Chapter 3: Fractionation

Rules of Thumb for Chemical Engineers, 5th Edition

by Stephen Hall

This Excel workbook includes Visual Basic for Application function subroutines.
Macros must be enabled for them to work.

Antoine Constants
B
8.1
1,582.3
8.1
1,592.9
760 mm Hg

A
Methyl Alcohol
Ethyl Alcohol
System Pressure

Mole Fraction Methyl Alcohol

X
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00

Y
Temp, deg C
0.00
78.29819185
0.16
76.62501972
0.30
75.03043901
0.42
73.50920087
0.53
72.05646384
0.63
70.66773418
0.72
69.33876498
0.80
68.06574323
0.88
66.84506145
0.94
65.67340091
1.00
64.54773254

C
239.7
226.2

Problem Statement:
Construct a table of vapor-liquid equilibrium values
for a system of methanol-ethanol at 1 atmosphere
pressure, assuming ideal behavior.

VP, mm Hg
Methyl
Ethyl
Alcohol
Alcohol
1,275.42
760.00
1,200.44
711.06
1,132.40
666.90
1,070.50
626.93
1,014.03
590.65
962.38
557.63
915.01
527.49
871.47
499.91
831.35
474.62
794.29
451.36
760.00
429.92

Partial Pressure
Methyl
Ethyl
Alcohol
Alcohol Difference
0.00
760.00
(0.00)
120.04
639.96
(0.00)
226.48
533.52
(0.00)
321.15
438.85
(0.00)
405.61
354.39
0.00
481.19
278.81
0.00
549.00
211.00
(0.00)
610.03
149.97
(0.00)
665.08
94.92
(0.00)
714.86
45.14
(0.00)
760.00
0.00
(0.00)

quid equilibrium values

anol at 1 atmosphere

A
Ethyl Alcohol
Water

Antoine Constants
B
8.1
1,592.9
8.0
1,701.8

Mole Fraction Ethyl Alcohol

X

VP, mm Hg

Y
0.00
0.03
0.06
0.10
0.15
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00

Solution Model
None
Margules
van Laar

Problem Statement:
Construct a table of vapor-liquid equilibrium values for
system of ethanol-water at 1 atmosphere pressure, us
Activity coefficients from the Margules model.

C
226.2
231.5

Temp, deg C

0.00
0.23
0.35
0.44
0.51
0.54
0.59
0.62
0.65
0.69
0.75
0.82
0.91
1.00

100.09
93.65
89.78
86.60
84.30
82.94
81.49
80.65
79.99
79.41
78.94
78.60
78.40
78.30

Ethyl Alcohol
1,699.09
1,355.04
1,177.22
1,046.49
959.27
910.83
861.00
833.48
812.34
794.18
779.45
769.13
763.19
760.00

Margules

Water
760.00
601.42
520.02
460.47
420.88
398.94
376.42
364.01
354.48
346.30
339.67
335.03
332.36
330.93

VLE Ethanol-Water
1
2
3

Source:

2
1.000
1.002
1.008
1.023
1.050
1.087
1.189
1.326
1.493
1.680
1.872
2.045
2.170
2.214

Reference Line
Y

0
0.056
0.091
0.189
0.286
0.323
0.331
0.419
0.512
0.62
0.704
0.715
0.798
0.843
0.847
0.849
0.884
0.908
0.922

1
4.964
4.314
3.781
3.212
2.671
2.268
1.729
1.411
1.220
1.107
1.043
1.012
1.001
1.000

0
0.366
0.448
0.539
0.582
0.6
0.605
0.627
0.666
0.712
0.759
0.764
0.818
0.851
0.854
0.856
0.886
0.907
0.92

Y
0
1

0
1

Kurihara, K., Nakamichi, M., Kojima, K., "Isobaric Vapor-Liquid Equilibria for Methanol + Ethanol

Margules Parameters van Laar Parameters

A12
A21
A12
A21
1.6022
0.7947
1.6798
0.9227

liquid equilibrium values for a

water at 1 atmosphere pressure, using
s from the Margules model.

