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

Page 1

Instructions

www.egr.msu.edu/~lira/thermtxt.htm

Page 2

253632124.xls.ms_office

Margules Equation
GE/RT = x1 x2 ( A21 x1 + A12 x2 )
Margules Parameters
Table x1 increment

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
6.430164
5.255585
4.353765
3.654328
3.106722
2.674258
2.330044
2.05418
1.831809
1.651745
1.5055
1.386587
1.290018
1.211938
1.149357
1.099951
1.061913
1.033846
1.014676
1.003593
1

A12_
1.861
0.05

gamma2
1
1.005171
1.020616
1.046455
1.083101
1.131256
1.191928
1.266457
1.356549
1.464331
1.592412
1.743965
1.922826
2.133614
2.381875
2.674258
3.018717
3.424761
3.903736
4.469169
5.137158

A21_
1.6365

activity1
0
0.262779
0.435377
0.548149
0.621344
0.668564
0.699013
0.718963
0.732724
0.743285
0.75275
0.762623
0.774011
0.78776
0.80455
0.824963
0.84953
0.878769
0.913208
0.953413
1

Page 3

activity2 G(mix) /RT

1
0
0.954912 -0.11065
0.918554 -0.15961
0.889487 -0.18973
0.866481 -0.20983
0.848442 -0.22392
0.834349
-0.2342
0.823197 -0.24194
0.813929 -0.24792
0.805382 -0.25255
0.796206 -0.25596
0.784784
-0.2581
0.76913
-0.2587
0.746765 -0.25727
0.714563 -0.25306
0.668564 -0.24497
0.603743 -0.23138
0.513714 -0.20976
0.390374 -0.17578
0.223458 -0.12025
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
VL (cm3/mol)
d (cal/cm3)1/2
Antoine Coeff
A
B
C
1 MeOH
8.08097 1582.27 239.726
40
14.5
2 benzene
6.87987 1196.76 219.161
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
0.026
0.05
0.088
0.164 0.28421
0.333
0.549
0.699
0.782
y1
0
0.267
0.371
0.457
0.526
0.559
0.595
0.633
0.665
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
F1
0 0.01199 0.02336 0.04202 0.08187 0.15289 0.18496 0.35622 0.51352 0.61985

Scatchard-Hildebrand model with zero binary interaction coefficient (x's from above) see plot ---->
x1
0
0.026
0.05
0.088
0.164 0.28421
0.333
0.549
0.699
0.782
g1
4.95691 4.89539 4.80679 4.6265 4.1889 3.44408 3.15202 2.05092 1.50662 1.28484
g2
1 1.00051 1.00198 1.0065 1.02537 1.09267 1.13891 1.62223 2.73115 4.33167
P1sat

1360.42 1106.07 952.138 793.176 624.096 515.235 495.453 476.601 481.258 471.905

P2sat

759.996 635.418 558.011 476.145 386.432 326.884 315.885 305.345 307.954 302.711

y1 calc

0 0.18524

0.4249 0.56413

0.6636 0.68426 0.70609 0.66688 0.62387

y2 calc

1 0.81476 0.69889 0.57509 0.43586

0.3364 0.31574 0.29395 0.33311 0.37612

T(K)
(Syi-1)2

0.3011

353.249 347.542 343.535 338.787 332.772 328.131 327.201 326.284 326.514 326.052
2.2E-11 2.5E-11 2.7E-11
3E-11 3.4E-11 3.8E-11 3.6E-12 1.4E-09 2.3E-10 1.9E-11
|

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

This table permits calculation of LLE if it exists as above in column G and M (LLE explained in Chap 12)
Dg*x
LLE
x1
g1*x1
0.00025 0.28421
g2*x2
0 0.97303
Scatchard-Hildebrand model with binary interaction coefficient kij=
-0.0331
x1
0
0.026
0.05
0.088
0.164 0.28421
0.333
0.549
0.699
g1
2.99688 2.94956 2.89995 2.81299 2.62008 2.29504 2.16324 1.62368 1.3191
g2
1 1.00035 1.00134 1.00439 1.01699 1.06134 1.09135 1.38606 1.9717
P1sat
1360.42 1206.11 1097.85 970.383 809.732 680.292 650.46 593.275 588.078
P2sat
759.996 684.868 631.325 567.276 484.774 416.591 400.627 369.732 366.904
y1 calc

0.782
1.18425
2.68889
588.256
367.001

0.1217 0.20945 0.31607 0.45781 0.58386 0.61653 0.69585 0.71347 0.71681

Page 4

Regular

y2 calc

0.99999 0.87802 0.79021 0.68372 0.54231 0.41643 0.38372 0.30411 0.28651 0.28306

T(K)
(Syi-1)2

353.249 349.904 347.34 344.037 339.317 334.908 333.793 331.532 331.317 331.325
3E-11 7.6E-08 1.1E-07 4.6E-08 1.5E-08 8.4E-08 6.5E-08 1.5E-09 1.8E-10 1.6E-08

