tbubble)
Tbubble := Find ( Tbubble)
Tbubble = 48.113
P1sat ( Tbubble)
P
x2 P2sat ( Tbubble)
y2 :=
P
x3 P3sat ( Tbubble)
y3 :=
P
y1 = 0.111
y1 :=
y2 = 0.81
y3 = 0.078

Water:
P1sat ( T) := exp 16.3872
3885.70
T + 230.170
n-Pentane:
P2sat ( T) := exp 13.7667
2451.88
T + 232.014
n-Heptane:
P3sat ( T) := exp 13.8622
2910.26
T + 216.432
P := 101.33
(a)
Guess:
Given
z1 := 0.32
z2 := 0.45
z3 := 1 z1 z2
Calculate dew point T and liquid composition

assuming the hydrocarbon layer forms first:
Tdew1 := 70
x2 := z2
x3 := 1 x2
P = x2 P2sat ( Tdew1) + x3 P3sat ( Tdew1)

z3 P = x3 P3sat ( Tdew1)
x2 + x3 = 1
x2
x3 := Find ( x2 , x3 , Tdew1)
Tdew1
Tdew1 = 65.122
x3 = 0.686
581
x2 = 0.314
Calculate dew point temperature assuming the water layer forms first:
x1 := 1
Tdew2 := 70
Guess:
x1 P1sat ( Tdew2) = z1 P
Given
Tdew2 := Find ( Tdew2)

Tdew2 = 70.854
Since Tdew1>Tdew2, a hydrocarbon layer forms first

(b) Calculate the temperature at which the second layer forms:
Guess:
Given
Tdew3 := 100
x2 := z2
x3 := 1 x2
y1 := z1
y2 := z2
y3 := z3
P = P1sat ( Tdew3) + x2 P2sat ( Tdew3) + x3 P3sat ( Tdew3)

y1 P = P1sat ( Tdew3)
y2
z2
=
y3
z3
y2 P = x2 P2sat ( Tdew3)
y1 + y2 + y3 = 1
x2 + x3 = 1
y1
y2
y3
:= Find ( y1 , y2 , y3 , Tdew3 , x2 , x3)
Tdew3
x2
x3
y1 = 0.24
y2 = 0.503
y3 = 0.257
Tdew3 = 64.298
x2 = 0.2099
x3 = 0.7901
(c)
Calculate the bubble point given the total

molar composition of the two phases
Tbubble := Tdew3
x2 :=
z2
z2 + z3
x2 = 0.662
582
x3 :=
z3
z2 + z3
x3 = 0.338
Given
P = P1sat ( Tbubble) + x2 P2sat ( Tbubble) + x3 P3sat ( Tbubble)
Tbubble := Find ( Tbubble)
Tbubble = 43.939
P1sat ( Tbubble)
P
x2 P2sat ( Tbubble)
y2 :=
P
x3 P3sat ( Tbubble)
y3 :=
P
y1 = 0.09
y1 :=
0.302
0.224
y2 = 0.861
y3 = 0.049
748.4
K
304.2
14.32 :=
40.51
bar
73.83
Tc :=
Pc :=
P := 10bar , 20bar .. 300bar
T
Tr :=
Tc
T := 353.15K
Use SRK EOS
From Table 3.1, p. 98 of text:

:= 1
:= 0
:= 0.08664
:= 0.42748
)(
:= 1 + 0.480 + 1.574 0.176 1 Tr

2
0.5
) 2
2
2
R Tc
Eq. (14.31)
a :=
Pc
R Tc
b :=
Pc
6.842 kg m5
a=
0.325 s2 mol2
1.331 10 4 m3
b=
2.968 10 5 mol
2 ( P) :=
z2 := 1
b2 P
R T
q2 :=
Eq. (14.33)
(guess)
583
a2
b2 R T
Eq. (14.32)
Eq. (14.34)
Given
z2 = 1 + 2 ( P) q2 2 ( P)
z2 2 ( P)
)(
z2 + 2 ( P) z2 + 2 ( P)
Eq. (14.36)
Z2 ( P) := Find ( z2)
Z 2 ( P) + 2 ( P)
I2 ( P) := ln
Z 2 ( P)
Eq. (6.65b)
For simplicity, let 1 represent the infinite-dilution value of the fugacity

coefficient of species 1 in solution.
l12 := 0.088
Eq. (14.103):

b1
( Z2 ( P) 1) ln ( Z2 ( P) 2 ( P) ) ...

