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.

NRTL Binary NRTL model.

NRTL5 Multicomponent NRTL with up to 5 components.

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.

Page 1
 Instructions

Copyright 1997-2012, 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 2
 484516603.xlsx

Margules Equation

GE/RT = x1 x2 ( A21 x1 + A12 x2 )

Margules Parameters A12_ A21_
1.861 1.6365
Table x1 increment 0.05

x1 x2 gamma1 gamma2 activity1 activity2 G(mix) /RT

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

Page 3
 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
Antoine Coeff A B C VL (cm3/mol) d (cal/cm3)1/2
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 0.898
y1 0 0.267 0.371 0.457 0.526 0.559 0.595 0.633 0.665 0.76
T (C) 80.1 70.67 66.44 62.87 60.2 58.64 58.02 58.1 58.47 59.9
Calculations based on data
T(K) 353.25 343.82 339.59 336.02 333.35 331.79 331.17 331.25 331.62 333.05
F1 0 0.01199 0.02336 0.04202 0.08187 0.15289 0.18496 0.35622 0.51352 0.61985 0.80007

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 0.898
g1 4.95691 4.89539 4.80679 4.6265 4.1889 3.44408 3.15202 2.05092 1.50662 1.28484 1.07217
g2 1 1.00051 1.00196 1.00634 1.02428 1.08727 1.13027 1.57493 2.57006 3.95629 9.88803
P1sat 1360.42 1106.07 952.138 793.176 624.096 515.235 495.453 476.601 481.258 471.905 438.819
P2sat 760 635.418 558.011 476.145 386.432 326.884 315.885 305.345 307.954 302.711 284.049
y1 calc 0 0.18524 0.3011 0.4249 0.56413 0.6636 0.68426 0.70609 0.66688 0.62387 0.55592
y2 calc 1 0.81476 0.69888 0.575 0.4354 0.33474 0.31334 0.28537 0.31346 0.34353 0.37695
T(K) 353.249 347.542 343.535 338.787 332.772 328.131 327.201 326.284 326.514 326.052 324.353
(Syi-1)2 2E-11 2E-11 4E-10 1E-08 2E-07 3E-06 6E-06 7E-05 0.00039 0.00106 0.00451
| <----- LLE region --->

This table permits calculation of LLE if it exists as above in column G and M (LLE explained in Chap 12)
LLE Dg*x 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 0.782 0.898
g1 2.99688 2.94956 2.89995 2.81299 2.62008 2.29504 2.16324 1.62368 1.3191 1.18425 1.04782
g2 1 1.00035 1.00134 1.00439 1.01699 1.06134 1.09135 1.38606 1.9717 2.68889 5.18562
P1sat 1360.42 1206.11 1097.85 970.383 809.732 680.292 650.46 593.275 588.078 588.256 598.28
P2sat 760 684.868 631.325 567.276 484.774 416.591 400.627 369.732 366.904 367 372.452
y1 calc 0 0.1217 0.20945 0.31607 0.45781 0.58386 0.61653 0.69585 0.71347 0.71681 0.74072

Page 4
 Regular

y2 calc 1 0.87802 0.79021 0.68372 0.54231 0.41643 0.38372 0.30411 0.28651 0.28306 0.25921
T(K) 353.249 349.904 347.34 344.037 339.317 334.908 333.793 331.532 331.317 331.325 331.737
(Syi-1)2 3E-11 8E-08 1E-07 5E-08 2E-08 8E-08 7E-08 1E-09 2E-10 2E-08 4E-09

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 591.288 g1 1.28533 A12 1.98475
P2sat 368.651 g2 2.06157 A21 1.7424
x1 0 0.026 0.05 0.088 0.164 0.28421 0.333 0.549 0.699 0.782 0.898
g1 7.27721 6.484 5.8508 5.00842 3.76577 2.56262 2.24017 1.41687 1.1611 1.07975 1.01645
g2 1 1.00152 1.00559 1.01723 1.05985 1.18411 1.25734 1.80067 2.50314 3.07897 4.22384
P1sat 1360.42 1035.63 885.787 759.286 653.482 605.458 599.369 591.838 593.207 602.28 644.91
P2sat 760 600.202 524.1 458.4 402.249 376.348 373.043 368.95 369.695 374.623 397.646
y1 calc 0 0.22972 0.34096 0.44033 0.53103 0.58022 0.58831 0.60575 0.63349 0.66913 0.77455
y2 calc 1 0.77037 0.65879 0.55956 0.46895 0.41971 0.41164 0.39424 0.36651 0.33086 0.22542
T(K) 353.249 345.77 341.64 337.674 333.908 332.028 331.781 331.473 331.529 331.9 333.581
(Syi-1)2 3E-11 1E-08 7E-08 1E-08 3E-10 4E-09 2E-09 8E-11 4E-11 6E-11 1E-09

