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Instructions

ACTCOEFF.XLS
This workbook will calculate activities, activity coefficients, and excess Gibbs energies
for several activity models.
Margules

Worksheet using the Margules equation with two adjustable parameters.

Regular

A spreadsheet to calculate VLE for methanol + benzene


using van Laar and Scatchard/Hildbrand theory.

UNIQUAC

A spreadsheet to use with the binary UNIQUAC activity coefficient model.

UNIQUAC5

A spreadsheet to use UNIQUAC with up to 5 components.

ANTOINE

Table of Antoine Coefficients.

UNIFAC (VLE)

A spreadsheet to use with the UNIFAC activity coefficient model


for VLE for up to 5 components.

aij-UNIFAC (VLE) Database of parameters used by UNIFAC for VLE.


UNIFAC (LLEa,b) Two spreadsheets to use with the UNIFAC activity coefficient model
for LLE for up to 5 components.
aij-UNIFAC (LLE) Database of parameters used by UNIFAC for LLE.
LLE

Liquid + Liquid equilibria: Water + MEK example used in the text.

Worksheets are protected. Values in blue may be changed without unlocking the spreadsheet, which will
permit most common calculations.
Copyright 1997-2000, Carl Lira, Richard Elliott
For use with "Introductory Chemical Engineering Thermodynamics" by J.R. Elliott, C.T. Lira
www.egr.msu.edu/~lira/thermtxt.htm

Page 1

133424545.xls
Margules Equation
GE/RT = x1 x2 ( A21 x1 + A12 x2 )
Margules Parameters
A12_
1.86
Table x1 increment
0.05

x1
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
0.75
0.8
0.85
0.9
0.95
1

x2
1
0.95
0.9
0.85
0.8
0.75
0.7
0.65
0.6
0.55
0.5
0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0

gamma1
6.43
5.26
4.35
3.65
3.11
2.67
2.33
2.05
1.83
1.65
1.51
1.39
1.29
1.21
1.15
1.1
1.06
1.03
1.01
1
1

gamma2
1
1.01
1.02
1.05
1.08
1.13
1.19
1.27
1.36
1.46
1.59
1.74
1.92
2.13
2.38
2.67
3.02
3.42
3.9
4.47
5.14

A21_
1.64

activity1
0
0.26
0.44
0.55
0.62
0.67
0.7
0.72
0.73
0.74
0.75
0.76
0.77
0.79
0.8
0.82
0.85
0.88
0.91
0.95
1

Page 2

activity2 G(mix) /RT


1
0
0.95
-0.11
0.92
-0.16
0.89
-0.19
0.87
-0.21
0.85
-0.22
0.83
-0.23
0.82
-0.24
0.81
-0.25
0.81
-0.25
0.8
-0.26
0.78
-0.26
0.77
-0.26
0.75
-0.26
0.71
-0.25
0.67
-0.24
0.6
-0.23
0.51
-0.21
0.39
-0.18
0.22
-0.12
0
0

Regular

The bubble temperatures and vapor compositions at each temperature are computed
using: (1) the Scatchard-Hildebrand model with zero binary interaction coefficient;
(2) the Scatchard-Hildebrand model with binary interaction coefficient chosen to match
the bubble pressure near the azeotrope; (3) the van Laar model; The system
illustrated below is the methanol+benzene system. The bubble temperatures are computed
by setting the target y1+y2=1 by changing the estimated temperature. This is repeated
for each composition for each model.
Pure Component Data
(cal/cm3)1/2
VL (cm3/mol)
Antoine Coeff
A
B
C
1 MeOH
8.08 1582.27 239.73
40
14.5
2 benzene
6.88 1196.76 219.16
88
9.2
Mixture data to be used in all sets:
Methanol+benzene data from Perry's 6th p13-12 and 13.59
P=
760 mm Hg
x1
0
0.03
0.05
0.09
0.16
0.28
0.33
0.55
0.7
0.78
y1
0
0.27
0.37
0.46
0.53
0.56
0.6
0.63
0.67
T (C)
80.1
70.67
66.44
62.87
60.2
58.64
58.02
58.1
58.47
Calculations based on data
T(K)
353.25 343.82 339.59 336.02 333.35
331.79 331.17 331.25 331.62
1
0
0.01
0.02
0.04
0.08
0.15
0.18
0.36
0.51
0.62

Scatchard-Hildebrand model with zero binary interaction coefficient (x's from above) see plot ---->
x1
0
0.03
0.05
0.09
0.16
0.28
0.33
0.55
0.7

0.78

4.96

4.9

4.81

4.63

4.19

3.44

3.15

2.05

1.51

1.28

1.01

1.03

1.09

1.14

1.62

2.73

4.33

1360.42 1106.07

952.14

793.18

624.1

515.24

495.45

476.6

481.26

471.9

P
P

sat
1
sat
2

y1 calc
y2 calc
T(K)
(yi-1)2

760

635.42

558.01

476.14

386.43

326.88

315.88

305.35

307.95

302.71

0.19

0.3

0.42

0.56

0.66

0.68

0.71

0.67

0.62

1
353.25

0.81
347.54

0.7
343.54

0.58
338.79

0.44
332.77

0.34
328.13

0.32
327.2

0.29
326.28

0.33
326.51

0.38
326.05

0
0
<----- LLE region --->

This table permits calculation of LLE if it exists as above in column G and M (LLE explained in Chap 12)
*x
LLE
x1
1*x1
0
0.28
2*x2
0
0.97
Scatchard-Hildebrand model with binary interaction coefficient kij=
x1
0
0.03
0.05
0.09
0.16
0.28

0.33

0.55

0.7

0.78

2.95

2.9

2.81

2.62

2.3

2.16

1.62

1.32

1.18

1.02

1.06

1.09

1.39

1.97

2.69

1360.42 1206.11 1097.85

P1sat

-0.03

970.38

809.73

680.29

650.46

593.28

588.08

588.26

P2sat

760

684.87

631.32

567.28

484.77

416.59

400.63

369.73

366.9

367

y1 calc

0.12

0.21

0.32

0.46

0.58

0.62

0.7

0.71

0.72

1
353.25

0.88
349.9

0.79
347.34

0.68
344.04

0.54
339.32

0.42
334.91

0.38
333.79

0.3
331.53

0.29
331.32

0.28
331.32

y2 calc
T(K)
(yi-1)2

Page 3

First, set this to 331.3 (close to


azeotrope T and composition),
then adjust kij until cell J48 = 0.

Regular

First, set this to 331.3 (close to


azeotrope T and composition),
then adjust kij until cell J48 = 0.