b2
0.5
b1
a1
+
I
(
P
)
(
)
2
12
b2
a2
1 ( P) := exp
Psat1 := 0.0102bar
V1 := 124.5
cm
mol
Eqs. (14.98) and (14.99), with sat1 = 1 and (P - Psat1) = P, combine to give:
y1 ( P) :=
Psat1
P 1 ( P)
P V 1
R T
exp
0.1
0.01
y1 ( P)
1 .10
1 .10
50
100
150
P
bar
584
200
250
300
0.302
0.038
748.4
K
126.2
14.33 :=
40.51
bar
34.00
Tc :=
Pc :=
P := 10bar , 20bar .. 300bar
T
Tr :=
Tc
T := 308.15K (K)
Use SRK EOS
From Table 3.1, p. 98 of text:

:= 1
:= 0
:= 0.08664
:= 0.42748
)(
2
0.5
:= 1 + 0.480 + 1.574 0.176 1 Tr
2
2
R Tc
a :=
Pc
R Tc
b :=
Pc
Eq. (14.31)
b2 P
R T
z2 := 1
Eq. (14.32)
1.331 10 4 m3
b=
2.674 10 5 mol
7.298 kg m5
a=
0.067 s2 mol2
2 ( P) :=
q2 :=
Eq. (14.33)
a2
b2 R T
Eq. (14.34)
(guess)
Given
z2 = 1 + 2 ( P) q2 2 ( P)
z2 2 ( P)
)(
z2 + 2 ( P) z2 + 2 ( P)
Eq. (14.36)
Z2 ( P) := Find ( z2)
Z 2 ( P) + 2 ( P)
I2 ( P) := ln
Z 2 ( P)
Eq. (6.65b)
For simplicity, let 1 represent the infinite-dilution value of the fugacity

coefficient of species 1 in solution.
585
l12 := 0.0
Eq. (14.103):

b1
( Z2 ( P) 1) ln ( Z2 ( P) 2 ( P) ) ...

b2
0.5
b1
a1
+
I
(
P
)
(
)
2
12
b2
a2
1 ( P) := exp
Psat1 := 2.9 10
V1 := 125
bar
cm
mol
Eqs. (14.98) and (14.99), with sat1 = 1 and (P - Psat1) = P, combine to

give:
y1 ( P) :=
Psat1
P 1 ( P)
P V 1
R T
exp
10
y1 ( P) 10
50
100
150
P
bar
Note: y axis is log scale.
586
200
250
300
14.45 A labeled diagram of the process is given below. The feed stream is taken as
the phase and the solvent stream is taken as the phase.
F
nF
xF1 = 0.99
xF2 = 0.01
R
nR
x1
x2 = 0.001
Feed
Mixer/
Settler
S
nS
xS3 = 1.0
E
nE
x2
x3
Solvent
Define the values given in the problem statement. Assume as a basis a feed
rate nF = 1 mol/s.
nF := 1
mol
s
xF1 := 0.99
xF2 := 0.01
xS3 := 1
x2 := 0.001
x1 := 1 x2
Apply mole balances around the process as well as an equilibrium relationship