Margules Model
Partial Pressure
Ethyl
Alcohol
Water
0.00
175.38
267.09
336.16
384.38
413.06
446.66
470.39
495.44
527.32
569.28
622.98
687.89
760.00

1
4.964
4.314
3.781
3.212
2.671
2.268
1.729
1.411
1.220
1.107
1.043
1.012
1.001
1.000

Difference

760.00
584.62
492.91
423.84
375.62
346.94
313.34
289.61
264.56
232.68
190.72
137.02
72.11
0.00

(0.00)
(0.00)
(0.00)
0.00
0.00
0.00
0.00
0.00
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
0.00
(0.00)

van Laar Model

2
1.000
1.002
1.008
1.023
1.050
1.087
1.189
1.326
1.493
1.680
1.872
2.045
2.170
2.214

1
5.364
4.506
3.851
3.197
2.618
2.211
1.699
1.409
1.235
1.128
1.063
1.025
1.006
1.000

2
1.000
1.003
1.010
1.026
1.056
1.094
1.194
1.320
1.469
1.639
1.830
2.041
2.270
2.516

Vapor-Liquid Equilibrium
1
0.9

Mole Fraction, Vapor Phase

0.8
0.7
0.6
Reference Line

0.5

Predicted
Experimental

0.4
0.3
0.2
0.1
0
0

0.1

0.2

0.3

0.4

0.5

0.6

Mole Fraction, Liquid Phase

0.7

0.8

0.9

apor-Liquid Equilibria for Methanol + Ethanol + Water and the Three Constituent Binary Systems," J. Chem Eng. Data 1993, Vol 38, p 446-449.

Reference Line

Experimental

A
Methyl Alcohol
Ethyl Alcohol

Antoine Constants
B
8.1
1,582.3
8.1
1,592.9

Molar Composition
Methyl Alcohol
Ethyl Alcohol

Bottoms

Feed
0.40
0.60

Mole Fraction Methyl Alcohol

X
0.40

Y
Temp, deg C
0.53
72.06

Minimum Reflux Ratio

alpha
1.716808
Rm
3.34

C
239.7
226.2
Distillate
0.98
0.02

VP, mm Hg
Methyl
Ethyl
Alcohol
Alcohol
1,014.03
590.65

Answer

Problem Statement:
Estimate the minimum reflux ratio for a binary fee
consisting of 40 mole% methanol and 60 mole%
ethanol at its bubble point. The desired distillate
composition is 98 mole % methanol.

Partial Pressure
Methyl
Ethyl
Alcohol
Alcohol Difference
405.61
354.39
0.00

mum reflux ratio for a binary feed

mole% methanol and 60 mole%
ble point. The desired distillate
mole % methanol.

A
n-hexane
n-heptane
n-octane

Antoine Constants
B
6.8
1,112.6
6.8
1,224.4
6.9
1,317.0

System Pressure
Temperature
Molar Composition
n-hexane
n-heptane
n-octane

760
102
Feed
0.10
0.50
0.40

mm Hg
deg C
VP, mm Hg
1,915.450
837.854
373.820
Difference

Feed Condition, q
Theta
Molar Composition
n-hexane
n-heptane
n-octane

1.00
1.30
Feed
0.10
0.50
0.40

Problem Statement:
Estimate the minimum reflux ratio for the tertiary
system n-hexane, n-heptane, n-octane, with the
feed at the bubble point and molar composition
0.1, 0.5, 0.4 respectively. 95% of the n
should be contained in the distillate and 99% of the
n-octane in the bottoms.

