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 View…Comment…to show or hide them.

As distributed, this cell

P de Bubb 12883 mmHg has a formula to
calculate the bubble
T( C)=o
200 C o
pressure.
Table 1. Antoine Coefficients (mmHg) log10(Psat)=A-B/(T+C) where T[=] oC
comp1 comp2 comp3 comp4 comp5
A 8.87829 8.07131 8.1122 6.87632 Enter Antoine constants
or vapor pressures if you
B 2010.33 1730.63 1592.9 1075.78
want bubble P and
C 252.636 233.426 226.18 233.205 vapor phase
Psat[mmHg] 27346.81 11978.5 23697 24718.11 concentrations
yi 1.00000 0.87930 0.00000 ### 0.00000 calculated automatically.
Table 2. Component Structure Information and Activity Coefficient Calculation.
Vapor phase mole
comp1 comp2 comp3 comp4 comp5 fractions calculated
IPA Water C2-COOH EtOH C5H12 automatically.

xi 0.100 0.900 0.000 0.000 0.000 Liquid phase mole fractions. Enter a very small number like
gi 1E-20 or smaller for absent compounds - don't use zero.
SubGroup 4.711 1.051 3.276 2.793 145.558
1 CH3 2 1 1 2
2 CH2 1 1 3 Enter the number of occurences of a chemical
3 CH 1 structure in this table for each component. Residual
9 ACH group interaction parameters are not available for all
10 AC groups, and are treated as zero if unavailable.
Check Table 1 on sheet "aij-UNIFAC (VLE)".
11 ACCH3
12 ACCH2
14 OH 1 1 The sub-groups available in this table may be
15 CH3OH changed in this column by changing the
16 H2O 1 SubGroup number. If you change a sub-group
here, be sure to edit the component structure
17 ACOH information in the table. Available subgroups and
18 CH3CO subgroup numbers are in Table 2 of sheet "aij-
20 CHO UNIFAC (VLE)".

21 CH3COO
29 CH2NH2
36 ACNH2
42 COOH 1
49 CCL2
51 CCL3
99 CON(CH2)2
Sknk(i)xi 0.4 0.9 3E-20 3E-20 5E-20
N groups 4 1 3 3 5
Note that columns H:AS are
hidden. They contain
q 3.1240 1.4000 2.6120 2.5880 3.3160
intermediate calculations.
r 3.2491 0.9200 2.8768 2.5755 3.8254 Unprotect the sheet and unhide
them to see the calculations.
qi 0.1987 0.8013 0.0000 0.0000 0.0000
Fi 0.2818 0.7182 0.0000 0.0000 0.0000
lng C
0.2940 0.0169 0.6630 0.2401 0.8734
lng Ro
1.1502 0.0000 0.9857 0.9552 0.0000
lng R
2.4061 0.0327 1.5093 1.7422 4.1072

CH3 CH2 CHNH

CH3 0 0 255.7
CH2 0 0 255.7
CHNH 65.33 65.33 0

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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 9 10 11
1 0 86.02 61.13 76.5 986.5 697.2 1318 1333 476.4 677 232.1
2 -35.36 0 38.81 74.15 524.1 787.6 270.6 526.1 182.6 448.8 37.85
3 -11.12 3.446 0 167 636.1 637.3 903.8 1329 25.77 347.3 5.994
4 -69.7 -113.6 -146.8 0 803.2 603.2 5695 884.9 -52.1 586.6 5688
5 156.4 457 89.6 25.82 0 -137.1 353.5 -259.7 84 -203.6 101.1
6 16.51 -12.52 -50 -44.5 249.1 0 -181 -101.7 23.39 306.4 -10.72
7 300 496.1 362.3 377.6 -229.1 289.6 0 324.5 -195.4 -116 72.87
8 275.8 217.5 25.34 244.2 -451.6 -265.2 -601.8 0 -356.1 -271.1 -449.4
9 26.76 42.92 140.1 365.8 164.5 108.7 472.5 -133.1 0 -37.36 -213.7
10 505.7 56.3 23.39 106 529 -340.2 480.8 -155.6 128 0 -110.3
11 114.8 132.1 85.84 -170 245.4 249.6 200.8 -36.72 372.2 185.1 0
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 -450.3 -294.8
20 315.3 1264 62.32 89.96 -151 339.8 -66.17 -11 -297.8 -165.5 -256.3
22 34.1 -23.5 121.3 140.8 527.6 669.9 708.7 82.86 190.6 -133
23 36.7 51.06 228.5 69.9 742.1 649.1 826.8 552.1 242.8 176.5
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 R Q
1 1 CH3 0.9011 0.848
2 1 CH2 0.6744 0.54