A12 := 1.5
From p. 585
2
2 ( x2) := exp A12 ( 1 x2)
A23 := 0.8
2
2 ( x2) := exp A23 ( 1 x2)
Material Balances
nS + nF = nE + nR
(Total)
nS = x3 nE
(Species 3)
xF1 nF = x1 nR
(Species 1)
Substituting the species balances into the total balance yields

xF1
1
nS + nF =
nS +
nF
x3
x1
Solving for the ratio of solvent to feed (nS/nF) gives
nS
nF
x1 xF1 x3
x
3 x1
587
We need x3. Assume exiting streams are at equilibrium. Here, the only
distributing species is 2. Then
x2 2 = x2 2
Substituting for 2 and 2
2
2
x2 exp A12 1 x2 = x2 exp A23 1 x2
Solve for x2 using Mathcad Solve Block

x2 := 0.5
Guess:
Given
2
2
x2 exp A12 1 x2 = x2 exp A23 1 x2
( )
x2 := Find x2
x2 = 0.00979
x3 := 1 x2
x3 = 0.9902
From above, the equation for the ratio nS/nF is:
x1 xF1 x3
x
3
x1
nSnF :=
a) nSnF = 0.9112
Ans.
b) x2 = 0.00979
Ans.
c) "Good chemistry" here means that species 2 and 3 "like" each other, as
evidenced by the negative GE23. "Bad chemistry" would be reflected in a
positive GE23, with values less than (essential) but perhaps near to GE12.
14.46 1 - n-hexane
2 - water
Since this is a dilute system in both phases, Eqns. (C) and (D) from Example
14.4 on p. 584 can be used to find 1 and 2.
x1 :=
520
6
x2 := 1 x1
x2 :=
10
2
6
10
588
x1 := 1 x2
1 :=
2 :=
x1
Ans.
Ans.
1 = 1.923 10
x1
1 x1
2 = 4.997 10
1 x1
cm
V1 := 90
mol
14.50 1 - butanenitrile Psat1 := 0.07287bar
Psat2 := 0.29871bar
2- benzene
B1 , 1 := 7993
cm
mol
T := 318.15K
i := 1 .. 2
V2 := 92
cm
mol
B2 , 2 := 1247
cm
mol
B1 , 2 := 2089
P := 0.20941bar
j := 1 .. 2
k := 1 .. 2
cm
mol
B2 , 1 := B1 , 2
x1 := 0.4819
y1 := 0.1813
x2 := 1 x1
y2 := 1 y1
Term A is calculated using the given data.

term_Ai :=
yi P
xi Psati
Term B is calculated using Eqns. (14.4) and (14.5)

j , i := 2 B j , i B j , j Bi , i
hati := exp
P
1
Bi , i +
2
R T
Bi , i Psati
R T
sati := exp
y jyk( 2 j , i j , k)
j
term_Bi :=
hati
sati
Term C is calculated using Eqn. (11.44)

fsati := sati Psati
1.081
1.108
term_A =
Vi ( P Psati)
fi := sati Psati exp
R T
0.986
1.006
term_B =
589
term_Ci :=
1
1
term_C =
fsati
fi
Ans.
14.51 a) Equivalent to d2(G/RT)/dx12 = 0, use d2(GE/RT)/dx12 = -1/x1x2

For GE/RT = Ax1x2 = A(x1-x12)
d(GE/RT)/dx1 = A(1-2x1)
d2(GE/RT)/dx12 = -2A
Thus, -2A = -1/x1x2 or 2Ax1x2 = 1.
Substituting for x2: x1-x12 = 1/(2A) or x12-x1+1/(2A) = 0.
1+
The solution to this equation yields two roots:
x1 =
2
A
2
1
and
x1 =
2
A
The two roots are symmetrical around x1 = 1/2

Note that for:
A<2: No real roots
A = 2: One root, x1 = 1/3 (consolute point)
A>2: Two real roots, x1 > 0 and x1 <1
b) Plot the spinodal curve along with the solubility curve
540K
T
+ 21.1 3 ln
T
K
Both curves are symmetrical around x1 = 1/2. Create functions to
represent the left and right halves of the curves.
From Fig. 14.15:
A ( T) :=
From above, the equations for the spinodal curves are:

xspr1 ( T) :=
1 1 A ( T) 2
+
2 2
A ( T)
xr := 0.7
xl := 0.3
xspl1 ( T) :=
1 1 A ( T) 2

2 2
A ( T)
From Eq. (E) in Example 14.5, the solubility curves are solved using
a Solve Block:
590
1 xr
xr
xr > 0.5
xr1 ( T) := Find ( xr)
1 xl
xl
xl < 0.5
xl1 ( T) := Find ( xl)
Given
A ( T) ( 1 2xr) = ln
Given
A ( T) ( 1 2xl) = ln
Find the temperature of the upper consolute point.