Van Laar model with A12 and A21 chosen to match the azeotrope. See plot ---->
For this calculation, experimental azeotrope is taken as x1 = y1 = 0.614, T(C) = 58.3
P1sat
1
A12
591.29
1.29
1.98
These values are calculated from the activitiy coefficient
P2sat

368.65

A21

2.06

1.74

and composition values at the azeotrope.

x1

0.03

0.05

0.09

0.16

0.28

0.33

0.55

0.7

0.78

7.28

6.48

5.85

5.01

3.77

2.56

2.24

1.42

1.16

1.08

1.01

1.02

1.06

1.18

1.26

1.8

2.5

3.08

1360.42 1035.63

P1sat

885.79

759.29

653.48

605.46

599.37

591.84

593.21

602.28

P2sat

760

600.2

524.1

458.4

402.25

376.35

373.04

368.95

369.69

374.62

y1 calc

0.23

0.34

0.44

0.53

0.58

0.59

0.61

0.63

0.67

1
353.25

0.77
345.77

0.66
341.64

0.56
337.67

0.47
333.91

0.42
332.03

0.41
331.78

0.39
331.47

0.37
331.53

0.33
331.9

y2 calc
T(K)
(yi-1)2

Page 4

Regular

0.9

0.97

0.76
59.9

0.91
62.7

1
64.7

333.05

335.85

337.85

0.94

0.8

0.97

0.94

360
0.97

0.97

1.07

1.01

1.01

11.65

29.02

29.01

39.8

438.82

515.2

515.06

759.99

284.05

326.86

326.79

458.77

0.56

0.66

0.66

0.44
324.35

0.34
328.13

0.34
328.12

0
|

350
340
T(K)

0.9

320
310

0
337.7 OBJ
0

330

300
0

Bubble temperatures can be


found across the composition
range using Solver by setting this
to zero and adjusting B30:O30

0.3

0.4

0.5
x-y

0.6

0.7

0.8

0.9

355

0.97

0.97

1.05

350

5.19

9.64

9.63

12.5

345

598.28

668.77

668.69

759.99

372.45

410.43

410.4

458.77

0.74

0.86

0.86

0.26
331.74

0.14
334.48

0.14
334.48

First, set this to 331.3 (close to


azeotrope T and composition),
then adjust kij until cell J48 = 0.

0.2

The cross-overs in the above diagram are indicative


of LLE. The points represent experimental data.
An interaction parameter is necessary to fit the data
without predicting LLE.

0.9

T(K)

340
335
330

0
337.7 OBJ
0

0.1

325
320
0

Then, use Solver to adjust


B47:O47 to calc bubble T's.

Page 5

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9


x-y

T(K)

335

330
Regular
325
First, set this to 331.3 (close to
azeotrope T and composition),
then adjust kij until cell J48 = 0.

320
Then, use Solver to adjust
B47:O47 to calc bubble T's.

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9


x-y

0.1

calculated from the activitiy coefficient


values at the azeotrope.

0.97

0.97

355

1.02

350

4.22

5.26

5.26

5.71

345

644.91

716.65

716.61

759.99

340

397.65

435.92

435.89

458.77

0.77

0.92

0.92

330

0.23
333.58

0.08
336.21

0.08
336.21

0
337.7 OBJ

325

T(K)

0.9

335

320
0.2

0.3

0.4

0.5
x-y

After determining the A12 and A21, the bubble


temperatures are calculated across the
composition range as before.

Page 6

0.6

0.7

0.8

0.9

.7

Regular

0.8

0.9

7 0.8 0.9

1
Page 7

Regular

7 0.8 0.9

0.8

0.9

Page 8

UNIQUAC
UNIQUAC Calculation

Note: This spreadsheet uses the form of equations that permits the q of the residual part to
of the combinatorial part. (Anderson, T.F., Prausnitz, J.,M., Ind. Eng. Chem. Process Des. D
The formulas look a little different because or the use of the intermediate variable 'l', howev
are consistent with the method described in the text if the user sets q'=q.
r
q
q'
l
l-(r/r)l
a12
a21
(1) Methanol
1.43
1.43
1.43
-0.43
-1.22
-32.78
529.57
(2) Benzene
3.19
2.4
2.4
1.76
2.72
Table x1 increment
0.05
x1
0.000000
0.050000
0.100000
0.150000
0.200000
0.250000
0.300000
0.350000
0.400000
0.450000
0.500000
0.550000
0.600000
0.650000
0.700000
0.750000
0.800000
0.850000
0.900000
0.950000
1.000000

x2
1
0.95
0.9
0.85
0.8
0.75
0.7
0.65
0.6
0.55
0.5
0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0

T(C)
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90
90

T(K)
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15
363.15

tau12
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09
1.09

tau21
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23
0.23

Page 9

theta1
0
0.03
0.06
0.1
0.13
0.17
0.2
0.24
0.28
0.33
0.37
0.42
0.47
0.53
0.58
0.64
0.7
0.77
0.84
0.92
1

theta2
1
0.97
0.94
0.9
0.87
0.83
0.8
0.76
0.72
0.67
0.63
0.58
0.53
0.47
0.42
0.36
0.3
0.23
0.16
0.08
0

theta'1
0
0.03
0.06
0.1
0.13
0.17
0.2
0.24
0.28
0.33
0.37
0.42
0.47
0.53
0.58
0.64
0.7
0.77
0.84
0.92
1

UNIQUAC

permits the q of the residual part to differ from q


,M., Ind. Eng. Chem. Process Des. Dev. 17, 1978, 552-561).
f the intermediate variable 'l', however the equations
he user sets q'=q.

theta'2
1
0.97
0.94
0.9
0.87
0.83
0.8
0.76
0.72
0.67
0.63
0.58
0.53
0.47
0.42
0.36
0.3
0.23
0.16
0.08
0

phi1
0
0.02
0.05
0.07
0.1
0.13
0.16
0.19
0.23
0.27
0.31
0.35
0.4
0.45
0.51
0.57
0.64
0.72
0.8
0.89
1

phi2
1
0.98
0.95
0.93
0.9
0.87
0.84
0.81
0.77
0.73
0.69
0.65
0.6
0.55
0.49
0.43
0.36
0.28
0.2
0.11
0

ln(gam1) ln(gam2)
1.96
0
1.71
0.01
1.49
0.02
1.29
0.05
1.12
0.09
0.97
0.13
0.83
0.19
0.71
0.24
0.6
0.31
0.5
0.38
0.41
0.46
0.33
0.55
0.26
0.64
0.2
0.74
0.15
0.85
0.11
0.97
0.07
1.1
0.04
1.24
0.02
1.39
0
1.55
0
1.73

gam1
7.12
5.53
4.44
3.65
3.07
2.63
2.29
2.03
1.82
1.65
1.51
1.4
1.3
1.23
1.16
1.11
1.07
1.04
1.02
1
1

