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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
(b)
x1 1 ( x1) Psat1
Pbubl ( x1)
x1 := 0.25
y1 ( x1) = 0.562
x1 := 0.50
y1 ( x1) = 0.731
x1 := 0.75
y1 ( x1) = 0.808
B11 := 963
cm
mol
B22 := 1523
cm
mol
1 ( P , T , y1 , y2) := exp
R T
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
0.558
y
2 = 0.442
P
63.757
kPa
y1
y2 := Find ( y1 , y2 , P)
P
x1 := 0.50
Given
y1
0.733
y2 = 0.267
P
79.621
kPa
y1
y2 := Find ( y1 , y2 , P)
P
x1 := 0.75
Given
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
ln 1 = A12
541
(b)
(c)
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
H1 := 50
Guesses:
A21 := 0.2
A12 := 0.4
0=
0=
2
d
H1
Pi x1 1 x1 , x2 , A12 , A21
...
i
i
i
exp
A
dA12
(
)
12
2
d
H1
Pi x1 1 x1 , x2 , A12 , A21
...
i
i
i
exp
A
dA21
(
)
12
2
d
H1
Pi x1 1 x1 , x2 , A12 , A21
...
i
i
i
exp
A
dH1
(
)
12
A12
A12 0.348
A
=
21 0.178
H
1 51.337
542
Ans.
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
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
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
12 2i
A12 0.375
A21 = 0.148
H
1 53.078
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
ln 2 = A21
545
H2 := 14
Guesses:
A21 := 0.148
A12 := 0.375
0=
0=
d
2
dA Pi x1i 1 x1i , x2i , A12 , A21 Psat1 ...
12
H2
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
A12 0.469
A
=
21 0.279
H
2 14.87
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
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 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
H2
Pcalc := x1 1 x1 , x2 Psat1 + x2 2 x1 , x2
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
(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
H1 := 35
Guesses:
A21 := 1.27
A12 := 0.70
0=
0=
2
d
H1
Pi x1 1 x1 , x2 , A12 , A21
...
i
i
i
exp
A
dA12
(
)
12
2
d
H1
Pi x1 1 x1 , x2 , A12 , A21
...
i
i
i
exp
A
dA21
( 12)
2
d
H1
Pi x1 1 x1 , x2 , A12 , A21
...
i
i
i
exp
A
dH1
(
)
12
A12
A12 0.731
A
=
21 1.187
H
1 32.065
550
Ans.
(d)
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
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
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
x
A
12 2i
A12 0.707
A
=
21 1.192
H
1 33.356
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
(c)
H2 := 4
Guesses:
A21 := 1.37
A12 := 0.68
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
H2
+
x
x
,
x
,
A
,
A
2
1
2
12
21
2
i
i
i
exp ( A21)
A12
A12 0.679
A
=
21 1.367
H
2 3.969
554
Ans.
H2
Pcalc := x1 1 x1 , x2 Psat1 + x2 2 x1 , x2
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
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 x1 ... x1 x2
i
i
i
+
A
12 2i
A12 0.845
A21 = 1.229
H
2 4.703
H2
Pcalc := x1 1 x1 , x2 Psat1 + x2 2 x1 , x2
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)
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
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
i=1
Ans.
2
GERTi A21 x1i + A12 x2i x1i x2i
n
x1 := 0 , 0.01 .. 1
0.1
GERT i
0.05
0.2
0.4
0.6
0.8
x1 , x1
i
cm
B11 := 1840
mol
cm
B22 := 1800
mol
cm
B12 := 1150
mol
( )
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
GERTi A21 x1i + A12 x2i x1i x2i
A12
:= Minimize ( f , A12 , A21)
A
21
RMS :=
A12 = 0.379
Ans.