Page 5
 Regular

0.97303 0.973 1
0.907 1
62.7 64.7

335.85 337.85
0.94253 0.94246 1

0.97303 0.973 1 360

350
T(K)

1.00571 1.00572 1
24.0457 24.0348 35.8576 340
515.2 515.063 759.995 330
320
326.865 326.789 458.773
0.66338 0.66319 1
310

0.27889 0.27903 0 300

328.129 328.123 337.698 OBJ
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

0.00333 0.00334 4E-11 3E-09 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.

0.97303 0.973 1 355

1.00384 1.00384 1
350
9.63552 9.63258 12.5016
T(K)

345
668.766 668.694 759.995
340
410.435 410.396 458.773
335
0.85951 0.8594 1
330
325
320 Page 6
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

x-y
 350

T(K)
345
340 Regular
335
330
0.14033 0.14044 0
334.482 334.48 337.698 OBJ 325

3E-08 3E-08 4E-11 5E-07 320

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

x-y

0.97303 0.973 1
355
1.00112 1.00112 1 350
T(K)
5.26252 5.26201 5.71104 345
716.653 716.608 759.995 340
335
435.917 435.893 458.773
330
0.91856 0.91848 1
325
0.0814 0.08149 0 320
336.213 336.211 337.698 OBJ 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
1E-09 1E-09 4E-11 1E-07
x-y

Page 7
Parameters Intermediate Calculations
Dg12/R(K) 200 t12 0.6708
Dg21/R(K) 200 t21 0.6708 4
a12 = a21 0.2 G12 0.87445
T (K) 298.15 G21 0.87445 gam
3.5 ma1
x1 x2 g1 g2
0 1 3.51622 1
0.05 0.95 3.10465 1.00319 3
0.1 0.9 2.76038 1.0128

gamma
0.15 0.85 2.47111 1.02894
0.2 0.8 2.22706 1.05188 2.5
0.25 0.75 2.02044 1.08204
0.3 0.7 1.84499 1.11997
0.35 0.65 1.69567 1.16642 2
0.4 0.6 1.56841 1.22232
0.45 0.55 1.45989 1.28884
0.5 0.5 1.36743 1.36743 1.5
0.55 0.45 1.28884 1.45989
0.6 0.4 1.22232 1.56841
0.65 0.35 1.16642 1.69567 1
0.7 0.3 1.11997 1.84499
0.75 0.25 1.08204 2.02044
0.8 0.2 1.05188 2.22706 0.5
0.85 0.15 1.02894 2.47111
0.9 0.1 1.0128 2.76038
0.95 0.05 1.00319 3.10465 0
1 0 1 3.51622 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

x1
NRTL MODEL
NOTE: The variable and sign conventions are the same as APSEN, not the original publication.
tij = aij + bij/T, other variables as defined on the binary sheet. To reproduce original NRTL, set aij = 0 and set bij = Dgij/R.

T(K) 298.15
Name HAc EtOH EtAc H2O PropAcid
x ### ### ### ### ###
gamma 0.90684 0.9286 1.78279 2.48217 0.82357
Intermediate Calculations
aij HAc EtOH EtAc H2O PropAcid
HAc 0 0 0 -1.9763 -3.0776 tau 0 -0.8468 -0.7891 0.06928 1.10785
EtOH 0 0 -1.2101 -0.9852 0 0.75625 0 0.6271 0.02851 0.94326
EtAc 0 -0.3981 0 -3.7198 0 1.73007 0.67315 0 0.59393 2.19087
H2O 3.3293 3.7555 9.4632 0 0 0.90137 1.48808 3.74231 0 2.70463
PropAcid 2.4452 0 0 0 0 -0.798 -1.2875 -1.0618 -0.434 0

bij HAc EtOH EtAc H2O PropAcid

HAc 0 -252.48 -235.28 609.889 1247.89 Gij 1 1.28923 1.26711 0.97943 0.71723
EtOH 225.476 0 547.762 302.237 281.232 0.79702 1 0.82851 0.99148 0.75354
EtAc 515.821 319.392 0 1286.14 653.208 0.5951 0.81714 1 0.888 0.51827
H2O -723.89 -676.03 -1705.7 0 806.384 0.76307 0.63991 0.47309 1 0.44424
PropAcid -966.96 -383.87 -316.59 -129.4 0 1.27049 1.47146 1.37514 1.13906 1