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3 1 CH 0.4469 0.228
4 1 C 0.2195 0
5 2 CH2=CH 1.3454 1.176
6 2 CH=CH 1.1167 0.867
7 2 CH2=C 1.1173 0.988
8 2 CH=C 0.8886 0.676
70 2 C=C 0.6605 0.485
9 3 ACH 0.5313 0.4
10 3 AC 0.3652 0.12
11 4 ACCH3 1.2663 0.968
12 4 ACCH2 1.0396 0.66
13 4 ACCH 0.8121 0.348
14 5 OH 1 1.2
15 6 CH3OH 1.4311 1.432
16 7 H2O 0.92 1.4
17 8 ACOH 0.8952 0.68
18 9 CH3CO 1.6724 1.488
19 9 CH2CO 1.4457 1.18
20 10 CHO 0.998 0.948
21 11 CH3COO 1.9031 1.728
22 11 CH2COO 1.6764 1.42
29 14 CH2NH2 1.3692 1.236
36 17 ACNH2 1.06 0.816
42 20 COOH 1.3013 1.224
49 22 CCL2 1.8016 1.448
51 23 CCL3 2.6401 2.184
99 46 CON(CH2)2 2.4054 1.812

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Table 3. Interaction Parameters to be used in the calculations for the selected group
Do not edit this table unless you want to reprogram. Change values in Tables 1 and

T= 200 C
aij (i=column, j=row)
Sub Main 1
14 17 20 22 23 46 GroupGroup R Q CH3
391.5 920.7 663.5 53.76 24.9 380.9 1 1 CH3 0.9011 0.848 0
240.9 749.3 318.9 58.55 -13.99 200.2 2 1 CH2 0.6744 0.54 0
161.7 648.2 537.4 -144.4 -231.9 3 1 CH 0.4469 0.228 0
19.02 664.2 872.3 -111 -80.25 9 3 ACH 0.5313 0.4 -11.12
8.642 -52.39 199 65.28 -98.12 -382.7 10 3 AC 0.3652 0.12 -11.12
359.3 489.7 -202 -102.5 -139.4 11 4 ACCH3 1.2663 0.968 -69.7
48.89 243.2 -14.09 370.4 353.7 835.6 12 4 ACCH2 1.0396 0.66 -69.7
119.9 408.9 14 5 OH 1 1.2 156.4
6201 669.4 -130.3 -354.6 15 6 CH3OH 1.4311 1.432 16.51
497.5 67.52 -483.7 16 7 H2O 0.92 1.4 300
475.5 660.2 108.9 -209.7 17 8 ACOH 0.8952 0.68 275.8
0 -200.7 18 9 CH3CO 1.6724 1.488 26.76
-15.07 0 -396 -111 20 10 CHO 0.998 0.948 505.7
493.8 0 -44.7 39.63 -322.3 21 11 CH3COO 1.9031 1.728 114.8
140.8 543.3 0 0 29 14 CH2NH2 1.3692 1.236 -30.48
504.2 -84.53 0 36 17 ACNH2 1.06 0.816 1139
-70.25 0 42 20 COOH 1.3013 1.224 315.3
49 22 CCL2 1.8016 1.448 34.1
51 23 CCL3 2.6401 2.184 36.7
99 46 CON(CH2)2 2.4054 1.812 27.97

Table 4. Matrix of Y values used in calculations on sheet "UNIFAC (VL

Do not edit this table unless you want to reprogram. Change values in
Y
CH3 CH2 CH
CH3 1 1 1

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aij-UNIFAC (VLE)

CH2 1 1 1
CH 1 1 1
ACH 1.0237804 1.0237804 1.0237804
AC 1.0237804 1.0237804 1.0237804
ACCH3 1.1587138 1.1587138 1.1587138
ACCH2 1.1587138 1.1587138 1.1587138
OH 0.718528 0.718528 0.718528
CH3OH 0.965708 0.965708 0.965708
H2O 0.53044 0.53044 0.53044
ACOH 0.558276 0.558276 0.558276
CH3CO 0.9450125 0.9450125 0.9450125
CHO 0.3434223 0.3434223 0.3434223
CH3COO 0.7845624 0.7845624 0.7845624
CH2NH2 1.0665395 1.0665395 1.0665395
ACNH2 0.0900608 0.0900608 0.0900608
COOH 0.5135618 0.5135618 0.5135618
CCL2 0.9304656 0.9304656 0.9304656
CCL3 0.9253666 0.9253666 0.9253666
CON(CH2)2 0.9425989 0.9425989 0.9425989