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
g1
A12
591.288
1.28533
1.98475
P2sat

g2

368.651

x1

0.026

g1

7.27721

6.484

g2

2.06157
0.05

0.088

A21

1.7424

0.164 0.28421

0.333

0.549

5.8508 5.00842 3.76577 2.56262 2.24017 1.41687

0.699

0.782

1.1611 1.07975

1 1.00152 1.00559 1.01723 1.05985 1.18411 1.25734 1.80067 2.50314 3.07897

P1sat

1360.42 1035.63 885.787 759.286 653.482 605.458 599.369 591.838 593.207

P2sat

759.996 600.202

524.1

458.4 402.249 376.348 373.043

602.28

368.95 369.695 374.623

y1 calc

0 0.22972 0.34096 0.44033 0.53103 0.58022 0.58831 0.60575 0.63349 0.66913

y2 calc

0.99999 0.77037 0.65879 0.55956 0.46895 0.41971 0.41164 0.39424 0.36651 0.33086

T(K)
(Syi-1)2

353.249 345.77 341.64 337.674 333.908 332.028 331.781 331.473 331.529

331.9
3E-11 9.6E-09 6.5E-08 1.3E-08
3E-10 4.3E-09 2.3E-09 8.3E-11 4.3E-11 6.1E-11

Page 5

0.898 0.97303

0.973

0.76

0.907

59.9

62.7

64.7

333.05
335.85
0.80007 0.94253 0.94246

337.85
1

0.898 0.97303

0.973

1.07217 1.00571 1.00572

11.648

29.023 29.0109 39.8016

438.819

515.2 515.063 759.995

284.049 326.865 326.789 458.773

0.55592 0.66338 0.66319 0.99999
0.44405 0.33662

0.3368

T(K)

Regular

355
350
345
340
335
330
325
320
0

324.353 328.129 328.123 337.698 OBJ

8.1E-10 2.7E-11 3.5E-11 4.4E-11 3E-09

0.2

0.4

0.6
x-y

|
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.

0.898 0.97303

0.973

1.04782 1.00384 1.00384

355
350

598.28 668.766 668.694 759.995

345

372.452 410.435 410.396 458.773

0.74072 0.85951

0.8594 0.99999

T(K)

5.18562 9.63552 9.63258 12.5016

340

Page 6

Regular

0.25921 0.14033 0.14044

335

331.737 334.482 334.48 337.698 OBJ

4E-09 2.7E-08 2.7E-08 4.4E-11 5E-07

330
0

0.2

0.4

0.6

0.8

0.6

0.8

x-y

0.898 0.97303

0.973

1.01645 1.00112 1.00112

355
350

644.91 716.653 716.608 759.995

397.646 435.917 435.893 458.773
0.77455 0.91856 0.91848 0.99999
0.22542

0.0814 0.08149

T(K)

4.22384 5.26252 5.26201 5.71104

345
340
335
330

333.581 336.213 336.211 337.698 OBJ

1.1E-09 1.4E-09 1.4E-09 4.4E-11 1E-07

0.2

0.4
x-y

Page 7

Regular

0.8

agram are indicative

perimental data.
essary to fit the data

Page 8

Regular

0.8

0.8

Page 9

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.
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 -1.21897
-32.78
529.57
(2) Benzene
3.19
2.4
2.4
1.76 2.71923
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

tau21

theta1

theta2

theta'1

1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447
1.09447

0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264
0.23264

0
0.03041
0.06209
0.09514
0.12965
0.1657
0.20341
0.2429
0.28429
0.32773
0.37337
0.42138
0.47195
0.52529
0.58164
0.64126
0.70443
0.7715
0.84283
0.91884
1

1
0.96959
0.93791
0.90486
0.87035
0.8343
0.79659
0.7571
0.71571
0.67227
0.62663
0.57862
0.52805
0.47471
0.41836
0.35874
0.29557
0.2285
0.15717
0.08116
0

0
0.03041
0.06209
0.09514
0.12965
0.1657
0.20341
0.2429
0.28429
0.32773
0.37337
0.42138
0.47195
0.52529
0.58164
0.64126
0.70443
0.7715
0.84283
0.91884
1

Page 10

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

phi1

phi2

ln(gam1)

ln(gam2)

gam1

gam2

1
0.96959
0.93791
0.90486
0.87035
0.8343
0.79659
0.7571
0.71571
0.67227
0.62663
0.57862
0.52805
0.47471
0.41836
0.35874
0.29557
0.2285
0.15717
0.08116
0

0
0.02305
0.04745
0.07331
0.10078
0.13
0.16116
0.19444
0.23009
0.26835
0.30952
0.35396
0.40206
0.4543
0.51124
0.57353
0.64198
0.71753
0.80137
0.89493
1