Page 10

gam2
1
1.01
1.02
1.05
1.09
1.14
1.2
1.28
1.36
1.47
1.59
1.73
1.9
2.1
2.35
2.64
3
3.45
4.01
4.72
5.65

UNIQUAC5
UNIQUAC5
This spreadsheet is constructed to calculate activity coefficients for up to 5 components
using the UNIQUAC activity coefficient expression. Antoine coeffients are optional.
Enter T, component names, aij's, r, q, and composition values.
1
2
3
4
5
Antoine A
8.07
7.28
Antoine B
1730.63
1434.2
Antoine C
233.43
246.5
Psat (mmHg)
23.69
99.57
1
1
1
y
0.2283
0.7717
0.0000
0.0000
0.0000 Unhide columns G-R for LLE iterations.
Pcalc (mm Hg)
98.49
T (K) =

298.15 Phase
1

Name
x

8.91E-01 9.89E-02 1.00E-02

1.00E-11

1.00E-11

Water

2
MEK

Acetic

1.07
0.95

7.72
0.76

0.08
0

4.27
0

1.19
0

0.92
1.4
0.7
0.8

3.25
2.88
0.28
0.18

2.2
2.07
0.02
0.01

3.19
2.4
0
0

1.43
1.43
0
0

1.16 ixiqi
1.55
aij matrix (i = row, j=column), enter 0's for unused cells
1
2
3
1
1
-2.09
254.15
2
345.53
1
-254.13
3
-301.02
-4.55
1
4
0
0
0
5
0
0
0

4
0
0
0
1
0

5
0
0
0
0
1

ij matrix (i = row, j=column)


1
1
1
2
0.31
3
2.74

4
1
1
1

5
1
1
1

r
q

ixiri

2
1.01
1
1.02

3
0.43
2.35
1

Page 11

UNIQUAC5
4
5

1
1

1
1

1
1

1
1

1
1

ln(comb)
i(iij)

0.03

0.63

0.46

1.68

0.31

0.9

1.01

0.79

j/i(iij)

0.9

0.18

0.02

1.09
0.03

0.5
1.41

2.66
-2.94

1.09
-0.23

1.09
-0.13

j{jkj/(iiij)}
ln(resid)

ZOOM in to see subscripts clearly, the i's and j's look the same when the font is small.

Page 12

Antoine coefficients for: log10(Psat[mmHg])=A-B/(T[oC]+C)


T[oC]

100

A
B
C
tMin[oC]
tMax[oC]
Source
Psat[mmHg]

methanol ethanol
1-propanol 1-propanol 2-propanol 1-butanol
1-butanol
8.08
8.11
7.74
8.38
8.88
7.81
7.75
1582.27
1592.86
1437.69
1788.02 2010.33
1522.56
1506.07
239.73
226.18
198.46
227.44
252.64
191.95
191.59
15
20
60
-15
-26
30
70
84
93
106
98
83
70
120
3
3
3
3
2
2
2651.42
1693.83
845.66
828.54 1504.62
393.68
387.53

A
B
C
tMin[oC]
tMax[oC]
Source
Psat[mmHg]

methane ethane
propane
n-butane
n-pentane n-pentane
n-hexane
6.64
6.83
6.8
6.81
6.85
6.88
6.88
395.74
663.72
804
935.77 1064.84
1075.78
1171.17
266.68
256.68
247.04
238.79
232.01
233.21
224.41
-182
-143
-108
-78
-50
-50
-25
-158
-84
-35.65
19
58
58
92
5
5
5
5
5
3
5
### 92966.74 30665.09 11108.55
4423.1
4443.62
1844.31

A
B
C
tMin[oC]
tMax[oC]
Source
Psat[mmHg]

cyclohexane
cyclohexane methylcyclohexane
isopentane toluene
benzene
m-xylene
7.26
6.85
7.12
8.11
6.95
6.88
7.01
1434.15
1206.47
1444.59
1592.86 1342.31
1196.76
1462.27
246.72
223.14
240.18
226.18
219.19
219.16
215.11
6.7
7
-3
20
-27
8
29
80.7
81
100
93
111
80
166
1
3
1
3
3
3
1344.1
1311.69
740.63
1693.83
556.5
1349.47
233.67
water

A
B
C
tMin[oC]
tMax[oC]
Source
Psat[mmHg]

8.07
1730.63
233.43
1
100
3
760.09

acetonitrile Triethylamineacetic acid acetic acid chloroform dichloromethane


7.34
5.86
8.02
8.27
6.95
7.08
1482.29
695.67
1936.01 2258.22
1170.97
1138.91
250.52
144.83
258.45
300.97
226.23
231.45
-27
50
18
118
-10
-44
82
95
118
227
60
59
3
3
3
3
3
3
1291.41
1040.85
416.83
431.97
2318.91
4407.13

Source
1. Fit to data of D.R. Stull, in Perry's Chemical Engineers' Handbook, 5th ed, pg 3-46 to 3-62. Originally published Ind. Eng. Ch
2. Fit to data of Handbook of Chemistry and Physics, 56th ed., R.C. Weast, ed., CRC Press, 1974-75, pp D191-D210.
3. Gmehling, J., Vapor-liquid Equilibrium Data Collection, DECHEMA, Frankfort, Germany, 1977-.
5. TRC Thermodynamic Tables, Hydrocarbons, M. Frenkel, N.M. Gadalla, K.R. Hall, X. Hong, K.N. Marsh, R.C. Wilhoit, eds., T

1-butanol 2-butanol 1-octanol ethylene glycol


7.36
7.2
8.37
7.25
1305.2
1157 2170.24 1448.57
173.43
168.28
205.92
134.12
89
72
55
80
126
107
150
200
3
3
1
1
389.21
773.81
18.7
11.6
hexane
n-heptane heptane n-octane n-nonane n-decane decane
6.91
6.9
6.89
6.92
6.94
6.94
7.44
1189.64
1264.9 1264.37 1351.99 1431.82 1495.17 1843.12
226.28
216.54
216.64
209.16
202.11
193.86
230.22
-30
-2
-3
19
39
58
17
170
123
127
152
178
203
174
3
5
3
5
5
5
3
1838.69
795.79
795.75
351.16
158.32
71.71
72.2

o-xylene
7
1476.39
213.87
63
145
3
198.49

p-xylene acetone acetone acrolein ethyl acetate


1,4-dioxane2-butanone2-butanone
6.99
7.63
7.12
7.07
7.1
7.43
7.28
7.06
1453.43 1566.69
1210.6 1204.95 1244.95 1554.68
1434.2 1261.34
215.31
273.42
229.66
235.35
217.88
240.34
246.5
221.97
27
57
-13
-65
16
20
-6.5
43
166
205
55
53
76
105
80
88
3
3
3
3
3
3
1
3
240.44 2727.54 2785.68 2977.13 1532.45
730.29
1385.3 1399.53

dichoromethane
tetrachloromethane
1,2-dichloroethane
Benzyl chloride
nitroethaneBiphenyl Naphthalene
7.41
6.84
7.03
7.6
7.19
13.54
8.62
1325.94 1177.91 1271.25 1961.47 1446.51 4993.37 2165.72
252.62
220.58
222.93
236.51
220.79
296.07
198.28
-40
-20
-31
22
1.5
20
20
40
77
99
180
94
40
40
3
3
3
1
1 solid
4(solid)
4455.24 1467.49 1226.42
58.66
484.67
8.48
23

