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

81464827.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
1
0.95
0.92
0.89
0.87
0.85
0.83
0.82
0.81
0.81
0.8
0.78
0.77
0.75
0.71
0.67
0.6
0.51
0.39
0.22
0

G(mix) /RT
0
-0.11
-0.16
-0.19
-0.21
-0.22
-0.23
-0.24
-0.25
-0.25
-0.26
-0.26
-0.26
-0.26
-0.25
-0.24
-0.23
-0.21
-0.18
-0.12
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)
Antoine Coeff
A
B
C
VL (cm3/mol)
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
y1

0
0.27
T (C)
80.1
70.67
Calculations based on data
T(K)
353.25
343.82
1
0
0.01

0.37
66.44

0.46
62.87

0.53
60.2

0.56
58.64

0.6
58.02

0.63
58.1

339.59

336.02

333.35

331.79

331.17

331.25

0.02

0.04

0.08

0.18

0.36

0.51

0.15

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

4.96

4.9

4.81

4.63

4.19

3.44

3.15

2.05

1.51

1.01

1.03

1.09

1.14

1.62

2.73

1360.42 1106.07

952.14

793.18

624.1

515.24

495.45

476.6

481.26

P1sat
P2sat

760

635.42

558.01

476.14

386.43

326.88

315.88

305.35

307.95

y1 calc

0.19

0.3

0.42

0.56

0.66

0.68

0.71

0.67

y2 calc

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

T(K)
(yi-1)2

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
1
3
2.95
2.9
2.81
2.62
2.3

0.33

0.55

0.7

2.16

1.62

1.32

2
P1sat

-0.03

1.02

1.06

1.09

1.39

1.97

1360.42 1206.11 1097.85

970.38

809.73

680.29

650.46

593.28

588.08

P2sat

760

684.87

631.32

567.28

484.77

416.59

400.63

369.73

366.9

y1 calc

0.12

0.21

0.32

0.46

0.58

0.62

0.7

0.71

y2 calc

0.88

0.79

0.68

0.54

0.42

0.38

0.3

0.29

Page 3

Regular
T(K)
(yi-1)2

353.25

349.9

347.34

344.04

339.32

334.91

333.79

331.53

331.32

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
P2sat

368.65

A21

2.06

1.74

First, set this to 331.3

azeotrope T and comp
then adjust kij until ce
0.

These values are calculated from the activi

coefficient and composition values at the a

x1

0.03

0.05

0.09

0.16

0.28

0.33

0.55

0.7

7.28

6.48

5.85

5.01

3.77

2.56

2.24

1.42

1.16

1.01

1.02

1.06

1.18

1.26

1.8

2.5

1360.42 1035.63

885.79

759.29

653.48

605.46

599.37

591.84

593.21

P1sat
P2sat

760

600.2

524.1

458.4

402.25

376.35

373.04

368.95

369.69

y1 calc

0.23

0.34

0.44

0.53

0.58

0.59

0.61

0.63

y2 calc

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

T(K)
(yi-1)2

Page 4

Regular

(cal/cm3)1/2

0.78

0.9

0.67
58.47

0.97

0.97

0.76
59.9

0.91
62.7

1
64.7

331.62

333.05

335.85

337.85

0.62

0.8

0.94

0.94

360
0.9

0.97

0.97

1.28

1.07

1.01

1.01

4.33

11.65

29.02

29.01

39.8

471.9

438.82

515.2

515.06

759.99

302.71

284.05

326.86

326.79

458.77

0.62

0.56

0.66

0.66

0.38
326.05

0.44
324.35

0.34
328.13

0.34
328.12

0
|

E region --->

350
340

T(K)

0.78

320
310

0
337.7 OBJ
0

330

300
-0.2

Bubble temperatures can be

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

0.2

0.4
x-y

0.6

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.

355

0.78

0.9

0.97

0.97

1.18

1.05

350

2.69

5.19

9.64

9.63

12.5

345

588.26

598.28

668.77

668.69

759.99

367

372.45

410.43

410.4

458.77

0.72

0.74

0.86

0.86

0.28

0.26

0.14

0.14

T(K)

340
335
330
325
Page 5

320
-0.2

0.2

0.4
x-y

0.6

345

Regular

T(K)

340
335
330
331.32

331.74

334.48

334.48

First, set this to 331.3 (close to

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

337.7 OBJ
0

325

320
-0.2

Then, use Solver to adjust

B47:O47 to calc bubble T's.

0.2

0.2

0.4
x-y

0.6

0.4

0.6

values are calculated from the activitiy

cient and composition values at the azeotrope.