aij HAc EtOH EtAc H2O PropAcid term1 0.26125 -0.2968 -0.034 0.02583 0.76847
HAc 0 0.3 0.3 0.3 0.3 term2 0.88514 1.04355 0.98877 0.99959 0.68666
EtOH 0.3 0 0.3 0.3 0.3 inv term21.12977 0.95827 1.01136 1.00041 1.45633
EtAc 0.3 0.3 0 0.2 0.3 sq inv t2 1.27638 0.91828 1.02285 1.00081 2.12091
H2O 0.3 0.3 0.2 0 0.3 part1 0.29516 -0.2844 -0.0344 0.02584 1.11914
PropAcid 0.3 0.3 0.3 0.3 0
x1 0.2 0.2 0.2 0.2 0.2
0.2 0.2 0.2 0.2 0.2
0.2 0.2 0.2 0.2 0.2
0.2 0.2 0.2 0.2 0.2
0.2 0.2 0.2 0.2 0.2
part2 -0.1665 0.45397 0.7743 1.04599 -0.9864
part3 0.22646 0.24364 0.16172 0.1627 0.32681
lngamma -0.0978 -0.0741 0.57818 0.90913 -0.1941
 UNIQUAC

UNIQUAC Calculation Note: This spreadsheet uses the form of equations that permits the q of the residual part to diff
of the combinatorial part. (Anderson, T.F., Prausnitz, J.,M., Ind. Eng. Chem. Process Des. Dev
The formulas look a little different because or the use of the intermediate variable 'l', however t
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) Methano 1.43 1.43 1.43 -0.43 ### -32.78 529.57
(2) Benzen 3.19 2.4 2.4 1.76 ###
Table x1 increment 0.05

x1 x2 T(C) T(K) tau12 tau21 theta1 theta2 theta'1 theta'2 phi1

0.000000 1 90 363.15 ### ### 0 1 0 1 0
0.050000 0.95 90 363.15 ### ### ### ### ### ### ###
0.100000 0.9 90 363.15 ### ### ### ### ### ### ###
0.150000 0.85 90 363.15 ### ### ### ### ### ### ###
0.200000 0.8 90 363.15 ### ### ### ### ### ### ###
0.250000 0.75 90 363.15 ### ### ### ### ### ### 0.13
0.300000 0.7 90 363.15 ### ### ### ### ### ### ###
0.350000 0.65 90 363.15 ### ### ### ### ### ### ###
0.400000 0.6 90 363.15 ### ### ### ### ### ### ###
0.450000 0.55 90 363.15 ### ### ### ### ### ### ###
0.500000 0.5 90 363.15 ### ### ### ### ### ### ###
0.550000 0.45 90 363.15 ### ### ### ### ### ### ###
0.600000 0.4 90 363.15 ### ### ### ### ### ### ###
0.650000 0.35 90 363.15 ### ### ### ### ### ### ###
0.700000 0.3 90 363.15 ### ### ### ### ### ### ###
0.750000 0.25 90 363.15 ### ### ### ### ### ### ###
0.800000 0.2 90 363.15 ### ### ### ### ### ### ###
0.850000 0.15 90 363.15 ### ### ### ### ### ### ###
0.900000 ### 90 363.15 ### ### ### ### ### ### ###
0.950000 ### 90 363.15 ### ### ### ### ### ### ###
1.000000 0 90 363.15 ### ### 1 0 1 0 1

Page 11
 UNIQUAC

of the residual part to differ from q

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

phi2 ln(gam1) ln(gam2) gam1 gam2

1 ### 0 ### 1
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
0.87 ### ### ### ###
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
### ### ### ### ###
0 0 ### 1 ###