-62. Originally published Ind. Eng. Chem, 39, 517(1947).


ess, 1974-75, pp D191-D210.

ong, K.N. Marsh, R.C. Wilhoit, eds., Thermodynamics Research Center, Texas A&M University, College Station, TX, 1950-1997.

3-pentanone
7.23
1477.02
237.52
36
102
3
715.32

e Station, TX, 1950-1997.

UNIFAC (VLE)

Instructions: Type the temperature of interest in centigrade. Then enter the number
of occurences of each functional group in each component.
Further instructions are given in comment boxes. Use ViewCommentto show or hide them.

As distributed, this cell has


a formula to calculate the
P=
745.52 mmHg
bubble pressure.
T(oC)=
80.37 oC
Table 1. Antoine Coefficients (mmHg) log10(Psat)=A-B/(T+C) where T[=] oC
A
B
C
Psat[mmHg]
yi

comp1
8.88
2010.33
252.64
694.02

comp2
8.07
1730.63
233.43
359.89

0.58963

0.41037

comp3

comp4
8.11
1592.86
226.18
824.46

comp5
6.88
1075.78
233.21
2790.14

0.00000 0.00000

0.00000

Enter Antoine constants or


vapor pressures if you
want bubble P and vapor
phase concentrations
calculated automatically.

Table 2. Component Structure Information and Activity Coefficient Calculation.

SubGroup

comp1

comp2

comp3

comp4

comp5

IPA

Water

C2-COOH

EtOH

C5H12

xi

0.500

0.500

0.000

0.000

0.000

1.267

1.700

0.980

1.107

12.607

CH3

2
3
9
10
11
12
14
15

CH2
CH
ACH
AC
ACCH3
ACCH2
OH
CH3OH

16

H2O

17

ACOH

18

CH3CO

20

CHO

21

CH3COO

29

CH2NH2

36

ACNH2

42

COOH

49

CCL2

51

CCL3

99

CON(CH2)2

2
1

Vapor phase mole fractions


calculated automatically.

Liquid phase mole fractions. Enter a very small number like 1E-20
or smaller for absent compounds - don't use zero.
Enter the number of occurences of a chemical structure in
this table for each component. Residual group interaction
parameters are not available for all groups, and are
treated as zero if unavailable. Check Table 1 on sheet
"aij-UNIFAC (VLE)".
The sub-groups available in this table may be
changed in this column by changing the SubGroup
number. If you change a sub-group here, be sure to
edit the component structure information in the table.
Available subgroups and subgroup numbers are in
Table 2 of sheet "aij-UNIFAC (VLE)".

kk(i)xi

0.5

N groups

3.1240

1.4000

2.6120

2.5880

3.3160

3.2491

0.9200

2.8768

2.5755

3.8254

0.6905

0.3095

0.0000

0.0000

0.0000

0.7793

0.2207

0.0000

0.0000

0.0000

lnC

0.0042

0.0994

0.1625

0.0152

0.2233

lnRo

1.3197

0.0000

1.1812

1.0915

0.0000

lnR

1.5520

0.4313

0.9983

1.1784

2.3110

Note that columns H:AS are hidden.


They contain intermediate
calculations. Unprotect the sheet
and unhide them to see the
calculations.

Page 16

aij-UNIFAC (VLE)
Parameters from "Chemical Engineering Thermodynamics", Y.V.C. Rao,
Sangam Books, London, 1997.
Table 1. Residual Group Interaction Parameters for Main Groups.
For a new main group, carefully replace all entries for the row and column associated with the new group. You must unprotect
the sheet, and then change only the values in blue. See Table 2 on this sheet for subgroup parameters.
(The chemical structures for the main groups listed here are shown in Table 2 below).
NOTE: BLANK CELLS MEAN THE VALUE IS UNAVAILABLE AND A VALUE OF ZERO IS USED IN CALCULATIONS.
1
2
3
4
5
6
7
8
1
0
86.02
61.13
76.5
986.5
697.2
1318
1333
2
-35.36
0
38.81
74.15
524.1
787.6
270.6
526.1
3
-11.12
3.45
0
167
636.1
637.3
903.8
1329
4
-69.7
-113.6
-146.8
0
803.2
603.2
5695
884.9
5
156.4
457
89.6
25.82
0
-137.1
353.5
-259.7
6
16.51
-12.52
-50
-44.5
249.1
0
-181
-101.7
7
300
496.1
362.3
377.6
-229.1
289.6
0
324.5
8
275.8
217.5
25.34
244.2
-451.6
-265.2
-601.8
0
9
26.76
42.92
140.1
365.8
164.5
108.7
472.5
-133.1
10
505.7
56.3
23.39
106
529
-340.2
480.8
-155.6
11
114.8
132.1
85.84
-170
245.4
249.6
200.8
-36.72
14
-30.48
1.16
-44.85
296.4
-242.8
-481.7
-330.4
17
1139
2000
247.5
762.8
-17.4
-118.1
-341.6
-253.1
20
315.3
1264
62.32
89.96
-151
339.8
-66.17
-11
22
34.1
-23.5
121.3
140.8
527.6
669.9
708.7
23
36.7
51.06
228.5
69.9
742.1
649.1
826.8
46
27.97
9.76
394.8
-509.3

Table 2. Sub-group Surface and Volume Parameters.