C
218.0
212.9
205.5

PP
191.545
418.927
149.528
760.000
0.000

5.12
2.24
1.00

(1 = feed at the Bubble Point)

xi i / (i - )
5.12
0.13
2.24
1.19
1.00
(1.33)
0.00
Difference
(0.00)

Distillate
0.173
0.820
0.007

xiD i / (i - )
0.23
1.96
(0.02)
2.17 = Rm + 1

Calculation of the distillate and bottoms compositions

Moles
Molar Composition
n-hexane
n-heptane
n-octane

Feed
0.10
0.50
0.40

Light Key

Heavy Key

x
x

Recovery of
Keys

95%
99%

Bottoms
0.00
2.50
39.60
42.10

Distillate
10.00
47.50
0.40
57.90

um reflux ratio for the tertiary

-octane, with the
oint and molar composition
vely. 95% of the n-heptane
in the distillate and 99% of the

Answer

Mole Fraction
Bottoms
0.00
0.06
0.94

Distillate
0.173
0.820
0.007

Feed

100 moles

A
Methyl Alcohol
Ethyl Alcohol
Molar Composition
Methyl Alcohol
Ethyl Alcohol
System Pressure

Antoine Constants
B
8.1
1,582.3
8.1
1,592.9
Bottoms

C
239.7
226.2
Feed
0.40
0.60

Distillate
0.98
0.02

Bottoms
0.01
0.99

Problem Statement:
Find the number of stages for a me
column, with 40 mole% methanol in
mole% methanol in the distillate, an
the bottoms, given a reflux ratio of 5

760

Mole Fraction Methyl Alcohol

X
Y
Temp, deg C
0.01
0.02
78.13
0.40
0.53
72.06
0.98
0.99
64.77

VP, mm Hg
Methanol
Ethanol
1,267.58
754.87
1,014.03
590.65
766.65
434.07

Minimum Reflux Ratio

alpha
1.679202
Rm
3.52

Minimum Number of Stages at Infinite Reflux

Fenske Equation

Nm

14.64

Molkanov Equation
Y = 1 exp[(1 + 54.4X)(X 1) / ((11 + 117.2X)(X0.5)]
Y = (N Nmin) / (N + 1)
X = (R Rmin) / (R + 1)
For R =
X=

5.0
0.25

N=
Y=

26.09
0.42

RHS =
Difference

0.42
(0.00)

Answer

Partial Pressure
Methanol Ethanol Difference
12.68
747.32
(0.00)
405.61
354.39
0.00
751.32
8.68
(0.00)
0.00

em Statement:
he number of stages for a methanol-ethanol
n, with 40 mole% methanol in the feed, 98
% methanol in the distillate, an 1% methanol in
ttoms, given a reflux ratio of 5.0

i
1.679
1.717
1.766

A
Ethyl Alcohol
Water

Antoine Constants
B
8.1
1,592.9
8.0
1,701.8

Mole Fraction Ethyl Alcohol

X

VP, mm Hg

Y
0.00
0.03
0.06
0.10
0.15
0.20
0.28
0.40
0.50
0.60
0.70
0.80
0.90
1.00

Temp, deg C Ethyl Alcohol

0.00
0.23
0.35
0.44
0.51
0.54
0.58
0.62
0.65
0.69
0.75
0.82
0.91
1.00

Molar Composition
Ethyl Alcohol
Water
Reflux Ratio
Feed, q

Problem Statement:
Construct a McCabe-Thiele Diagram for a system
water at 1 atmosphere pressure, using Activity coe
from the Margules model.

C
226.2
231.5

100.09
93.65
89.78
86.60
84.30
82.94
81.72
80.65
79.99
79.41
78.94
78.60
78.40
78.30

1,699.09
1,355.04
1,177.22
1,046.49
959.27
910.83
869.00
833.48
812.34
794.18
779.45
769.13
763.19
760.00

Bottoms
0.02
0.98

Water
760.00
601.42
520.02
460.47
420.88
398.94
380.04
364.01
354.48
346.30
339.67
335.03
332.36
330.93

Feed
0.40
0.60

Margules
1
4.964
4.314
3.781
3.212
2.671
2.268
1.824
1.411
1.220
1.107
1.043
1.012
1.001
1.000

2
1.000
1.002
1.008
1.023
1.050
1.087
1.164
1.326
1.493
1.680
1.872
2.045
2.170
2.214