1
0.97695
0.95255
0.92669
0.89922
0.87
0.83884
0.80556
0.76991
0.73165
0.69048
0.64604
0.59794
0.5457
0.48876
0.42647
0.35802
0.28247
0.19863
0.10507
0

1.96347
1.71089
1.48976
1.29481
1.12198
0.96811
0.83071
0.70778
0.59772
0.49924
0.41129
0.33303
0.26379
0.20306
0.15043
0.10567
0.06863
0.03932
0.01786
0.00458
0

0
0.00638
0.02423
0.05201
0.08861
0.13323
0.1853
0.24445
0.31045
0.3832
0.46275
0.54923
0.64289
0.74412
0.85341
0.97145
1.09907
1.23736
1.38769
1.55181
1.73198

7.12403
5.5339
4.43604
3.65029
3.07092
2.63296
2.29494
2.02948
1.81797
1.64747
1.50877
1.39519
1.30186
1.22514
1.16234
1.11146
1.07104
1.0401
1.01802
1.00459
1

1
1.0064
1.02453
1.05339
1.09266
1.14251
1.20358
1.27691
1.36403
1.46698
1.58844
1.73192
1.90197
2.10458
2.34765
2.64176
3.00137
3.44649
4.00558
4.72001
5.65183

Page 11

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.
Antoine A
Antoine B
Antoine C
Psat (mmHg)
y
Pcalc (mm Hg)
T (K) =

1
2
8.07131 7.280662
1730.63 1434.201
233.426 246.499
23.68641 99.57149
0.2283
0.7717
98.49289
298.15 Phase a
1

Name

Water

1
0.0000

1
0.0000

1.00E-02

1.00E-11

1.00E-11

2
MEK

1
0.0000 Unhide columns G-R for LLE iterations.

Acetic

8.91E-01

9.89E-02

g
xg

1.065208 7.717527 0.084035

4.2692434 1.1873165

0.949193 0.763362

4.269E-11

1.187E-11

0.92
3.2479
2.2024
3.19
1.4
2.876
2.072
2.4
0.704851 0.276213 0.018936 2.743E-11
0.803446 0.18321 0.013344 1.546E-11
1.163083 Sixiqi
1.552715
aij matrix (i = row, j=column), enter 0's for unused cells

1.43
1.43
1.229E-11
9.21E-12

0.00084

r
q
F
q
Sixiri

1
2
3
4
5

1
1
345.53
-301.02
0
0

2
-2.0882
1
-4.5537
0
0

3
254.15
-254.13
1
0
0

4
0
0
0
1
0

5
0
0
0
0
1

tij matrix (i = row, j=column)

1

Page 12

UNIQUAC5

1
1 1.007028 0.42638
2 0.313827
1 2.345166
3 2.744574 1.01539
1
4
1
1
1
5
1
1
1

1
1
1
1
1

1
1
1
1
1

ln(gcomb)
Si(qitij)

0.032001 0.630614 0.46027

0.897566 1.005852 0.785576

1.6776811 0.3064997
1
1

qj/Si(qitij)

0.895138 0.182144 0.016987

1.546E-11

Sj{qjtkj/(Siqitij)}

1.085805 0.502899 2.658706

1.0942685 1.0942685

resid

ln(g

0.031169

1.41288

-2.93679 -0.2262445

9.21E-12
-0.134804

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

Page 13

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

T[oC]

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

100

methanol ethanol
1-propanol 1-propanol 2-propanol 1-butanol
1-butanol
8.08097
8.1122
7.74416
8.37895 8.87829
7.81028
7.75328
1582.27
1592.864 1437.686
1788.02 2010.33
1522.56
1506.07
239.726
226.184
198.463
227.438 252.636
191.95
191.593
15
20
60
-15
-26
30
70
84
93
106
98
83
70
120
3
3
3
3
2
2
2651.42
1693.832 845.6573 828.5394 1504.62 393.677343 387.531406

methane ethane
propane
n-butane
n-pentane n-pentane
n-hexane
A
6.6438
6.82915
6.80338
6.80776 6.85296
6.87632
6.87601
B
395.74
663.72
804
935.77 1064.84
1075.78
1171.17
C
266.681
256.681
247.04
238.789 232.012
233.205
224.408
o
tMin[ C]
-182
-143
-108
-78
-50
-50
-25
tMax[oC]
-158
-84
-35.65
19
58
58
92
Source
5
5
5
5
5
3
5
Psat[mmHg]
366903 92966.736 30665.09 11108.55
4423.1 4443.62085 1844.31002

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

cyclohexanecyclohexane methylcyclohexane
isopentane toluene
benzene
m-xylene
7.26475
6.85146
7.1161
8.1122 6.95087
6.87987
7.00909
1434.15
1206.47
1444.59 1592.864 1342.31
1196.76
1462.266
246.721
223.136
240.184
226.184 219.187
219.161
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 1311.6888 740.6346 1693.832 556.502 1349.47157 233.666366