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 aij-UNIFAC (VLE)

e calculations for the selected groups as indicated on sheet "UNIFAC (VLE)".

am. Change values in Tables 1 and 2 unless you want to reprogram.

aij (i=column, j=row)

1 1 3 3 4 4 5 6 7 8 9 10
CH2 CH ACH AC ACCH3 ACCH2 OH CH3OH H2O ACOH CH3CO CHO
0 0 61.13 61.13 76.5 76.5 986.5 697.2 1318 1333 476.4 677
0 0 61.13 61.13 76.5 76.5 986.5 697.2 1318 1333 476.4 677
0 0 61.13 61.13 76.5 76.5 986.5 697.2 1318 1333 476.4 677
-11.12 -11.12 0 0 167 167 636.1 637.3 903.8 1329 25.77 347.3
-11.12 -11.12 0 0 167 167 636.1 637.3 903.8 1329 25.77 347.3
-69.7 -69.7 -146.8 -146.8 0 0 803.2 603.2 5695 884.9 -52.1 586.6
-69.7 -69.7 -146.8 -146.8 0 0 803.2 603.2 5695 884.9 -52.1 586.6
156.4 156.4 89.6 89.6 25.82 25.82 0 -137.1 353.5 -259.7 84 -203.6
16.51 16.51 -50 -50 -44.5 -44.5 249.1 0 -181 -101.7 23.39 306.4
300 300 362.3 362.3 377.6 377.6 -229.1 289.6 0 324.5 -195.4 -116
275.8 275.8 25.34 25.34 244.2 244.2 -451.6 -265.2 -601.8 0 -356.1 -271.1
26.76 26.76 140.1 140.1 365.8 365.8 164.5 108.7 472.5 -133.1 0 -37.36
505.7 505.7 23.39 23.39 106 106 529 -340.2 480.8 -155.6 128 0
114.8 114.8 85.84 85.84 -170 -170 245.4 249.6 200.8 -36.72 372.2 185.1
-30.48 -30.48 -44.85 -44.85 296.4 296.4 -242.8 -481.7 -330.4 0 0 0
1139 1139 247.5 247.5 762.8 762.8 -17.4 -118.1 -341.6 -253.1 -450.3 0
315.3 315.3 62.32 62.32 89.96 89.96 -151 339.8 -66.17 -11 -297.8 -165.5
34.1 34.1 121.3 121.3 140.8 140.8 527.6 669.9 708.7 0 82.86 190.6
36.7 36.7 228.5 228.5 69.9 69.9 742.1 649.1 826.8 0 552.1 242.8
27.97 27.97 0 0 0 0 394.8 0 -509.3 0 0 0

calculations on sheet "UNIFAC (VLE).

nt to reprogram. Change values in Tables 1 and 2 unless you want to reprogram.

ACH AC ACCH3 ACCH2 OH CH3OH H2O ACOH CH3CO CHO CH3COO CH2NH2
0.8788 0.8788 0.8507114 0.8507114 0.1243118 0.2291156 0.0616929 0.0597678 0.3653612 0.239109 0.6122944 0.43717

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 aij-UNIFAC (VLE)