Distillate
0.80
0.20

10
0.9999

Reference Line
Slope
Intercept
X
0.00
1.00

Stripping
1.00 Slope
0.00 Intercept
Y
X
0.00
0.02
1.00
0.40

Feed
Rectification
1.10 Slope
9,999.00 Slope
(0.00) Intercept
(3,999.20) Intercept
Y
X
Y
X
0.02
0.40
0.40
0.80
0.44
0.40
0.44
0.40

Step Data
Y
0.02
0.02
0.16
0.16
0.48
0.48
0.63

McCabe-Thiele Diagram

0.02
0.17
0.17
0.51
0.51
0.65
0.65

1.00
0.90
0.80
raction, Vapor Phase

Mole Fraction, Vapor Phase

0.71
0.71
0.75
0.75
0.78
0.78
0.80
0.80
0.82
0.82
0.84
0.84
0.85
0.85
0.87
0.87
0.88
0.88
0.90
0.90
0.91
0.91
0.93
0.93
0.94
0.94
0.96
0.96
0.97
0.97
0.99
0.99
1.01
1.01
1.03
1.03
1.05
1.05
1.07
1.07
1.09
1.09
1.11
1.11
1.13
1.13
1.14
1.14
1.15
1.15
1.16
1.16

0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0.00

0.10

0.20

0.30

0.40

0.50

0.60

Mole Fraction, Liquid Phase

McCabe-Thiele Diagram
1.00
0.90
0.80

Mole Fraction, Vapor Phase

0.63
0.70
0.70
0.74
0.74
0.78
0.78
0.80
0.80
0.82
0.82
0.84
0.84
0.86
0.86
0.88
0.88
0.89
0.89
0.91
0.91
0.92
0.92
0.94
0.94
0.96
0.96
0.97
0.97
0.99
0.99
1.01
1.01
1.03
1.03
1.05
1.05
1.08
1.08
1.10
1.10
1.12
1.12
1.14
1.14
1.16
1.16
1.18
1.18
1.19
1.19
1.20

0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0.00

0.10

0.20

0.30

0.40

0.50

0.60

Mole Fraction, Liquid Phase

0.70

1.20
1.21
1.21
1.21
1.21
1.21
1.21
1.22
1.22
1.22
1.22
1.22
1.22
1.22
1.22
1.22
1.22
1.22
1.22

1.17
1.17
1.17
1.17
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18

Thiele Diagram for a system of ethanolhere pressure, using Activity coefficients

Margules Parameters van Laar Parameters

A12
A21
A12
A21
1.6022
0.7947
1.6798
0.9227

Margules Model
Partial Pressure
Ethyl
Alcohol
Water
0.00
175.38
267.09
336.16
384.38
413.06
440.72
470.39
495.44
527.32
569.28
622.98
687.89
760.00

760.00
584.62
492.91
423.84
375.62
346.94
319.28
289.61
264.56
232.68
190.72
137.02
72.11
0.00

Difference
(0.00)
(0.00)
(0.00)
0.00
0.00
0.00
(0.00)
0.00
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
0.00
(0.00)

1
4.964
4.314
3.781
3.212
2.671
2.268
1.824
1.411
1.220
1.107
1.043
1.012
1.001
1.000

2
1.000
1.002
1.008
1.023
1.050
1.087
1.164
1.326
1.493
1.680
1.872
2.045
2.170
2.214

van Laar Model

1
5.364
4.506
3.851
3.197
2.618
2.211
1.787
1.409
1.235
1.128
1.063
1.025
1.006
1.000

2
1.000
1.003
1.010
1.026
1.056
1.094
1.170
1.320
1.469
1.639
1.830
2.041
2.270
2.516

Murphree Tray Efficiency:

Segment 1 Origin
Rectification
0.91
0.07
Y
0.80
0.44

Step
Reboiler
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15

X
0.02
0.16
0.48
0.63
0.70
0.74
0.78
0.80
0.82
0.84
0.86
0.88
0.89
0.91
0.92
0.94

Y
0.02
0.17
0.51
0.65
0.71
0.75
0.78
0.80
0.82
0.84
0.85
0.87
0.88
0.90
0.91
0.93

Segment 2 Origin
Murphree
Y
X
0.02
0.17
0.16
0.51
0.48
0.65
0.63
0.71
0.70
0.75
0.74
0.78
0.78
0.80
0.80
0.82
0.82
0.84
0.84
0.85
0.86
0.87
0.88
0.88
0.89
0.90
0.91
0.91
0.92
0.93
0.94
0.94