All sub-groups within a main group use the same residual group interaction parameters from Table 1.
To add a new sub-group, unprotect the sheet and overwrite one of the existing rows unless you want to reprogram. If the new
sub-group belongs to a main group that is not already listed, a row and column in Table 1 will also need to be changed.
SubGroup

MainGroup
1
2
3
4

R
1 CH3
1 CH2
1 CH
1C

Q
0.9
0.67
0.45
0.22

0.85
0.54
0.23
0

Page 17

9
476.4
182.6
25.77
-52.1
84
23.39
-195.4
-356.1
0
128
372.2

10
677
448.8
347.3
586.6
-203.6
306.4
-116
-271.1
-37.36
0
185.1

-450.3
-297.8
82.86
552.1

-165.5
190.6
242.8

aij-UNIFAC (VLE)
5
6
7
8
70
9
10
11
12
13
14
15
16
17
18
19
20
21
22
29
36
42
49
51
99

2 CH2=CH
2 CH=CH
2 CH2=C
2 CH=C
2 C=C
3 ACH
3 AC
4 ACCH3
4 ACCH2
4 ACCH
5 OH
6 CH3OH
7 H2O
8 ACOH
9 CH3CO
9 CH2CO
10 CHO
11 CH3COO
11 CH2COO
14 CH2NH2
17 ACNH2
20 COOH
22 CCL2
23 CCL3
46 CON(CH2)2

1.35
1.12
1.12
0.89
0.66
0.53
0.37
1.27
1.04
0.81
1
1.43
0.92
0.9
1.67
1.45
1
1.9
1.68
1.37
1.06
1.3
1.8
2.64
2.41

1.18
0.87
0.99
0.68
0.49
0.4
0.12
0.97
0.66
0.35
1.2
1.43
1.4
0.68
1.49
1.18
0.95
1.73
1.42
1.24
0.82
1.22
1.45
2.18
1.81

Page 18

aij-UNIFAC (VLE)

Table 3. Interaction Parameters to be used in the calculations


Do not edit this table unless you want to reprogram. Change va
T=

11
232.1
37.85
5.99
5688
101.1
-10.72
72.87
-449.4
-213.7
-110.3
0
-294.8
-256.3
-133
176.5

14
391.5
240.9
161.7
19.02
8.64
359.3
48.89

0
-15.07

17
920.7
749.3
648.2
664.2
-52.39
489.7
243.2
119.9
6201
475.5
-200.7
0
493.8
140.8

20
663.5
318.9
537.4
872.3
199
-202
-14.09
408.9
669.4
497.5
660.2

22
53.76
58.55
-144.4
-111
65.28
-102.5
370.4

23
24.9
-13.99
-231.9
-80.25
-98.12
-139.4
353.7

-130.3
67.52
108.9

-354.6
-483.7
-209.7

-396
0
543.3
504.2
-70.25

-111
-44.7
0
-84.53

39.63
0
0

46
380.9
200.2

-382.7
835.6

-322.3

80.37 C

Sub Main
Group Group
1
1
2
1
3
1
9
3
10
3
11
4
12
4
14
5
15
6
16
7
17
8
18
9
20
10
21
11
29
14
36
17
42
20
49
22
51
23
99
46

R
CH3
CH2
CH
ACH
AC
ACCH3
ACCH2
OH
CH3OH
H2O
ACOH
CH3CO
CHO
CH3COO
CH2NH2
ACNH2
COOH
CCL2
CCL3
CON(CH2)2

0.9
0.67
0.45
0.53
0.37
1.27
1.04
1
1.43
0.92
0.9
1.67
1
1.9
1.37
1.06
1.3
1.8
2.64
2.41

Table 4. Matrix of values used in calculations


Do not edit this table unless you want to reprogr

CH3
CH3
1
CH2
1
CH
1

Page 19

aij-UNIFAC (VLE)
ACH
AC
ACCH3
ACCH2
OH
CH3OH
H2O
ACOH
CH3CO
CHO
CH3COO
CH2NH2
ACNH2
COOH
CCL2
CCL3
CON(CH2)2

Page 20

1.03
1.03
1.22
1.22
0.64
0.95
0.43
0.46
0.93
0.24
0.72
1.09
0.04
0.41
0.91
0.9
0.92

aij-UNIFAC (VLE)

ers to be used in the calculations for the selected groups as indicated on sheet "UNIFAC (VLE)".
you want to reprogram. Change values in Tables 1 and 2 unless you want to reprogram.

aij (i=column, j=row)


1
1
Q
CH3
CH2
0.85
0
0
0.54
0
0
0.23
0
0
0.4
-11.12
-11.12
0.12
-11.12
-11.12
0.97
-69.7
-69.7
0.66
-69.7
-69.7
1.2
156.4
156.4
1.43
16.51
16.51
1.4
300
300
0.68
275.8
275.8
1.49
26.76
26.76
0.95
505.7
505.7
1.73
114.8
114.8
1.24
-30.48
-30.48
0.82
1139
1139
1.22
315.3
315.3
1.45
34.1
34.1
2.18
36.7
36.7
1.81
27.97
27.97

1
CH
0
0
0
-11.12
-11.12
-69.7
-69.7
156.4
16.51
300
275.8
26.76
505.7
114.8
-30.48
1139
315.3
34.1
36.7
27.97

3
ACH
61.13
61.13
61.13
0
0
-146.8
-146.8
89.6
-50
362.3
25.34
140.1
23.39
85.84
-44.85
247.5
62.32
121.3
228.5
0

3
AC
61.13
61.13
61.13
0
0
-146.8
-146.8
89.6
-50
362.3
25.34
140.1
23.39
85.84
-44.85
247.5
62.32
121.3
228.5
0

4
ACCH3
76.5
76.5
76.5
167
167
0
0
25.82
-44.5
377.6
244.2
365.8
106
-170
296.4
762.8
89.96
140.8
69.9
0

4
ACCH2
76.5
76.5
76.5
167
167
0
0
25.82
-44.5
377.6
244.2
365.8
106
-170
296.4
762.8
89.96
140.8
69.9
0

5
OH
986.5
986.5
986.5
636.1
636.1
803.2
803.2
0
249.1
-229.1
-451.6
164.5
529
245.4
-242.8
-17.4
-151
527.6
742.1
394.8

6
CH3OH
697.2
697.2
697.2
637.3
637.3
603.2
603.2
-137.1
0
289.6
-265.2
108.7
-340.2
249.6
-481.7
-118.1
339.8
669.9
649.1
0

7
H2O
1318
1318
1318
903.8
903.8
5695
5695
353.5
-181
0
-601.8
472.5
480.8
200.8
-330.4
-341.6
-66.17
708.7
826.8
-509.3

x of values used in calculations on sheet "UNIFAC (VLE).


s table unless you want to reprogram. Change values in Tables 1 and 2 unless you want to reprogram.
CH2