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

water
acetonitrile Triethylamineacetic acid acetic acid chloroform
dichloromethane
8.07131
7.33986
5.85879
8.021 8.26735
6.95465
7.0803
1730.63
1482.29
695.666
1936.01 2258.22
1170.966
1138.91
233.426
250.523
144.832
258.451
300.97
226.232
231.45
1
-27
50
18
118
-10
-44
100
82
95
118
227
60
59
3
3
3
3
3
3
3
760.086 1291.4118 1040.851 416.8261 431.969 2318.91137 4407.12923

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
7.36366 7.20131 8.36605 7.25162
1305.198
1157 2170.24 1448.57
173.427 168.279 205.921 134.118
89
72
55
80
126
107
150
200
3
3
1
1
389.20746 773.812 18.7041 11.5957
hexane
n-heptane heptane n-octane n-nonane n-decane decane
6.91058 6.89677 6.89386 6.91868 6.93893 6.94363
7.44
1189.64
1264.9 1264.37 1351.99 1431.82 1495.17 1843.12
226.28 216.544
216.64 209.155
202.11 193.858
230.22
-30
-2
-3
19
39
58
17
170
123
127
152
178
203
174
3
5
3
5
5
5
3
1838.6927 795.795 795.749 351.157 158.318 71.7068 72.1953

o-xylene
p-xylene acetone
acetone
acrolein
ethyl acetate
1,4-dioxane2-butanone2-butanone
7.00154 6.99053
7.6313 7.11714 7.06691 7.10179 7.43155 7.28066 7.06356
1476.393 1453.43 1566.69
1210.6 1204.95 1244.95 1554.68
1434.2 1261.34
213.872
215.31 273.419 229.664
235.35 217.881 240.337 246.499 221.969
63
27
57
-13
-65
16
20
-6.5
43
145
166
205
55
53
76
105
80
88
3
3
3
3
3
3
3
1
3
198.48788 240.438 2727.54 2785.68 2977.13 1532.45 730.285
1385.3 1399.53
dichoromethane
tetrachloromethane
1,2-dichloroethane
Benzyl chloride
nitroethaneBiphenyl Naphthalene
7.40916 6.84093
7.0253 7.59716 7.19458 13.5354 8.62233
1325.938 1177.91 1271.25 1961.47 1446.51 4993.37 2165.72
252.616 220.576 222.927 236.511 220.795 296.072 198.284
-40
-20
-31
22
1.5
20
20
40
77
99
180
94
40
40
3
3
3
1
1 solid
4(solid)
4455.2409 1467.49 1226.42 58.6575 484.666 8.47563 23.0003

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

ss, 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
7.23064
1477.02
237.517
36
102
3
715.323

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.

P=
T(oC)=

745.516 mmHg
o
80.37 C

Table 1. Antoine Coefficients (mmHg) log10(Psat)=A-B/(T+C) where T[=] oC

A
B
C
Psat[mmHg]
yi

comp1
8.87829
2010.33
252.636
694.01962
0.58963

comp2
8.07131
1730.63
233.426
359.8872
0.41037

comp3

comp4
8.1122
1592.86
226.184
824.459
0.00000 0.00000

comp5
6.87632
1075.78
233.205
2790.137
0.00000

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

gi

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

1
1

S knk(i)xi

0.5

3E-20

3E-20

5E-20

N groups

3.1240

1.4000

2.6120

2.5880

3.3160

3.2491

0.9200

2.8768

2.5755

3.8254

qi

0.6905

0.3095

0.0000

0.0000

0.0000

Fi

0.7793

0.2207

0.0000

0.0000

0.0000

lngC

0.0042

0.0994

0.1625

0.0152

0.2233

lngRo

1.3197

0.0000

1.1812

1.0915

0.0000

lngR

1.5520

0.4313

0.9983

1.1784

2.3110

Page 17

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
3.446
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
1.163
-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
9.755
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

R
1 CH3

Q
0.9011

0.848

Page 18

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)

2
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
1
1
2
2
2
2
2
3
3
4
4
4
5
6
7
8
9
9
10
11
11
14
17
20
22
23
46

CH2
CH
C
CH2=CH
CH=CH
CH2=C
CH=C
C=C
ACH
AC
ACCH3
ACCH2
ACCH
OH
CH3OH
H2O
ACOH
CH3CO
CH2CO
CHO
CH3COO
CH2COO
CH2NH2
ACNH2
COOH
CCL2
CCL3
CON(CH2)2

0.6744
0.4469
0.2195
1.3454
1.1167
1.1173
0.8886
0.6605
0.5313
0.3652
1.2663
1.0396
0.8121
1
1.4311
0.92
0.8952
1.6724
1.4457
0.998
1.9031
1.6764
1.3692
1.06
1.3013
1.8016
2.6401
2.4054

0.54
0.228
0
1.176
0.867
0.988
0.676
0.485
0.4
0.12
0.968
0.66
0.348
1.2
1.432
1.4
0.68
1.488
1.18
0.948
1.728
1.42
1.236
0.816
1.224
1.448
2.184
1.812