Page 12
 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 8.07131 7.280662
Antoine B 1730.63 1434.201
Antoine C 233.426 246.499
Psat (mmHg) 23.68641 99.57149 1 1 1
y 0.2283 0.7717 0.0000 0.0000 0.0000 Unhide columns G-R for LLE iterations.
Pcalc (mm Hg) 98.49289
T (K) = 298.15 Phase a
1 2 3 4 5
Name Water MEK Acetic
x 8.91E-01 9.89E-02 1.00E-02 1.00E-11 1.00E-11
g 1.065208 7.717527 0.084035 4.2692434 1.1873165
xg 0.949193 0.763362 0.00084 4.269E-11 1.187E-11

r 0.92 3.2479 2.2024 3.19 1.43

q 1.4 2.876 2.072 2.4 1.43
F 0.704851 0.276213 0.018936 2.743E-11 1.229E-11
q 0.803446 0.18321 0.013344 1.546E-11 9.21E-12
Sixiri 1.163083 Sixiqi 1.552715
aij matrix (i = row, j=column), enter 0's for unused cells
1 2 3 4 5
1 1 -2.0882 254.15 0 0
2 345.53 1 -254.13 0 0
3 -301.02 -4.5537 1 0 0
4 0 0 0 1 0
5 0 0 0 0 1

tij matrix (i = row, j=column)

1 2 3 4 5

Page 13
 UNIQUAC5

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

ln(gcomb) 0.032001 0.630614 0.46027 1.6776811 0.3064997

Si(qitij) 0.897566 1.005852 0.785576 1 1
qj/Si(qitij) 0.895138 0.182144 0.016987 1.546E-11 9.21E-12
Sj{qjtkj/(Siqitij)}1.085805 0.502899 2.658706 1.0942685 1.0942685
ln(gresid) 0.031169 1.41288 -2.93679 -0.2262445 -0.134804

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

Page 14
 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.

P= 745.516 mmHg
T(oC)= 80.37 oC
Table 1. Antoine Coefficients (mmHg) log10(Psat)=A-B/(T+C) where T[=] oC
comp1 comp2 comp3 comp4 comp5 Enter Antoine constants
A 8.87829 8.07131 8.1122 6.87632 or vapor pressures if
B 2010.33 1730.63 1592.86 1075.78 you want bubble P and
C 252.636 233.426 226.184 233.205 vapor phase
Psat[mmHg] 694.0196 359.8872 824.459 2790.137 concentrations
calculated
yi 0.58963 0.41037 0.00000 0.00000 0.00000 automatically.
Table 2. Component Structure Information and Activity Coefficient Calculation. Vapor phase mole
comp1 comp2 comp3 comp4 comp5 fractions calculated
automatically.
IPA Water C2-COOH EtOH C5H12
xi 0.500 0.500 0.000 0.000 0.000 Liquid phase mole fractions. Enter a very small number like 1E-
gi 20 or smaller for absent compounds - don't use zero.
SubGroup 1.267 1.700 0.980 1.107 12.607
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.
11 ACCH3 Check Table 1 on sheet "aij-UNIFAC (VLE)".
12 ACCH2
14 OH 1 1 The sub-groups available in this table may be
15 CH3OH changed in this column by changing the
SubGroup number. If you change a sub-group
16 H2O 1
here, be sure to edit the component structure
17 ACOH information in the table. Available subgroups
18 CH3CO and subgroup numbers are in Table 2 of sheet
20 CHO "aij-UNIFAC (VLE)".

21 CH3COO
29 CH2NH2
36 ACNH2
42 COOH 1
49 CCL2
51 CCL3
99 CON(CH2)2
Sknk(i)xi 2 0.5 3E-20 3E-20 5E-20
N groups 4 1 3 3 5

q 3.1240 1.4000 2.6120 2.5880 3.3160

r 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 15
 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 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

Page 16
 aij-UNIFAC (VLE)

2 1 CH2 0.6744 0.54

3 1 CH 0.4469 0.228
4 1C 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

Page 17
 aij-UNIFAC (VLE)

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= 80.37 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

Page 18
aij-UNIFAC (VLE)

CH3 1 1 1
CH2 1 1 1
CH 1 1 1
ACH 1.031955 1.031955 1.031955
AC 1.031955 1.031955 1.031955
ACCH3 1.2179389 1.2179389 1.2179389
ACCH2 1.2179389 1.2179389 1.2179389
OH 0.6424876 0.6424876 0.6424876
CH3OH 0.954372 0.954372 0.954372
H2O 0.4280102 0.4280102 0.4280102
ACOH 0.4583355 0.4583355 0.4583355
CH3CO 0.9270981 0.9270981 0.9270981
CHO 0.2391963 0.2391963 0.2391963
CH3COO 0.7227195 0.7227195 0.7227195
CH2NH2 1.0900446 1.0900446 1.0900446
ACNH2 0.0398799 0.0398799 0.0398799
COOH 0.4098815 0.4098815 0.4098815
CCL2 0.9080476 0.9080476 0.9080476
CCL3 0.9013938 0.9013938 0.9013938
CON(CH2)2 0.9239304 0.9239304 0.9239304