i=1
RMS = 9.187 10
A21 = 0.216
2
GERTi A21 x1i + A12 x2i x1i x2i
RMS Error:
2 :=
y2 2 Pi
x1 := 0 , 0.01 .. 1
0.1
GERT i
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
:= 0
:= 0.08664
:= 0.42748
( Tr) := Tr
q ( Tr) :=
( Tr )
Tr
Table 3.1
a ( Tr) :=
Eq. (3.54)
( Tr , Pr) :=
Table 3.1
( Tr ) R Tc
Guess:
Eq. (3.45)
Pc
Pr
Eq. (3.53)
Tr
zv := 0.9
Eq. (3.52)
zv ( Tr , Pr)
( zv + ( Tr , Pr) ) ( zv + ( Tr , Pr) )
Guess:
zl := 0.01
)(
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
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)
1bar
Pc
Psatr = 0.026
Zl ( Tr , Psatr) = 4.742 10
Psat := Psatr Pc
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
Tc := 308.3K
Pc := 61.39bar
:= 0
Tr :=
T
Tc
Tr = 0.614
Tn := 189.4K
:= 0.08664
561
:= 0.42748
Table 3.1
2
2
( Tr , ) := 1 + ( 0.480 + 1.574 0.176 ) 1 Tr
Tr ,
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 ( Tr , Pr)
( zv + ( Tr , Pr) ) ( zv + ( Tr , Pr) )
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
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)
562
Eq. (6.65b)
2bar
Pc
Psatr = 0.017
Psat := Psatr Pc
Zl ( Tr , Psatr) = 3.108 10
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 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 (K) Psat (bar) 0.85 Tc (K) Psat (bar) Psat (bar) % Difference
@ Tn
@ 0.85 Tc Lit. Values
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%
Tc := 308.3K
Pc := 61.39bar
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
Tr , R Tc
Eq. (3.45)
Eq. (3.54)
( Tr , Pr) :=
Guess:
Pr
Tr
Eq. (3.53)
zv := 0.9
Eq. (3.52)
zv ( Tr , Pr)
( zv + ( Tr , Pr) ) ( zv + ( Tr , Pr) )
Guess:
zl := 0.01
)(
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
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)
564
Eq. (6.65b)
Guess Psat:
Psatr :=
Given
Psatr = 0.018
Zl ( Tr , Psatr) = 2.795 10
Psat := Psatr Pc
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 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)
:= 0
q ( Tr) :=
Given
Tn (K) Psat (bar) 0.85 Tc (K) Psat (bar) Psat (bar) % Difference
@ Tn
@ 0.85 Tc Lit. Values
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
( Tr) := 1
27
64
zv := 0.9 (guess)
zv ( Tr , Pr)
( zv)
565
Eq. (3.52)
(guess)
2 1 + ( Tr , Pr) zl
zl = ( Tr , Pr) + ( zl)
Given
q ( Tr) ( Tr , Pr)
Eq. (3.56)
zl < 0.2
( Tr , Pr)
Zv ( Tr , Pr)
Il ( Tr , Pr) :=
( Tr , Pr)
Zl ( Tr , Pr)
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) = 0.839
Zl ( Tr , Psatr) = 0.05
:= 1 log ( Psatr)
= 0.302
(b)
Psatr = 0.2
Ans.
:= 1
:= 0
:= 0.08664
:= 0.42748
.5
( Tr) := Tr
q ( Tr) :=
( Tr)
( Tr , Pr) :=
Tr
Pr
Tr
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)
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
= 0.058
x2 := 1 x1
A12 := 2
Psatr = 0.087
( Tr , Psatr) = 0.011
Ans.
x1 := 0.9
x2 := 1 x1
A21 := 2
567
Given
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
Given
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
568
Ans.
Given
A12
:= Find ( A12 , A21)
A
21
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 +
x2
21
2
2
a21 x2
a21 x2
exp a21 1 +
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 +
x2
21
2
2
a21 x2
a21 x2
exp a21 1 +
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 +
x2
21
2
2
a21 x2
a21 x2
exp a21 1 +
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
x := 0.25
1 x
x
A ( T) ( 1 2 x) = ln
x 0.5
x1 ( T) := Find ( x)
570
A ( UCST) = 2
UCST = 272.93
LCST = 391.21
A ( LCST) = 2
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
0.7
0.8
Guess:
x := 0.25
Given
A ( T) ( 1 2 x) = ln
1 x
x
x0
x 0.5
x1 ( T) := Find ( x)
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
0.7
0.8
Guess:
x := 0.25
Given
A ( T) ( 1 2 x) = ln
1 x
x
x0
x 0.5
x1 ( T) := Find ( x)
Given
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
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.