Page 19

aij-UNIFAC (VLE)

Table 3. Interaction Parameters to be used in the calculations

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

11
232.1
37.85
5.994
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
8.642
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

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

R
0.9011
0.6744
0.4469
0.5313
0.3652
1.2663
1.0396
1
1.4311
0.92
0.8952
1.6724
0.998
1.9031
1.3692
1.06
1.3013
1.8016
2.6401
2.4054

Table 4. Matrix of Y values used in calculation

Do not edit this table unless you want to reprog
Y
CH3

Page 20

aij-UNIFAC (VLE)

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

Page 21

1
1
1
1.03195502
1.03195502
1.21793888
1.21793888
0.64248759
0.954372
0.42801019
0.45833548
0.92709813
0.23919631
0.7227195
1.09004459
0.0398799
0.40988145
0.9080476
0.90139377
0.92393036

aij-UNIFAC (VLE)

ters 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.

a ij (i=column, j=row)
1
Q
0.848
0.54
0.228
0.4
0.12
0.968
0.66
1.2
1.432
1.4
0.68
1.488
0.948
1.728
1.236
0.816
1.224
1.448
2.184
1.812

CH3

1
CH2

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

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

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

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

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

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

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

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

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

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

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

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

CH

ACH

AC

ACCH3

ACCH2

Page 22

OH

CH3OH

H2O

ACOH

CH3CO

aij-UNIFAC (VLE)

1
1
1
1.03195502
1.03195502
1.21793888
1.21793888
0.64248759
0.954372
0.42801019
0.45833548
0.92709813
0.23919631
0.7227195
1.09004459
0.0398799
0.40988145
0.9080476
0.90139377
0.92393036

1
1
1
1.03195502
1.03195502
1.21793888
1.21793888
0.64248759
0.954372
0.42801019
0.45833548
0.92709813
0.23919631
0.7227195
1.09004459
0.0398799
0.40988145
0.9080476
0.90139377
0.92393036

0.84120652
0.84120652
0.84120652
1
1
1.51475289
1.51475289
0.77611777
1.1519253
0.35885534
0.93082954
0.67280478
0.93597814
0.78441653
1.13526595
0.49653474
0.83837966
0.70955262
0.52395125
1

0.84120652
0.84120652
0.84120652
1
1
1.51475289
1.51475289
0.77611777
1.1519253
0.35885534
0.93082954
0.67280478
0.93597814
0.78441653
1.13526595
0.49653474
0.83837966
0.70955262
0.52395125
1

0.80541701
0.80541701
0.80541701
0.62350908
0.62350908
1
1
0.92956654
1.13414254
0.34365571
0.50119144
0.35532004
0.74093558
1.61749398
0.43239101
0.11558744
0.77532783
0.67147389
0.82059489
1

0.80541701
0.80541701
0.80541701
0.62350908
0.62350908
1
1
0.92956654
1.13414254
0.34365571
0.50119144
0.35532004
0.74093558
1.61749398
0.43239101
0.11558744
0.77532783
0.67147389
0.82059489
1

Page 23

0.06139009
0.06139009
0.06139009
0.16540927
0.16540927
0.10310502
0.10310502
1
0.49429254
1.91181654
3.58743813
0.627934
0.22393952
0.49949306
1.98735969
1.05045067
1.53285627
0.22482812
0.12255762
0.32733587

0.13915517
0.13915517
0.13915517
0.16484876
0.16484876
0.18154197
0.18154197
1.47375562
1
0.44078861
2.11735935
0.73529826
2.61776733
0.49359394
3.9062664
1.39663922
0.38243739
0.15032701
0.15943715
1

0.0240356
0.0240356
0.0240356
0.07757005
0.07757005
1.0087E-07
1.0087E-07
0.36790025
1.66861454
1
5.48659703
0.26274848
0.25665148
0.5666566
2.54619627
2.6281547
1.20583793
0.13470129
0.09644673
4.22345703

0.0230371
0.0230371
0.0230371
0.02329924
0.02329924
0.08182998
0.08182998
2.08467278
1.33332818
0.3993523
1
1.45717439
1.55293211
1.10945583
1
2.04611428
1.03160479
1
1
1

0.2598658
0.2598658
0.2598658
0.92969802
0.92969802
1.15878839
1.15878839
0.7885099
0.93597814
1.73798581
2.7381925
1
0.69623163
0.34894533
1
3.57427026
2.32189847
0.79105672
0.20977451
1

aij-UNIFAC (VLE)