0.9

0.97

0.97

355

1.08

1.02

350

3.08

4.22

5.26

5.26

5.71

345

602.28

644.91

716.65

716.61

759.99

340

374.62

397.65

435.92

435.89

458.77

0.67

0.77

0.92

0.92

330

0.33
331.9

0.23
333.58

0.08
336.21

0.08
336.21

0
337.7 OBJ

325

T(K)

0.78

After determining the A12 and A21, the

bubble temperatures are calculated across
the composition range as before.

Page 6

335

320
-0.2

x-y

.2

Regular

0.4
x-y

0.6

0.8

bove diagram are indicative

sent experimental data.
r is necessary to fit the data

0.2

0.4
x-y

0.6

0.8

Page 7

0.2

.2

Regular

0.4
x-y

0.6

0.8

0.4

0.6

0.8

x-y

Page 8

UNIQUAC
UNIQUAC Calculation

Note: This spreadsheet uses the form of equations that permits the q of the residual part
of the combinatorial part. (Anderson, T.F., Prausnitz, J.,M., Ind. Eng. Chem. Process De
The formulas look a little different because or the use of the intermediate variable 'l', how
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

Page 9

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

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

ts the q of the residual part to differ from q

d. Eng. Chem. Process Des. Dev. 17, 1978, 552-561).
ntermediate variable 'l', however the equations

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)
1.96
1.71
1.49
1.29
1.12
0.97
0.83
0.71
0.6
0.5
0.41
0.33
0.26
0.2
0.15
0.11
0.07
0.04
0.02
0
0

ln(gam2)
0
0.01
0.02
0.05
0.09
0.13
0.19
0.24
0.31
0.38
0.46
0.55
0.64
0.74
0.85
0.97
1.1
1.24
1.39
1.55
1.73

Page 10

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

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
298.15 Phase

T (K) =

1
Name

Water

x
r
q

ixiri

2
MEK

Acetic

8.91E-01

9.89E-02

1.00E-02

1.00E-11

1.00E-11

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

4
0
0
0
1
0

5
0
0
0
0
1

4
1

5
1

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
ij matrix (i = row, j=column)
1

1
1

2
1.01

3
0.43

Page 11

UNIQUAC5
2
3
4
5

0.31
2.74
1
1

1
1.02
1
1

2.35
1
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
366903.01
92966.74
30665.09
11108.55
4423.1
4443.62
1844.31

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

cyclohexanecyclohexane 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
6.91
1189.64
226.28
-30
170
3
1838.69

o-xylene
7
1476.39
213.87
63
145
3
198.49

n-heptane heptane
n-octane
n-nonane n-decane decane
6.9
6.89
6.92
6.94
6.94
7.44
1264.9
1264.37
1351.99
1431.82
1495.17
1843.12
216.54
216.64
209.16
202.11
193.86
230.22
-2
-3
19
39
58
17
123
127
152
178
203
174
5
3
5
5
5
3
795.79
795.75
351.16
158.32
71.71
72.2

p-xylene
acetone
acetone
acrolein
ethyl acetate1,4-dioxane 2-butanone 2-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
nitroethane Biphenyl
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

nally published Ind. Eng. Chem, 39, 517(1947).

-75, pp D191-D210.
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

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

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

comp1
8.88
2010.33
252.64
694.02
0.58963

comp2
8.07
1730.63
233.43
359.89
0.41037

comp3

0.00000

comp4
8.11
1592.86
226.18
824.46
0.00000

comp5
6.88
1075.78
233.21
2790.14
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 1E20 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
1
0
86.02
61.13
76.5
986.5
697.2
1318
2
-35.36
0
38.81
74.15
524.1
787.6
270.6
3
-11.12
3.45
0
167
636.1
637.3
903.8
4
-69.7
-113.6
-146.8
0
803.2
603.2
5695
5
156.4
457
89.6
25.82
0
-137.1
353.5
6
16.51
-12.52
-50
-44.5
249.1
0
-181
7
300
496.1
362.3
377.6
-229.1
289.6
0
8
275.8
217.5
25.34
244.2
-451.6
-265.2
-601.8
9
26.76
42.92
140.1
365.8
164.5
108.7
472.5
10
505.7
56.3
23.39
106
529
-340.2
480.8
11
114.8
132.1
85.84
-170
245.4
249.6
200.8
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
20
315.3
1264
62.32
89.96
-151
339.8
-66.17
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

8
1333
526.1
1329
884.9
-259.7
-101.7
324.5
0
-133.1
-155.6
-36.72

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

-253.1
-11

-450.3
-297.8
82.86
552.1

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

R
1 CH3
1 CH2

Q
0.9
0.67

0.85
0.54

Page 17

aij-UNIFAC (VLE)
3
4
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

1 CH
1C
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

0.45
0.22
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

0.23
0
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 u

Do not edit this table unless you want
T=

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

-165.5
190.6
242.8

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

Page 19

80.37

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

aij-UNIFAC (VLE)

Page 20

aij-UNIFAC (VLE)

ble 3. Interaction Parameters to be used in the calculations for the selected groups as indicated on sheet "UNIFAC (VLE)".
not edit this table unless you want to reprogram. Change values in Tables 1 and 2 unless you want to reprogram.
C

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

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

Table 4. Matrix of values used in calculations on sheet "UNIFAC (VLE).