0.70

0.80

0.90

16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38

1.00

on, Liquid Phase

Thiele Diagram

Liquid Phase

Reference Line
VLE Curve
Stripping
Feed
Rectification
Tray Steps
Murphree VLE

0.70

0.80

0.90

1.00

0.96
0.97
0.99
1.01
1.03
1.05
1.08
1.10
1.12
1.14
1.16
1.18
1.19
1.20
1.21
1.21
1.21
1.22
1.22
1.22
1.22
1.22
1.22

0.94
0.96
0.97
0.99
1.01
1.03
1.05
1.07
1.09
1.11
1.13
1.14
1.15
1.16
1.17
1.17
1.18
1.18
1.18
1.18
1.18
1.18
1.18

0.96
0.97
0.99
1.01
1.03
1.05
1.08
1.10
1.12
1.14
1.16
1.18
1.19
1.20
1.21
1.21
1.21
1.22
1.22
1.22
1.22
1.22
1.22

0.96
0.97
0.99
1.01
1.03
1.05
1.07
1.09
1.11
1.13
1.14
1.15
1.16
1.17
1.17
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18

Solution Model
None
Margules
van Laar

VLE Y
0.17
0.51
0.65
0.71
0.75
0.78
0.80
0.82
0.84
0.85
0.87
0.88
0.90
0.91
0.93
0.94

1
2
3

VP, mm Hg
Temp, deg
Ethyl
C
Alcohol
Water
95.42 1,443.10
641.88
84.03
949.32
416.37
80.09
815.38
355.85
79.25
789.19
344.06
78.94
779.41
339.65
78.77
774.31
337.36
78.67
771.16
335.94
78.60
769.00
334.97
78.54
767.40
334.25
78.50
766.15
333.69
78.47
765.14
333.24
78.44
764.29
332.85
78.42
763.55
332.52
78.39
762.90
332.23
78.37
762.31
331.96
78.36
761.76
331.72

Margules
1
4.516
2.596
1.243
1.083
1.043
1.027
1.018
1.012
1.009
1.006
1.004
1.003
1.002
1.001
1.001
1.000

2
1.001
1.055
1.465
1.740
1.872
1.952
2.007
2.047
2.079
2.105
2.127
2.146
2.162
2.176
2.188
2.198

Partial Pressure
Ethyl
Alcohol
Water
130.35
629.65
390.10
369.89
491.25
268.75
539.14
220.86
569.44
190.56
591.53
168.47
609.10
150.90
623.93
136.07
637.04
122.96
649.03
110.97
660.34
99.66
671.28
88.72
682.07
77.93
692.92
67.08
704.01
55.99
715.50
44.50

Difference
0.00
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)

0.96
0.97
0.99
1.01
1.03
1.05
1.07
1.09
1.11
1.13
1.14
1.15
1.16
1.17
1.17
1.18
1.18
1.18
1.18
1.18
1.18
1.18
1.18

78.34
78.32
78.31
78.29
78.27
78.25
78.22
78.19
78.15
78.11
78.08
78.04
78.01
77.99
77.97
77.96
77.96
77.95
77.95
77.94
77.94
77.94
77.94

761.25
760.74
760.24
759.70
759.11
758.44
757.64
756.71
755.65
754.51
753.37
752.33
751.46
750.79
750.30
749.96
749.74
749.59
749.50
749.44
749.40
749.38
749.36

331.49
331.26
331.03
330.79
330.53
330.22
329.87
329.45
328.97
328.46
327.95
327.48
327.09
326.79
326.57
326.42
326.31
326.25
326.21
326.18
326.16
326.15
326.15