10

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

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

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

CHO

CH3COO

CH2NH2

11
CH3COO
232.1
232.1
232.1
5.994
5.994
5688
5688
101.1
-10.72
72.87
-449.4
-213.7
-110.3
0
0
-294.8
-256.3
-133
176.5
0

ACNH2

14
CH2NH2
391.5
391.5
391.5
161.7
161.7
19.02
19.02
8.642
359.3
48.89
0
0
0
0
0
-15.07
0
0
0
0

COOH

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

Page 24

20

22

23

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

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

CCL3
24.9
24.9
24.9
-231.9
-231.9
-80.25
-80.25
-98.12
-139.4
353.7
0
-354.6
-483.7
-209.7
0
0
39.63
0
0
0

CCL3

CON(CH2)2

46
CON(CH2)2
380.9
380.9
380.9
0
0
0
0
-382.7
0
835.6
0
0
0
0
0
0
-322.3
0
0
0

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

aij-UNIFAC (VLE)

0.147338
0.147338
0.147338
0.37440936
0.37440936
0.19026983
0.19026983
1.77877007
0.42033136
1.38836742
2.15299311
1.11146617
1
0.59238927
1
1
1.59703519
0.58324431
0.50318018
1

0.51864277
0.51864277
0.51864277
0.98318774
0.98318774
1.0289E-07
1.0289E-07
0.7512769
1.03078805
0.81372977
3.56518237
1.83032211
1.36616149
1
1
2.30227801
2.06471942
1.45676225
0.6069769
1

0.33040576
0.33040576
0.33040576
0.6329272
0.6329272
0.94761994
0.94761994
0.9758508
0.36191357
0.87084187
1
1
1
1
1
1.04355006
1
1
1
1

0.07394906
0.07394906
0.07394906
0.15984357
0.15984357
0.15277046
0.15277046
1.15973936
0.25027084
0.50261116
0.71236815
2.4108E-08
1
0.26052821
1.76423813
1
0.24738505
0.67147389
1
1

0.15307326
0.15307326
0.15307326
0.2186812
0.2186812
0.08479913
0.08479913
0.56954917
1.77073771
1.04066122
0.31453715
0.15053977
0.24480938
0.15450884
1
3.06535361
1
0.21506185
0.24021338
1.21983521

0.85892763
0.85892763
0.85892763
1.50450427
1.50450427
1.36886929
1.36886929
0.83138927
1.33634886
0.35072657
1
1.44567865
0.82613801
0.73488239
1
1.36886929
1.13478435
1
1.27011764
1

Page 25

0.93198879
0.93198879
0.93198879
1.92701891
1.92701891
1.25483328
1.25483328
1.31989407
1.48337513
0.36769218
1
2.72659885
3.92842829
1.80972914
1
1
0.89395383
1
1
1

0.34046272
0.34046272
0.34046272
1
1
1
1
2.95217238
1
0.09407557
1
1
1
1
1
1
2.48852002
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.

P=

Note: hidden
columns with ->
intermediate calcs

86.446 mmHg
o
25 C

<-

T(oC)=
Antoine Coefficients (mmHg) log10(Psat)=A-B/(T+C) where T[=] oC
A
B
C
sat
P [mmHg]
yi

comp1
8.07131
1730.63
233.426
23.68641
0.26079

comp2
7.2806621
1434.2011
246.49905
99.571488
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.

1
0.00158

1
0.00000

1
0.00000

a 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

gi
CH3
CH2

1.147

6.414
1
1

1.951
1
1

1.705
1
1

199.114
2
3

Follow text instructions to create macro

1

a
i,old

CH

ACH

xai,new

ACCH2

xbi,old

ACCH3
OH
2-Propanol
H2O

Ki,old
Ki,new

i,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
Sknk(i)xi

0.21

3E-20

5E-20

1.4000

2.8760

2.6120

2.5880

3.3160

0.9200

3.2479

2.8768

2.5755

3.8254

qi

0.7120

0.1759

0.1120

0.0000

0.0000

Fi

0.5923

0.2515

0.1562

0.0000

0.0000

lngC

0.0606

0.4430

0.3795

0.0676

0.4747

lngRo

0.0000

0.8719

1.1448

1.2862

0.0000

lngR

0.0761

2.2874

1.4339

1.7522

4.8192

N groups

0.830153 0.2995423

Page 26

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.

P=

Note: hidden
columns with ->
intermediate calcs

85.603 mmHg
o
25 C

<-

T(oC)=
Antoine Coefficients (mmHg) log10(P sat)=A-B/(T+C) where T[=] oC
A
B
C
Psat[mmHg]
yi

comp1
8.07131
1730.63
233.426
23.68641
0.26079

comp2
7.2806621
1434.2011
246.49905
99.571488
0.73763

comp3

comp4
0
0
0
0
0
0
1
1
0.00158 0.00000

comp5

comp1

comp2

comp3

comp4

comp5

Water

MEK

c2-COOH

EtOH

C5H12

0
0
0
1
0.00000

0.773

0.139

0.088

0.000

0.000

gi
CH3
CH2
CH
ACH
ACCH2
ACCH3
OH
2-Propanol
H2O

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

0.417 0.264251

3E-20

5E-20

S knk(i)xi
N groups

0.772916
1

1.4000

2.8760

2.6120

2.5880

3.3160

0.9200

3.2479

2.8768

2.5755

3.8254

qi

0.6321

0.2335

0.1344

0.0000

0.0000

Fi

0.5022

0.3188

0.1790

0.0000

0.0000

lngC

0.0909

0.3122

0.2677

0.0150

0.3208

lngRo

0.0000

0.8719

1.1448

1.2862

0.0000

lngR

0.1204

2.0730

1.3059

1.6049

4.3303

b phase

Page 27

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 a ij matrix.
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,
Ind. Eng. Chem. Process Des. Dev., 1981, 20, 331-339.
T=
25 C