Do not edit this table unless you want to reprogram. Change values in Tables 1 and 2 unless you want to reprogram.

CH3
CH2
CH
ACH
AC
ACCH3
ACCH2
OH
CH3
1
1
1
0.84
0.84
0.81
0.81

Page 21

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

CH3OH
0.06

0.14

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

1
1
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
1.03
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
1.03
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

0.84
0.84
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

0.84
0.84
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

Page 22

0.81
0.81
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

0.81
0.81
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

0.06
0.06
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

0.14
0.14
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

aij-UNIFAC (VLE)

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

H2O

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

ACOH
0.02

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

CH3CO
0.02

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
0.26

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

CH3COO
CH2NH2
ACNH2
COOH
0.52
0.33
0.07

Page 23

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

CCL2
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

0.93

aij-UNIFAC (VLE)
0.02
0.02
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
0.02
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

0.26
0.26
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

0.15
0.15
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

0.52
0.52
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

0.33
0.33
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

Page 24

0.07
0.07
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

0.15
0.15
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

0.86
0.86
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

0.93
0.93
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

aij-UNIFAC (VLE)

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

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

CON(CH2)2
0.34

Page 25

aij-UNIFAC (VLE)
0.34
0.34
1
1
1
1
2.95
1
0.09
1
1
1
1
1
1
2.49
1
1
1

Page 26

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.

P=
T(oC)=

Note: hidden
columns with ->
intermediate calcs

86.45 mmHg
25 oC

This sheet does not yet have the

cabability for specification of other
functional groups without editing
"aij-UNIFAC (LLE)". That will be
provided in the future.

<-

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

1
0.00158

comp5

1
0.00000

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.

1
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
1.147

0.100
6.414
1
1

0.070
1.951
1
1

0.000
1.705
1
1

0.000
199.114
2
3

Follow text instructions to create macro

1
Ki,old
Ki,new
xi,old
xi,new
xi,old
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 27

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

columns with ->

<P=
85.6 mmHg
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
0.26079

comp2
7.28
1434.2
246.5
99.57
0.73763

comp3

comp4

comp1

comp2

comp3

comp4

comp5

Water

MEK

c2-COOH

EtOH

C5H12

0
0
0
1
0.00158

comp5

0
0
0
1
0.00000

0
0
0
1
0.00000

0.773
1.235
0
0
0
0
0
0
0
0
1

0.139
4.541
1
1
0
0
0
0
0
0
0

0.088
1.535
1
1
0
0
0
0
0
0
0

0.000
1.396
1
1
0
0
0
0
1
0
0

0.000
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

CH3
CH2
CH
ACH
ACCH2
ACCH3
OH
2-Propanol
H2O

kk(i)xi
N groups

phase

Page 28

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

NOTE: Blank cells mean value is unavailable

CH2

CH

3
ACH

ACCH2

ACCH3

5
OH

2-Propanol H2O

9
ACOH

10
CH3CO

11
CHO

13
COOH

1 CH3

0.9

0.85

-114.8

-115.7

-115.7

644.6

310.7

1300

2255

472.6

158.1

139.4

CH2

0.67

0.54

-114.8

-115.7

-115.7

644.6

310.7

1300

2255

472.6

158.1

139.4

CH

0.45

0.23

-114.8

-115.7

-115.7

644.6

310.7

1300

2255

472.6

158.1

139.4

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

1.04

0.66

104.4

104.4

104.4

-146.8

4000

906.8

5695

292.6

916.7

1218

339.1

1.27

0.97

104.4

104.4

104.4

-146.8

4000

906.8

5695

292.6

916.7

1218

339.1

1.2

328.2

328.2

328.2

-9.21

1.27

1.27

991.3

28.73

-195.5

67.07

1409

-104

3.12 -131.9

-131.9

-131.9

-252

-273.6

-273.6 -268.8

5.89

-153.2

353.8 -338.6

-57.98

342.4

342.4

342.4

372.8

203.7

203.7 -122.4

104.9

344.5

-171.8 -349.9

-465.7

0.68 -159.8

-159.8

-159.8

-473.2

-470.4

-470.4 -63.15

-547.2

-595.9

-73.87

-568

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

1
3.25
0.92

1.4

0.9

-825.7

1.67

1.49

66.56

66.56

66.56

-78.31

-73.87

216

-127.6

634.8

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

1744

75.49

147.3

147.3

118.4

349.1

652.3

-101.3

1051

1.9

1.73 -320.1

-320.1

-320.1

114.8

-170

-170

180.6

-152.8

385.9

58.84

1090

1417

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

-465.7

793.2

-825.7

370.4

857.7

681.4

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

33.61

418.4

1.06

0.82

175.8

175.8

175.8

-218.9

-15.41

-15.41

529

-239.8

-337.3

-860.3

0 -37.36

1247

CH3
CH3

CH2
1

CH
1

ACH
1

ACCH2
1.47

ACCH3

1.47

Page 29

1.47

OH

2-PropanolH2O
0.12

0.35

ACOH
0.01

CH3CO
0

0.2

CHO
0.59

COOH
0.63

aij-UNIFAC (LLE)