CH
1
1
1

ACH
1
1
1

AC
0.84
0.84
0.84

ACCH3
0.84
0.84
0.84

ACCH2
0.81
0.81
0.81

OH
0.81
0.81
0.81

Page 21

CH3OH
0.06
0.06
0.06

H2O
0.14
0.14
0.14

ACOH
0.02
0.02
0.02

CH3CO
0.02
0.02
0.02

0.26
0.26
0.26

aij-UNIFAC (VLE)
1.03
1.03
1.22
1.22
0.64
0.95
0.43
0.46
0.93
0.24
0.72
1.09
0.04
0.41
0.91
0.9
0.92

1.03
1.03
1.22
1.22
0.64
0.95
0.43
0.46
0.93
0.24
0.72
1.09
0.04
0.41
0.91
0.9
0.92

1
1
1.51
1.51
0.78
1.15
0.36
0.93
0.67
0.94
0.78
1.14
0.5
0.84
0.71
0.52
1

1
1
1.51
1.51
0.78
1.15
0.36
0.93
0.67
0.94
0.78
1.14
0.5
0.84
0.71
0.52
1

0.62
0.62
1
1
0.93
1.13
0.34
0.5
0.36
0.74
1.62
0.43
0.12
0.78
0.67
0.82
1

0.62
0.62
1
1
0.93
1.13
0.34
0.5
0.36
0.74
1.62
0.43
0.12
0.78
0.67
0.82
1

Page 22

0.17
0.17
0.1
0.1
1
0.49
1.91
3.59
0.63
0.22
0.5
1.99
1.05
1.53
0.22
0.12
0.33

0.16
0.16
0.18
0.18
1.47
1
0.44
2.12
0.74
2.62
0.49
3.91
1.4
0.38
0.15
0.16
1

0.08
0.08
0
0
0.37
1.67
1
5.49
0.26
0.26
0.57
2.55
2.63
1.21
0.13
0.1
4.22

0.02
0.02
0.08
0.08
2.08
1.33
0.4
1
1.46
1.55
1.11
1
2.05
1.03
1
1
1

0.93
0.93
1.16
1.16
0.79
0.94
1.74
2.74
1
0.7
0.35
1
3.57
2.32
0.79
0.21
1

aij-UNIFAC (VLE)

8
ACOH
1333
1333
1333
1329
1329
884.9
884.9
-259.7
-101.7
324.5
0
-133.1
-155.6
-36.72
0
-253.1
-11
0
0
0

CHO
0.15
0.15
0.15

9
CH3CO
476.4
476.4
476.4
25.77
25.77
-52.1
-52.1
84
23.39
-195.4
-356.1
0
128
372.2
0
-450.3
-297.8
82.86
552.1
0

10
CHO
677
677
677
347.3
347.3
586.6
586.6
-203.6
306.4
-116
-271.1
-37.36
0
185.1
0
0
-165.5
190.6
242.8
0

11
CH3COO
232.1
232.1
232.1
5.99
5.99
5688
5688
101.1
-10.72
72.87
-449.4
-213.7
-110.3
0
0
-294.8
-256.3
-133
176.5
0

14
CH2NH2
391.5
391.5
391.5
161.7
161.7
19.02
19.02
8.64
359.3
48.89
0
0
0
0
0
-15.07
0
0
0
0

17
ACNH2
920.7
920.7
920.7
648.2
648.2
664.2
664.2
-52.39
489.7
243.2
119.9
6201
0
475.5
-200.7
0
493.8
140.8
0
0

CH3COO
CH2NH2
ACNH2
COOH
CCL2
0.52
0.33
0.07
0.15
0.52
0.33
0.07
0.15
0.52
0.33
0.07
0.15

20
COOH
663.5
663.5
663.5
537.4
537.4
872.3
872.3
199
-202
-14.09
408.9
669.4
497.5
660.2
0
-396
0
543.3
504.2
-70.25

CCL3
0.86
0.86
0.86

Page 23

0.93
0.93
0.93

22
CCL2
53.76
53.76
53.76
-144.4
-144.4
-111
-111
65.28
-102.5
370.4
0
-130.3
67.52
108.9
0
-111
-44.7
0
-84.53
0

CON(CH2)2
0.34
0.34
0.34

23
46
CCL3
CON(CH2)2
24.9
380.9 CH3
24.9
380.9 CH2
24.9
380.9 CH
-231.9
0 ACH
-231.9
0 AC
-80.25
0 ACCH3
-80.25
0 ACCH2
-98.12
-382.7 OH
-139.4
0 CH3OH
353.7
835.6 H2O
0
0 ACOH
-354.6
0 CH3CO
-483.7
0 CHO
-209.7
0 CH3COO
0
0 CH2NH2
0
0 ACNH2
39.63
-322.3 COOH
0
0 CCL2
0
0 CCL3
0
0 CON(CH2)2

aij-UNIFAC (VLE)
0.37
0.37
0.19
0.19
1.78
0.42
1.39
2.15
1.11
1
0.59
1
1
1.6
0.58
0.5
1

0.98
0.98
0
0
0.75
1.03
0.81
3.57
1.83
1.37
1
1
2.3
2.06
1.46
0.61
1

0.63
0.63
0.95
0.95
0.98
0.36
0.87
1
1
1
1
1
1.04
1
1
1
1

0.16
0.16
0.15
0.15
1.16
0.25
0.5
0.71
0
1
0.26
1.76
1
0.25
0.67
1
1

0.22
0.22
0.08
0.08
0.57
1.77
1.04
0.31
0.15
0.24
0.15
1
3.07
1
0.22
0.24
1.22

1.5
1.5
1.37
1.37
0.83
1.34
0.35
1
1.45
0.83
0.73
1
1.37
1.13
1
1.27
1

Page 24

1.93
1.93
1.25
1.25
1.32
1.48
0.37
1
2.73
3.93
1.81
1
1
0.89
1
1
1

1
1
1
1
2.95
1
0.09
1
1
1
1
1
1
2.49
1
1
1

UNIFAC (LLEa)

Liquid-liquid calculation using UNIFAC LLE. Sheet for first liquid phase. See also "UNIFAC (LLEb)".
Instructions: Type the temperature of interest in centigrade. Then enter the number
of occurences of each functional group in each component. If you have less than 5
components, type a samll number like 1E-20 for the mole fractions of the absent components. If you want
the pressure to be computed automatically, you must enter the Antoine coefficients of
the components. To use different functional groups than those provided,
follow the instructions on the aij-UNIFAC sheet.
This sheet does not yet have the
cabability for specification of other
functional groups without editing "aijUNIFAC (LLE)". That will be provided
in the future.