0.8788 0.8788 0.8507114 0.8507114 0.1243118 0.2291156 0.0616929 0.0597678 0.3653612 0.239109 0.6122944 0.43717
0.8788 0.8788 0.8507114 0.8507114 0.1243118 0.2291156 0.0616929 0.0597678 0.3653612 0.239109 0.6122944 0.43717
1 1 0.7026098 0.7026098 0.2606977 0.2600373 0.1480543 0.0602752 0.9469919 0.4799772 0.9874116 0.7105243
1 1 0.7026098 0.7026098 0.2606977 0.2600373 0.1480543 0.0602752 0.9469919 0.4799772 0.9874116 0.7105243
1.363781 1.363781 1 1 0.18313 0.2794701 5.925E-06 0.154088 1.1164043 0.2894491 6.013E-06 0.9605986
1.363781 1.363781 1 1 0.18313 0.2794701 5.925E-06 0.154088 1.1164043 0.2894491 6.013E-06 0.9605986
0.827481 0.827481 0.9468918 0.9468918 1 1.3361069 0.4737288 1.7313034 0.8373329 1.5377303 0.8076114 0.981901
1.1114603 1.1114603 1.0986152 1.0986152 0.5906855 1 1.4660072 1.2397905 0.9517674 0.5233134 1.0229153 0.4679571
0.4649994 0.4649994 0.4502035 0.4502035 1.6228788 0.5422284 1 0.5036725 1.51131 1.2778326 0.8572631 0.9018304
0.9478529 0.9478529 0.5968345 0.5968345 2.5972526 1.7515459 3.5676285 1 2.1225442 1.7735238 2.5852042 1
0.7437126 0.7437126 0.4615724 0.4615724 0.706332 0.7947427 0.3683852 1.3248591 1 1.0821612 1.570908 1
0.9517674 0.9517674 0.7992908 0.7992908 0.3269204 2.0524021 0.3619793 1.389383 0.7629771 1 1.262531 1
0.834083 0.834083 1.432318 1.432318 0.5953227 0.5900616 0.6541689 1.0806984 0.455371 0.6762396 1 1
1.0994282 1.0994282 0.5344913 0.5344913 1.670556 2.7678487 2.0103295 1 1 1 1 1
0.5926864 0.5926864 0.1994536 0.1994536 1.0374594 1.2835167 2.058484 1.707321 2.5901263 1 1.8646218 1.032363
0.8765926 0.8765926 0.8268517 0.8268517 1.3759408 0.487646 1.1501012 1.0235208 1.8764819 1.4187602 1.7189071 1
0.773858 0.773858 0.7426131 0.7426131 0.3278891 0.2427241 0.2236141 1 0.8393528 0.6684243 1.3245792 1
0.6169708 0.6169708 0.8626612 0.8626612 0.2083732 0.2536324 0.1742198 1 0.3113429 0.5986031 0.6886433 1
1 1 1 1 0.4341315 1 2.9341061 1 1 1 1 1

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 aij-UNIFAC (VLE)

11 14 17 20 22 23 46
CH3COO CH2NH2 ACNH2 COOH CCL2 CCL3 CON(CH2)2
232.1 391.5 920.7 663.5 53.76 24.9 380.9 CH3
232.1 391.5 920.7 663.5 53.76 24.9 380.9 CH2
232.1 391.5 920.7 663.5 53.76 24.9 380.9 CH
5.994 161.7 648.2 537.4 -144.4 -231.9 0 ACH
5.994 161.7 648.2 537.4 -144.4 -231.9 0 AC
5688 19.02 664.2 872.3 -111 -80.25 0 ACCH3
5688 19.02 664.2 872.3 -111 -80.25 0 ACCH2
101.1 8.642 -52.39 199 65.28 -98.12 -382.7 OH
-10.72 359.3 489.7 -202 -102.5 -139.4 0 CH3OH
72.87 48.89 243.2 -14.09 370.4 353.7 835.6 H2O
-449.4 0 119.9 408.9 0 0 0 ACOH
-213.7 0 6201 669.4 -130.3 -354.6 0 CH3CO
-110.3 0 0 497.5 67.52 -483.7 0 CHO
0 0 475.5 660.2 108.9 -209.7 0 CH3COO
0 0 -200.7 0 0 0 0 CH2NH2
-294.8 -15.07 0 -396 -111 0 0 ACNH2
-256.3 0 493.8 0 -44.7 39.63 -322.3 COOH
-133 0 140.8 543.3 0 0 0 CCL2
176.5 0 0 504.2 -84.53 0 0 CCL3
0 0 0 -70.25 0 0 0 CON(CH2)2

ACNH2 COOH CCL2 CCL3 CON(CH2)2

0.1428594 0.2460295 0.8925958 0.9487348 0.4470745

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 aij-UNIFAC (VLE)

0.1428594 0.2460295 0.8925958 0.9487348 0.4470745

0.1428594 0.2460295 0.8925958 0.9487348 0.4470745
0.2541153 0.3211676 1.3568809 1.6325112 1
0.2541153 0.3211676 1.3568809 1.6325112 1
0.2456658 0.1582465 1.2644003 1.1848402 1
0.2456658 0.1582465 1.2644003 1.1848402 1
1.1170888 0.6566623 0.8711258 1.2304453 2.2452894
0.3552341 1.5325391 1.2418885 1.3426176 1
0.5980973 1.030227 0.4571067 0.4735286 0.1710095
0.7761511 0.4213852 1 1 1
2.033E-06 0.2429807 1.3170421 2.1158258 1
1 0.349426 0.8670114 2.7795731 1
0.3660568 0.2477515 0.7944068 1.5576836 1
1.5283342 1 1 1 1
1 2.3092987 1.2644003 1 1
0.3521692 1 1.0990797 0.919654 1.976207
0.7426131 0.3171877 1 1 1
1 0.3445128 1.1956066 1 1
1 1.1600615 1 1 1

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