1.000
1.000
1.000
1.000
1.000
1.000
0.999
0.998
0.997
0.995
0.993
0.991
0.988
0.987
0.985
0.984
0.984
0.983
0.983
0.983
0.983
0.983
0.983

2.206
2.211
2.214
2.213
2.207
2.195
2.177
2.153
2.123
2.089
2.054
2.022
1.995
1.973
1.957
1.946
1.939
1.934
1.931
1.929
1.927
1.927
1.926

727.52
740.22
753.67
767.93
782.96
798.59
814.47
830.11
844.83
857.97
869.00
877.72
884.20
888.80
891.92
893.99
895.33
896.19
896.73
897.07
897.29
897.42
897.51

32.48
19.78
6.33
(7.93)
(22.96)
(38.59)
(54.47)
(70.11)
(84.83)
(97.97)
(109.00)
(117.72)
(124.20)
(128.80)
(131.92)
(133.99)
(135.33)
(136.19)
(136.73)
(137.07)
(137.29)
(137.42)
(137.51)

(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)
(0.00)

Difference
Total

781.53

Problem Statement:
Determine a column pressure that fits within available
steam and cooling water temperatures

A
Light
Heavy

Ethane
Isobutane
Water

LP Steam Pressure
MP Steam Pressure
HP Steam Pressure
Tower Water Temp.
Chilled Water Temp.
Reboiler approach
Condenser approach

Antoine Constants
B
6.8
656.4
6.7
882.8
8.0
1,701.8

Pressure
1
5
15

bar (gauge)
bar (gauge)
bar (gauge)

C
256.0
240.0
231.5

Temperature
121
159
202
40
15
15
10

Mole Fraction Ethane

X
Bottoms

0.05
0.05
0.05

VP, mm Hg
Y
0.25
0.21
0.19

Bubble Point
Temp, deg C
105.7
144.3
186.7

Maximum
Pressure
19,741.5
34,124.1
55,837.9

Y
0.95
0.95

Dew Point
Temp, deg C
50.0
25.0

Minimum
Pressure
32,477.9
19,382.8

Mole Fraction Ethane

X
Distillate

C
C
C
C
C
C
C

Pressure, mm Hg
Maximum Minimum
19,741.5
34,124.1
55,837.9
32,477.9
19,382.8

Ethane
Isobutane
97,291.98 #######
######### #######
######### #######
VP, mm Hg

Results

Partial Pressure
Ethane
4,864.60
7,277.32
10,445.14

Isobutane Difference
########
0.00
########
0.00
########
0.00

y/P*

Ethane
Isobutane
Ethane
Isobutane Difference
45,444.98 5,057.80 0.00002090
0.00
0.00
29,283.80 2,610.82 0.00003244
0.00
0.00

Therefore, to operate this co

atmospheric pressure (760 m
MP or HP steam for the rebo
water for the condenser.

Therefore, to operate this column at close to

atmospheric pressure (760 mm Hg), choose
MP or HP steam for the reboiler, and tower
water for the condenser.

Methyl Alcohol
Water
Methane
Ethane
Propane
Toluene
Acetic Acid
Isobutane
n-Butane
Isopentane
n-Pentane
n-Hexane
n-Heptane
n-Octane
Ethyl Alcohol

Antoine Coefficients
A
B
8.08097
1582.271
8.01352769 1701.78587
6.61182948 389.926958
6.80265848 656.401366
6.95916997 857.736201
7.05282866
1397.197
7.49044999 1604.16592
6.74811109 882.803422
6.96820966 1000.63935
6.78967307 1020.01442
6.83902998 1059.01668
6.76098367 1112.56081
6.81342209 1224.41518
6.85804739 1316.95574
8.1122
1592.864

C
239.726
231.466749
265.99
255.99
252.414186
224.2974
229.902701
240
245.310958
233.1
231.448959
218.029908
212.94937
205.523542
226.184

Mol Wt
MW
32.042
18.015
16.043
30.07
44.097
92.141
60.052
58.124
58.124
72.151
72.151
86.178
100.21
114.232
46.069