Note: hidden
<P=
86.45 mmHg columns with ->
intermediate calcs
T(oC)=
25 oC
Antoine Coefficients (mmHg) log10(Psat)=A-B/(T+C) where T[=] oC
A
B
C
Psat[mmHg]
yi

x
i

comp1
8.07
1730.63
233.43
23.69

comp2
7.28
1434.2
246.5
99.57

0.26079

0.73763

comp3

comp4

comp5

Note: MeOH is not a unique group in the citation used to


develop this sheet.
T. Magnussen, P. Rasmussen, A. Fredenslund,
Ind. Eng. Chem. Process Des. Dev., 1981, 20, 331-339.

0.00158 0.00000

0.00000

phase

comp4

comp5

Table for LLE as described in text.

Water

MEK

c2-COOH

EtOH

C5H12

Can be used for binary or ternary.

0.830

0.100

0.070

0.000

0.000

1.147

6.414

1.951

1.705

199.114

Follow text instructions to create macro

CH3

Ki,old

CH2

Ki,new

CH

xi,old

ACH

xi,new

ACCH2

xi,old

ACCH3
OH
2-Propanol
H2O

xi,new
1
1

To avoid having the screen jump to follow the

ACOH

cursor during macro execution, just hide ALL

CH3CO

of the columns that contain the activity coefficient

CHO

calculations before executing the macro.

COOH

CH3COO
CH2O
CHCL2
CCL3
ACNH2
kk(i)xi

0.83

0.3

0.21

1.4000

2.8760

2.6120

2.5880

3.3160

0.9200

3.2479

2.8768

2.5755

3.8254

0.7120

0.1759

0.1120

0.0000

0.0000

0.5923

0.2515

0.1562

0.0000

0.0000

lnC

0.0606

0.4430

0.3795

0.0676

0.4747

lnRo

0.0000

0.8719

1.1448

1.2862

0.0000

lnR

0.0761

2.2874

1.4339

1.7522

4.8192

N groups

Page 25

UNIFAC (LLEb)

Second liquid phase for LLE calculations.


This sheet should be used in conjunction with "UNIFAC (LLEa)".
The liquid phase mole fractions are the only variables that should be changed on this sheet.
All component information is entered on "UNIFAC (LLEa)" and replicated here automatically.

Note: hidden
<P=
85.6 mmHg columns with ->
intermediate calcs
T(oC)=
25 oC
Antoine Coefficients (mmHg) log10(Psat)=A-B/(T+C) where T[=] oC
A
B
C
Psat[mmHg]
yi

x
i
CH3
CH2
CH
ACH
ACCH2
ACCH3
OH
2-Propanol
H2O

comp1
8.07
1730.63
233.43
23.69
0.26079

comp2
7.28
1434.2
246.5
99.57
0.73763

comp3

comp4
0
0
0
1

comp5
0
0
0
1

0.00158 0.00000

0
0
0
1
0.00000

comp1

comp2

comp3

comp4

comp5

Water

MEK

c2-COOH

EtOH

C5H12

0.773

0.139

0.088

0.000

0.000

1.235
0
0
0
0
0
0
0
0
1

4.541
1
1
0
0
0
0
0
0
0

1.535
1
1
0
0
0
0
0
0
0

1.396
1
1
0
0
0
0
1
0
0

104.701
2
3
0
0
0
0
0
0
0

ACOH

CH3CO

CHO

COOH

CH3COO

CH2O

CHCL2

CCL3

ACNH2

0.77

0.42

0.26

1.4000

2.8760

2.6120

2.5880

3.3160

0.9200

3.2479

2.8768

2.5755

3.8254

0.6321

0.2335

0.1344

0.0000

0.0000

0.5022

0.3188

0.1790

0.0000

0.0000

lnC

0.0909

0.3122

0.2677

0.0150

0.3208

lnRo

0.0000

0.8719

1.1448

1.2862

0.0000

lnR

0.1204

2.0730

1.3059

1.6049

4.3303

kk(i)xi
N groups

phase

Page 26

aij-UNIFAC (LLE)

These parameters are used for the spreadsheet UNIFAC (LLE)


To change functional groups, trade for one of the functional groups listed unless you want to reprogram.
If you want to use a different subgroup, you may just change the R and Q parameters, and leave the aijmatrix.
For a new main group, carefully replace all entries for the row and column associated with the new group. You must unprotect
the sheet, and then change only the values in blue.
Parameters from T. Magnussen, P. Rasmussen, A. Fredenslund,
T=
25 C
Ind. Eng. Chem. Process Des. Dev., 1981, 20, 331-339.

aij (i=column, j=row)