T := 300K
Given
A ( T) = 2
Tu := Find ( T)
0.3
0.5
Tu = 345.998 K
T := 250K .. 346K
360
340
320
300
280
260
240
0.1
0.2
0.4
0.6
0.7
0.8
xl1
xr1
xspl1
xpr1
14.54 The solution is presented for one of the systems given. The solutions for the
other systems follow in the same manner.
f) 1- Carbon tetrachloride
1 := 0.193
Tc1 := 556.4K
Pc1 := 45.60bar
A1 := 14.0572
B1 := 2914.23
C1 := 232.148
Psat1 ( T) := exp A1
kPa
T 273.15 + C
1
K
B1
591
2 - n-heptane
2 := 0.350
Tc2 := 540.2K
Pc2 := 27.40bar
A2 := 13.8622
B2 := 2910.26
C2 := 216.432
Psat2 ( T) := exp A2
kPa
T 273.15 + C
2
K
B2
T := ( 100 + 273.15)K
Tr1 :=
T
Tc1
Tr1 = 0.671
Psat1r :=
Tr2 :=
T
Tc2
Tr2 = 0.691
Psat2r :=
Psat1 ( T)
Pc1
Psat2 ( T)
Pc2
12 := 1.5410
Using Wilson's equation
Psat1r = 0.043
Psat2r = 0.039
21 := 0.5197
1 ( x1) := exp ln x1 + ( 1 x1) 12 ...
12
21
+ 1 x
(
1)
x
+
1
x
+
x
(
)
(
)
1
1
1
1
12
21
2 ( x1) := exp ln ( 1 x1) + x1 21 ...
12
21
+ x
(
1)
x1 + ( 1 x1) 12 ( 1 x1) + x1 21
For part i, use the modified Raoult's Law. Define the pressure and vapor
mole fraction y1 as functions of the liquid mole fraction, x 1.
Pi ( x1) := x1 1 ( x1) Psat1 ( T) + ( 1 x1) 2 ( x1) Psat2 ( T)
yi1 ( x1) :=
x1 1 ( x1) Psat1 ( T)
Pi ( x1)
Modified Raoult's Law: Eqn. (10.5)
592
For part ii, assume the vapor phase is an ideal solution. Use Eqn. (11.68)
and the PHIB function to calculate hat and sat.
sat1 := PHIB Tr1 , Psat1r , 1
sat1 = 0.946
hat1 ( P) := PHIB Tr1 ,

, 1
P
c1
sat2 := PHIB Tr2 , Psat2r , 2
1 ( P) :=
c2
sat1
sat2 = 0.95
hat2 ( P) := PHIB Tr2 ,

, 2
P
hat1 ( P)
2 ( P) :=
hat2 ( P)
sat2
Solve Eqn. (14.1) for y1 and P given x1.

Guess:
y1 := 0.5
P := 1bar
Given
y1 1 ( P) P = x1 1 ( x1) Psat1 ( T)
( 1 y1) 2 (P) P = ( 1 x1) 2 ( x1) Psat2 (T)
Eqn. (14.1)
fii ( x1) := Find ( P , y1)

fii is a vector containing the values of P and y 1. Extract the pressure, P and
vapor mole fraction, y1 as functions of the liquid mole fraction.
Pii ( x1) := fii ( x1) 0
yii1 ( x1) := fii ( x1) 1
Plot the results in Mathcad
x1 := 0 , 0.1 .. 1.0
593
2
1.9
1.8
Pi ( x1 )
1.7
bar
Pi ( x1 )
1.6
bar
Pii ( x1 )
bar
Pii ( x1 )
bar
1.5
1.4
1.3
1.2
1.1
1
0.2
0.4
0.6
x1 , yi1 ( x1 ) , x1 , yii1 ( x1 )
P-x Raoult's
P-y Raoult's
P-x Gamma/Phi
P-y Gamma/Phi
594
0.8