5363.7
T
water
2048.97
T
SF6
P := 1600
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
600
700
288
286
TI
Tstar
284
282
280
650
700
750
800
850
900
950
1000
1050
3056.96
T + 217.625
3885.70
P2sat ( T) := exp 16.3872
T + 230.170
Toluene
P := 101.33
Water
Guess:
P = P1sat ( T) + P2sat ( T)
Given
y1star :=
P1sat ( Tstar)
P
Tstar := Find ( T)
y1star = 0.444
Guess:
y1 = 1
Tdew := Tstar
P2sat ( Tdew)
P
575
Ans.
Tstar = 84.3
y1 := 0.7
Guess:
y1 =
Given
Tdew := Tstar
P1sat ( Tdew)
P
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
2910.26
T + 216.432
n-heptane
3885.70
T + 230.170
water
P := 101.33
T := 50
Given
P = P1sat ( T) + P2sat ( T)
y1star :=
P1sat ( Tstar)
P
Tstar := Find ( T)
Tstar = 79.15
y1star = 0.548
P2sat ( T)
P
Guess:
y1 ( Tdew) = y10
Tdew := Tstar
Tdew := Find ( Tdew)
Tdew = 88.34
Define the path of vapor mole fraction above and below the dew point.
y1path ( T) := if ( T > Tdew , y10 , y1 ( T) )
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
P2sat := 110
A := 2.25
2
1 ( x1) := exp A ( 1 x1)
2 ( x1) := exp A x1
x1 := 0.1
Given
A ( 1 2 x1) = ln
1 x1
x1
x1 = 0.224
x1 := 1 x1
x1 := Find ( x1)
x1 = 0.776
Given
Pstar := P1sat
y1star := 0.5
Pstar
:= Find ( Pstar , y1star)
y1star
Pstar = 160.699
x1 := 0.1
P := 50
577
y1star = 0.405
Given
P ( x1) := Find ( P)
y1 ( x1) :=
x1 1 ( x1) P1sat
P ( x1)
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
3885.70
T + 230.170
n-Pentane:
2451.88
T + 232.014
n-Heptane:
2910.26
T + 216.432
P := 101.33
z1 := 0.45
(a)
z2 := 0.30
z3 := 1 z1 z2
Guess:
Tdew1 := 100
x2 := z2
x3 := 1 x2
Given
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
Given
Tdew3 := 100
x2 := z2
x3 := 1 x2
y1 := z1
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
3885.70
T + 230.170
n-Pentane:
2451.88
T + 232.014
n-Heptane:
2910.26
T + 216.432
P := 101.33
(a)
Guess:
Given
z1 := 0.32
z2 := 0.45
z3 := 1 z1 z2
x2 := z2
x3 := 1 x2
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
Given
Tdew3 := 100
x2 := z2
x3 := 1 x2
y1 := z1
y2 := z2
y3 := z3
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)
Tbubble := Tdew3
x2 :=
z2
z2 + z3
x2 = 0.662
582
x3 :=
z3
z2 + z3
x3 = 0.338
Given
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 :=
T
Tr :=
Tc
T := 353.15K
Use SRK EOS
:= 0
:= 0.08664
:= 0.42748
)(
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)
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 :=
T
Tr :=
Tc
T := 308.15K (K)
Use SRK EOS
:= 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)
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
Psat1
P 1 ( P)
P V 1
R T
exp
10
y1 ( P) 10
50
100
150
P
bar
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
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)
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
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
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
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
yi P
xi Psati
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
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.
x1 =
2
A
2
1
and
x1 =
2
A
A ( 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
1 xl
xl
xl < 0.5
Given
A ( T) ( 1 2xr) = ln
Given
A ( T) ( 1 2xl) = ln
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
Psat1r = 0.043
Psat2r = 0.039
21 := 0.5197
12
21
+ 1 x
(
1)
x
+
1
x
+
x
(
)
(
)
1
1
1
1
12
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)
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 = 0.946
c1
1 ( P) :=
c2
sat1
sat2 = 0.95
hat1 ( P)
2 ( P) :=
hat2 ( P)
sat2
y1 := 0.5
P := 1bar
Given
y1 1 ( P) P = x1 1 ( x1) Psat1 ( T)
Eqn. (14.1)
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