Main
Group

1
R

CH3

0
CH2

NOTE: Blank cells mean value is unavailable

0
CH

3
ACH

4
ACCH2

0
ACCH3

OH 2-Propanol H2O

9
ACOH

10
CH3CO

11
CHO

13

14

15

COOH CH3COO CH2O

1 CH3

0.9

0.85

-114.8

-115.7

-115.7 644.6

310.7

1300

2255

472.6 158.1

139.4

972.4

662.1

CH2

0.67

0.54

-114.8

-115.7

-115.7 644.6

310.7

1300

2255

472.6 158.1

139.4

972.4

662.1

CH

0.45

0.23

3 ACH
4 ACCH2
ACCH3

5 OH
7 2-Propanol
8 H2O
9 ACOH
10 CH3CO
11 CHO
13 COOH
14 CH3COO
15 CH2O
17 CHCL2
18 CCL3
22 ACNH2

-114.8

-115.7

-115.7 644.6

310.7

1300

2255

472.6 158.1

139.4

972.4

662.1

0.53

0.4 156.5

156.5

156.5

167

167 703.9

577.3

859.4

1649

593.7 362.3

461.8

32.14

1.04

0.66 104.4

104.4

104.4

-146.8

5695

292.6

916.7

1218

339.1

5688

213.1

1.27

0.97 104.4

104.4

104.4

-146.8

1.2 328.2

328.2

328.2

-9.21

3.12 -131.9 -131.9

-131.9

-252

-273.6

3.25
0.92

1.4 342.4

0.9

4000

906.8

4000

906.8

5695

292.6

916.7

1218

339.1

5688

213.1

1.27

1.27

991.3

28.73 -195.5

67.07

1409

-104

195.6

262.5

-273.6 -268.8

5.89 -153.2

353.8 -338.6 -57.98

487.1

1970

-6.32

64.42

342.4

342.4

372.8

203.7

203.7 -122.4

104.9

344.5

0.68 -159.8 -159.8

-159.8

-473.2

-470.4

-470.4 -63.15

-547.2

-595.9

-78.31

-73.87

-73.87

216

-127.6

634.8

-568

1.67

1.49 66.56

66.56

66.56

-171.8 -349.9 -465.7


-825.7

-898.3

0 -37.36

1247

258.7
-245.8

5.2

0.95 146.1

146.1

146.1

-75.3

223.2

223.2 -431.3

231.4

623.7

128

0.75

1.3

1.22

1744

1744

75.49

147.3

147.3 118.4

349.1

652.3

-101.3

1051

-117.6 -96.62

1.9

1.73 -320.1 -320.1

-320.1

114.8

-170

-170 180.6

-152.8

385.9 -337.3

58.84

1090

1417

0 -235.7

52.13

65.69

65.69 137.1

-218.1

212.8

52.38

1402

669.2

-401.6

740.4

550.6

437.7

-132.9 -197.7

33.61 418.4

-465.7

793.2

-825.7

370.4

-898.3 -20.93

857.7

681.4

1744

0.92

0.78

1571

1571

1571

2.06

1.68

27.9

27.9

27.9

2.64

2.18 21.23

21.23

21.23

288.5

33.61

1.06

0.82 175.8

175.8

175.8

-218.9

-15.41

-15.41

529

-239.8 -860.3

461.3

CH3

CH2

CH

ACH

ACCH2 ACCH3

OH

2-Propanol
H2O

ACOH CH3CO

CHO

COOH CH3COO CH2O

CH3

1.47

1.47

1.47

0.12

0.35

0.01

0.2

0.59

0.63

0.04

0.11

CH2

1.47

1.47

1.47

0.12

0.35

0.01

0.2

0.59

0.63

0.04

0.11

Page 27

aij-UNIFAC (LLE)

CH
ACH
ACCH2
ACCH3

1.47

1.47

1.47

0.12

0.35

0.01

0.2

0.59

0.63

0.04

0.11

0.59

0.59

0.59

0.57

0.57

0.09

0.14

0.06

0.14

0.3

0.21

0.98

0.9

0.7

0.7

0.7

1.64

0.05

0.37

0.05

0.02

0.32

0.49

0.7

0.7

0.7

1.64

0.05

0.37

0.05

0.02

0.32

0.49

OH

0.33

0.33

0.33

1.03

0.04

0.91

1.93

0.8

0.01

1.42

0.52

0.41

2-Propanol

1.56

1.56

1.56

2.33

2.5

2.5

2.46

0.98

1.67

0.31

3.11

1.21

0.2

H2O

0.32

0.32

0.32

0.29

0.5

0.5

1.51

0.7

0.31

1.78

3.23

4.77

1.02

0.81

ACOH

1.71

1.71

1.71

4.89

4.84

4.84

1.24

6.27

7.38

15.95

20.35

0.8

0.8

0.8

1.3

1.28

1.28

0.48

1.53

0.12

6.72

1.13

0.02

0.42

0.98

0.61

0.61

0.61

1.29

0.47

0.47

4.25

0.46

0.12

0.65

2.28

0.78

0.61

0.61

0.67

0.31

0.11

1.4

0.03

1.48

1.38

CH3COO

2.93

2.93

2.93

0.68

1.77

1.77

0.55

1.67

0.27

3.1

0.82

0.03

0.01

2.2

CH2O

0.01

0.01

0.01

0.84

0.8

0.8

0.63

2.08

0.49

0.84

0.01

0.21

CHCL2

0.91

0.91

0.91

0.11

3.85

0.08

0.16

0.23

1.56

1.94

CCL3

0.93

0.93

0.93

0.38

0.89

0.89

0.25

4.77

0.07

15.95

0.29

20.35

1.07

ACNH2

0.55

0.55

0.55

2.08

1.05

1.05

0.17

2.24

17.91

0.06

0.1

CH3CO
CHO
COOH

Page 28

aij-UNIFAC (LLE)

17

18

CHCL2 CCL3

22
ACNH2

-243.9

7.5

902.2 CH3

-243.9

7.5

902.2 CH2

7.5

902.2 CH

-243.9

-231.9
-12.14
-12.14
272.2 -61.57
507.8

1544

370.7

356.8

1.64 ACH
689.6 ACCH2
689.6 ACCH3
-348.2 OH
2-Propanol
-109.8 H2O
-851.6 ACOH

-301

12.01

1010 CH3CO

1670

48.15

942.2 COOH

CHO

108.9 -209.7

CH3COO

137.8 -154.3

CH2O

CHCL2
0

-75.5 CCL3

-216.3

CHCL2 CCL3

0 ACNH2

ACNH2

2.27

0.98

0.05

2.27

0.98

0.05

Page 29

aij-UNIFAC (LLE)

2.27

0.98

0.05

2.18

0.99

1.04

0.1

1.04

0.1

0.4

1.23

3.22

0.18

0.01

0.29

0.3

1.45

17.4

2.74

0.96

0.03

0.85

0.04

0.69

2.02

0.63

1.68

1.29

2.07

Page 30

LLE
Water(1)+mek(2) at 298K by UNIFAC (cf Arce, JCEDat,40:226)
Summary of calculations for Example in Textbook
w
mek
w*xw
mek*xmek
x1 Gmix/RT
0.00
0 23.55
1
0
1
0.05
-0.06 12.21
1.02
0.61
0.97
0.10
-0.07
7.89
1.05
0.79
0.95
0.15
-0.08
5.75
1.1
0.86
0.93
0.20
-0.08
4.52
1.16
0.9
0.93
0.25
-0.08
3.73
1.22
0.93
0.92
0.30
-0.08
3.18
1.3
0.95
0.91
0.35
-0.08
2.78
1.39
0.97
0.9
0.40
-0.07
2.47
1.49
0.99
0.89
0.45
-0.07
2.22
1.61
1
0.89
0.50
-0.06
2.01
1.76
1.01
0.88
0.55
-0.05
1.84
1.95
1.01
0.88
0.60
-0.05
1.68
2.19
1.01
0.88
0.65
-0.04
1.55
2.51
1.01
0.88
0.70
-0.03
1.43
2.97
1
0.89
0.75
-0.03
1.32
3.66
0.99
0.91
0.80
-0.03
1.23
4.74
0.98
0.95
0.85
-0.03
1.14
6.64
0.97
1
0.90
-0.03
1.07 10.36
0.97
1.04
0.95
-0.03
1.02 19.09
0.97
0.95
1.00
0
1 45.76
1
0

Coexistence calculation
@x1~0.35

Gm/RT

-0.05
-0.1
-0.15
-0.2
-0.25
0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

xw
1.2
1

xigi

0.8
0.6
0.4
0.2

Page 31

0.80

0.90

1.00

0.8
xigi

LLE

0.6
0.4
0.2
0
0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

xw

Page 32

0.80

0.90

1.00