a ij (i=column, j=row)
Main

Group

3
4
5
7
8
9
10
11
13
14
15
17
18
22

CH3

NOTE: Blank cells mean value is unavailable

3

CH2

CH

ACH

4
ACCH2

5
ACCH3

OH 2-Propanol H2O

9
ACOH

10
CH3CO

11
CHO

13

14

15

COOH CH3COO CH2O

CH3

0.901

0.848

-114.8

-115.7

-115.7

644.6

310.7

1300

2255

472.6

158.1

139.4

972.4

662.1

CH2

0.674

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

0.447

0.228

-114.8

-115.7

-115.7

644.6

310.7

1300

2255

472.6

158.1

139.4

972.4

662.1

ACH

0.531

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

ACCH2

1.04

0.66

104.4

104.4

104.4

-146.8

4000

906.8

5695

292.6

916.7

1218

339.1

5688

213.1

ACCH3

1.266

0.968

104.4

104.4

104.4

-146.8

4000

906.8

5695

292.6

916.7

1218

339.1

5688

213.1

1.2

328.2

328.2

328.2

-9.21

1.27

1.27

991.3

28.73

-195.5

67.07

1409

-104

195.6

262.5

3.124 -131.9

-131.9

-131.9

-252

-273.6

-273.6 -268.8

5.89

-153.2

353.8 -338.6

-57.98

487.1

1970

-171.8 -349.9

-465.7

-6.32

64.42

OH
2-Propanol
H2O

3.249
0.92

342.4

342.4

342.4

372.8

203.7

203.7 -122.4

104.9

344.5

0.68 -159.8

1.4

-159.8

-159.8

-473.2

-470.4

-470.4 -63.15

-547.2

-595.9

66.56

66.56

66.56

-78.31

-73.87

-73.87

216

-127.6

634.8

-568

0.948

146.1

146.1

146.1

-75.3

223.2

223.2 -431.3

231.4

623.7

128

1.301

1.224

1744

1744

1744

75.49

147.3

147.3

118.4

349.1

652.3

CH3COO

1.903

1.728 -320.1

-320.1

-320.1

114.8

-170

-170

180.6

-152.8

385.9

CH2O

0.918

0.78

1571

1571

52.13

65.69

65.69

137.1

-218.1

212.8

CHCL2

ACOH

0.895

CH3CO

1.672

1.488

CHO

0.998

COOH

1571

-337.3

-825.7

-898.3

0 -37.36

1247

258.7

5.202

0.75

-245.8

-101.3

1051

-117.6

-96.62

58.84

1090

1417

-235.7

52.38

1402

461.3

2.061

1.684

27.9

27.9

27.9

669.2

-401.6

740.4

550.6

437.7

-132.9

-197.7

CCL3

2.64

2.184

21.23

21.23

21.23

288.5

33.61

33.61

418.4

-465.7

793.2

-825.7

370.4

-898.3

-20.93

ACNH2

1.06

0.816

175.8

175.8

175.8

-218.9

-15.41

-15.41

529

857.7

681.4

-239.8

-860.3

Y
CH3

CH2

CH

ACH

ACCH2 ACCH3

Page 28

OH

2-Propanol
H2O

ACOH CH3CO

CHO

COOH CH3COO CH2O

aij-UNIFAC (LLE)