CH2

1.47

1.47

1.47

0.12

0.35

0.01

0.2

0.59

0.63

CH

1.47

1.47

1.47

0.12

0.35

0.01

0.2

0.59

0.63

0.59

0.59

0.59

0.57

0.57

0.09

0.14

0.06

0.14

0.3

0.21

0.7

0.7

0.7

1.64

0.05

0.37

0.05

0.02

0.32

ACH
ACCH2
ACCH3

0.7

0.7

0.7

1.64

0.05

0.37

0.05

0.02

0.32

OH

0.33

0.33

0.33

1.03

0.04

0.91

1.93

0.8

0.01

1.42

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

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

ACOH

1.71

1.71

1.71

4.89

4.84

4.84

1.24

6.27

7.38

15.95

0.8

0.8

0.8

1.3

1.28

1.28

0.48

1.53

0.12

6.72

1.13

0.02

0.61

0.61

0.61

1.29

0.47

0.47

4.25

0.46

0.12

0.65

CH3CO
CHO
COOH

0.78

0.61

0.61

0.67

0.31

0.11

1.4

0.03

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

CH2O

0.01

0.01

0.01

0.84

0.8

0.8

0.63

2.08

0.49

0.84

0.01

CHCL2

0.91

0.91

0.91

0.11

3.85

0.08

0.16

0.23

CCL3

0.93

0.93

0.93

0.38

0.89

0.89

0.25

4.77

0.07

15.95

0.29

ACNH2

0.55

0.55

0.55

2.08

1.05

1.05

0.17

2.24

17.91

0.06

0.1

Page 30

aij-UNIFAC (LLE)

Fredenslund,

14
CH3COO

15
CH2O

17

18

CHCL2 CCL3

22
ACNH2

972.4

662.1

-243.9

7.5

902.2 CH3

972.4

662.1

-243.9

7.5

902.2 CH2

972.4

662.1

-243.9

7.5

902.2 CH

32.14

-231.9

5688

213.1

-12.14

689.6 ACCH2

5688

213.1

-12.14

689.6 ACCH3

195.6

262.5

272.2

-61.57

487.1

1970

507.8

1544

-6.32

64.42

370.7

356.8

-898.3
258.7

1.64 ACH

-348.2 OH
2-Propanol
-109.8 H2O
-851.6 ACOH

5.2

-301

12.01

1010 CH3CO

-245.8

CHO

-117.6

-96.62

1670

48.15

-235.7

108.9

-209.7

CH3COO

-154.3

CH2O

461.3

137.8

-132.9

-197.7

-898.3

-20.93

942.2 COOH

CHCL2
0

-75.5 CCL3

-216.3

CH3COO
0.04

CH2O
0.11

CHCL2 CCL3
2.27

0.98

0 ACNH2

ACNH2
0.05

Page 31

aij-UNIFAC (LLE)

0.04

0.11

2.27

0.98

0.05

0.04

0.11

2.27

0.98

0.05

0.98

0.9

2.18

0.99

0.49

1.04

0.1

0.49

1.04

0.1

0.52

0.41

0.4

1.23

3.22

0.2

0.18

0.01

1.02

0.81

0.29

0.3

1.45

20.35

17.4

0.42

0.98

2.74

0.96

0.03

2.28

1.48

1.38

0.85

0.04

2.2

0.69

2.02

0.21

0.63

1.68

1.56

1.94

20.35

1.07

1.29

2.07

Page 32

LLE
Water(1)+mek(2) at 298K by UNIFAC (cf Arce, JCEDat,40:226)
Summary of calculations for Example in Textbook
Gmix/RT
w
mek
w*xw
mek*xmek
x1
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
-0.10

0.00

0.10

0.20

0.30

0.40

0.50

0.60

xw
1.2
1

xigi

0.8
0.6
0.4
0.2

Page 33

0.70

0.80

0.90

1.00

0.8

xigi

LLE

0.6
0.4
0.2
0
-0.10

0.00

0.10

0.20

0.30

0.40

0.50

0.60

xw

Page 34

0.70

0.80

0.90

1.00