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Chapter 14 - Section A - Mathcad Solutions

2 ( x1) := exp x1 A21 + 2 ( A12 A21) ( 1 x1)

Psat1 := 82.37 kPa

Psat2 := 37.31 kPa

BUBL P calculations based on Eq. (10.5):

Pbubl ( x1) = 64.533 kPa

Pbubl ( x1) = 80.357 kPa

Pbubl ( x1) = 85.701 kPa

BUBL P calculations with virial coefficients:

12 := 2 B12 B11 B22

B11 ( P Psat1) + P y22 12

B22 ( P Psat2) + P y12 12

y1 1 ( P , T , y1 , y2) P = x1 1 ( x1) Psat1

y1 1 ( P , T , y1 , y2) P = x1 1 ( x1) Psat1

y1 1 ( P , T , y1 , y2) P = x1 1 ( x1) Psat1

It follows immediately from Eq. (12.10a) that:

Combining this with Eq. (12.10a) yields the required expression

Henry's constant will be found as part of the solution to Part (c)

BARKER'S METHOD by non-linear least squares.

2 ( x1 , x2 , A12 , A21) := exp ( x1) A21 + 2 ( A12 A21) x2

Mininize the sums of the squared errors by

+ x2i 2 x1i , x2i , A12 , A21 Psat2

+ x2i 2 x1i , x2i , A12 , A21 Psat2

+ x2i 2 x1i , x2i , A12 , A21 Psat2

A21 := Find ( A12 , A21 , H1)

(d) 1 ( x1 , x2) := exp x22 A12 + 2 ( A21 A12) x1

) exp( A12) + x2i 2 ( x1i , x2i) Psat2

Fit GE/RT data to Margules eqn. by least squares:

... A21 x1 ... x1 x2

A21 := Find ( A12 , A21 , H1)

... A21 x1 ... x1 x2

... A21 x1 ... x1 x2

1 ( x1 , x2) := exp x2 A12 + 2 ( A21 A12) x1

2 ( x1 , x2) := exp x1 A21 + 2 ( A12 A21) x2

(a) It follows immediately from Eq. (12.10a) that:

Combining this with Eq. (12.10a) yields the required expression.

(c) BARKER'S METHOD by non-linear least squares.

2 ( x1 , x2 , A12 , A21) := exp ( x1) A21 + 2 ( A12 A21) x2

Mininize the sums of the squared errors by

dA21 Pi x1 1 ( x1 , x2 , A12 , A21) Psat1 ...

+ x2i 2 x1i , x2i , A12 , A21 exp ( A21)

A21 := Find ( A12 , A21 , H2)

(d) 1 ( x1 , x2) := exp x22 A12 + 2 ( A21 A12) x1

Fit GE/RT data to Margules eqn. by least squares:

A21 := Find ( A12 , A21 , H2)

1 ( x1 , x2) := exp x2 A12 + 2 ( A21 A12) x1

2 ( x1 , x2) := exp x1 A21 + 2 ( A12 A21) x2

It follows immediately from Eq. (12.10a) that:

Combining this with Eq. (12.10a) yields the required expression

2 ( x1 , x2 , A12 , A21) := exp ( x1) A21 + 2 ( A12 A21) x2

Mininize the sums of the squared errors by

+ x2i 2 x1i , x2i , A12 , A21 Psat2

+ x2i 2 x1i , x2i , A12 , A21 Psat2

+ x2i 2 x1i , x2i , A12 , A21 Psat2

A21 := Find ( A12 , A21 , H1)

1 ( x1 , x2) := exp x2 A12 + 2 ( A21 A12) x1

2 ( x1 , x2) := exp x1 A21 + 2 ( A12 A21) x2

) exp( A12) + x2i 2 ( x1i , x2i) Psat2

Fit GE/RT data to Margules eqn. by least squares:

... A21 x1 ... x1 x2

A21 := Find ( A12 , A21 , H1)

... A21 x1 ... x1 x2

... A21 x1 ... x1 x2

1 ( x1 , x2) := exp x2 A12 + 2 ( A21 A12) x1