CH3

1.4697 1.47412 1.474118

0.115 0.35272 0.0128 0.0005

0.20493

0.588 0.6265 0.038333 0.1085

CH2

1.4697 1.47412 1.474118

0.115 0.35272 0.0128 0.0005

0.20493

0.588 0.6265 0.038333 0.1085

CH

1.4697 1.47412 1.474118

0.115 0.35272 0.0128 0.0005

0.20493

0.588 0.6265 0.038333 0.1085

0.094 0.14424

0.004

0.13652

0.297 0.2125 0.980077 0.8978

ACH

0.592 0.5916 0.59161

ACCH2

0.705 0.7046 0.70458

1.6362

1 1E-06 0.04777

5E-09 0.3748

0.04621

0.017 0.3207

5.18E-09 0.4893

ACCH3

0.705 0.7046 0.70458

1.6362

1 1E-06 0.04777

5E-09 0.3748

0.04621

0.017 0.3207

5.18E-09 0.4893

OH

0.333 0.3326 0.33261

1.0314 0.99575 0.995749

1 0.03598 0.9081 1.9265

0.79855

0.009 1.4174 0.518899 0.4146

2-Propanol

1.556 1.5564 1.55643

2.3285 2.50342 2.503423

2.463

0.30524

3.113 1.2147 0.195198 0.0014

H2O

0.317 0.3171 0.31714

0.2864 0.50499 0.504992

1.508

1.7793

3.234 4.7682 1.021424 0.8057

ACOH

1.709 1.7091 1.70911

4.8896 4.84394 4.843944

1.236 6.26713 7.3791

15.9492

0.8 0.7999 0.79992

1.3004 1.28115 1.281154

0.485 1.53414 0.1189

6.72

CHO

0.613 0.6126 0.61261

1.2873 0.47302 0.473021

4.249 0.46019 0.1235

0.65096

COOH

0.003 0.0029 0.00288

0.7763 0.61015 0.610152

0.672 0.31009 0.1122

1.40461

CH3COO

2.926

0.6804 1.76859

0.546 1.66945 0.2741 3.0997

0.8209

CH2O

0.005 0.0051 0.00515

CHCL2

0.911 0.9107 0.91067

CCL3
ACNH2

CH3CO

2.926 2.92595

1 0.57114

0.57114

1.76859

0.8396 0.80226 0.802258

0.056

1 0.9804 1.6717
0.7034

1 0.3149

1 20.34658

1.133 0.0153 0.419923 0.9827

1 0.9975 2.280551
0.029

1 1.483542 1.3827

0.026 0.0086

1 2.2046

0.631 2.07822 0.4898

0.83888

1 0.0091 0.212841

0.106 3.84577 0.0835

0.15775

1 0.2304 1.561659 1.9408

0.931 0.9313 0.93127

0.38 0.89339 0.893393

0.246 4.76818 0.0699

15.9492

1 0.2887 20.34658 1.0727

0.555 0.5545 0.55453

2.0838 1.05304 1.053044

1 2.2351 17.912

0.05632

1 0.1017

Page 29

0.17

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

1.64 ACH

-12.14

689.6 ACCH2

-12.14

689.6 ACCH3

272.2

-61.57

507.8

1544

370.7

356.8

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

-301

12.01

1010 CH3CO
CHO

1670

48.15

942.2 COOH

108.9

-209.7

CH3COO

137.8

-154.3

CH2O

-75.5 CCL3

CHCL2

-216.3

CHCL2 CCL3

0 ACNH2

ACNH2

Page 30

aij-UNIFAC (LLE)

2.2661 0.9752 0.04851

2.2661 0.9752 0.04851
2.2661 0.9752 0.04851
1 2.1767 0.99451
1 1.0416 0.09897
1 1.0416 0.09897
0.4013 1.2294 3.21513
0.1821 0.0056

0.2884 0.3022 1.44523

1

1 17.3967

2.7444 0.9605 0.03379

1

0.0037 0.8509 0.04242

0.694 2.0205

0.6299 1.6779

1 1.28818

1 2.0657

Page 31

LLE

Water(1)+mek(2) at 298K by UNIFAC (cf Arce, JCEDat,40:226)

Summary of calculations for Example in Textbook
gw
gmek
gw*xw
gmek*xmek
x1 DGmix/RT

Gm/RT

0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00

0
-0.0585
-0.0732
-0.0794
-0.0819
-0.0821
-0.0804
-0.0774
-0.073
-0.0676
-0.0613
-0.0544
-0.0472
-0.0402
-0.0339
-0.029
-0.0261
-0.0258
-0.0284
-0.031
0

23.55
12.21
7.886
5.753
4.52
3.729
3.18
2.777
2.466
2.217
2.01
1.835
1.683
1.549
1.429
1.322
1.226
1.142
1.072
1.021
1

1
1.016
1.052
1.1
1.157
1.223
1.299
1.387
1.489
1.611
1.76
1.947
2.189
2.515
2.973
3.656
4.743
6.637
10.36
19.09
45.76

0
0.6102643
0.7886256
0.8629652
0.9040903
0.9322211
0.9540354
0.9718231
0.9862733
0.9974616
1.0052472
1.0094566
1.0099893
1.0068982
1.0004766
0.9913773
0.9808008
0.9708322
0.9651083
0.9703055
1

@x1~0.35

0
-0.01
-0.02
-0.03
-0.04
-0.05
-0.06
-0.07
-0.08
-0.09
0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

xw

1.2
1
0.8
ig i

Coexistence calculation

1
0.96501291
0.94656461
0.93479922
0.92573172
0.91758482
0.90959788
0.90156504
0.89363852
0.88624657
0.88007151
0.87606799
0.87551553
0.88010222
0.89201968
0.91396674
0.94861074
0.99553493
1.03626755
0.95438317
0

0.6
Page 32

0.80

0.90

1.00

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 33

0.80

0.90

1.00