Page 19
 aij-UNIFAC (VLE)

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

m. 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

Page 20
 aij-UNIFAC (VLE)

0.8412065 0.8412065 0.805417 0.805417 0.0613901 0.1391552 0.0240356 0.0230371 0.2598658 0.147338 0.5186428 0.3304058
0.8412065 0.8412065 0.805417 0.805417 0.0613901 0.1391552 0.0240356 0.0230371 0.2598658 0.147338 0.5186428 0.3304058
0.8412065 0.8412065 0.805417 0.805417 0.0613901 0.1391552 0.0240356 0.0230371 0.2598658 0.147338 0.5186428 0.3304058
1 1 0.6235091 0.6235091 0.1654093 0.1648488 0.07757 0.0232992 0.929698 0.3744094 0.9831877 0.6329272
1 1 0.6235091 0.6235091 0.1654093 0.1648488 0.07757 0.0232992 0.929698 0.3744094 0.9831877 0.6329272
1.5147529 1.5147529 1 1 0.103105 0.181542 1.009E-07 0.08183 1.1587884 0.1902698 1.029E-07 0.9476199
1.5147529 1.5147529 1 1 0.103105 0.181542 1.009E-07 0.08183 1.1587884 0.1902698 1.029E-07 0.9476199
0.7761178 0.7761178 0.9295665 0.9295665 1 1.4737556 0.3679003 2.0846728 0.7885099 1.7787701 0.7512769 0.9758508
1.1519253 1.1519253 1.1341425 1.1341425 0.4942925 1 1.6686145 1.3333282 0.9359781 0.4203314 1.030788 0.3619136
0.3588553 0.3588553 0.3436557 0.3436557 1.9118165 0.4407886 1 0.3993523 1.7379858 1.3883674 0.8137298 0.8708419
0.9308295 0.9308295 0.5011914 0.5011914 3.5874381 2.1173593 5.486597 1 2.7381925 2.1529931 3.5651824 1
0.6728048 0.6728048 0.35532 0.35532 0.627934 0.7352983 0.2627485 1.4571744 1 1.1114662 1.8303221 1
0.9359781 0.9359781 0.7409356 0.7409356 0.2239395 2.6177673 0.2566515 1.5529321 0.6962316 1 1.3661615 1
0.7844165 0.7844165 1.617494 1.617494 0.4994931 0.4935939 0.5666566 1.1094558 0.3489453 0.5923893 1 1
1.1352659 1.1352659 0.432391 0.432391 1.9873597 3.9062664 2.5461963 1 1 1 1 1
0.4965347 0.4965347 0.1155874 0.1155874 1.0504507 1.3966392 2.6281547 2.0461143 3.5742703 1 2.302278 1.0435501
0.8383797 0.8383797 0.7753278 0.7753278 1.5328563 0.3824374 1.2058379 1.0316048 2.3218985 1.5970352 2.0647194 1
0.7095526 0.7095526 0.6714739 0.6714739 0.2248281 0.150327 0.1347013 1 0.7910567 0.5832443 1.4567623 1
0.5239512 0.5239512 0.8205949 0.8205949 0.1225576 0.1594372 0.0964467 1 0.2097745 0.5031802 0.6069769 1
1 1 1 1 0.3273359 1 4.223457 1 1 1 1 1

Page 21
 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

Page 22
 aij-UNIFAC (VLE)

0.0739491 0.1530733 0.8589276 0.9319888 0.3404627

0.0739491 0.1530733 0.8589276 0.9319888 0.3404627
0.0739491 0.1530733 0.8589276 0.9319888 0.3404627
0.1598436 0.2186812 1.5045043 1.9270189 1
0.1598436 0.2186812 1.5045043 1.9270189 1
0.1527705 0.0847991 1.3688693 1.2548333 1
0.1527705 0.0847991 1.3688693 1.2548333 1
1.1597394 0.5695492 0.8313893 1.3198941 2.9521724
0.2502708 1.7707377 1.3363489 1.4833751 1
0.5026112 1.0406612 0.3507266 0.3676922 0.0940756
0.7123681 0.3145371 1 1 1
2.411E-08 0.1505398 1.4456786 2.7265988 1
1 0.2448094 0.826138 3.9284283 1
0.2605282 0.1545088 0.7348824 1.8097291 1
1.7642381 1 1 1 1
1 3.0653536 1.3688693 1 1
0.2473851 1 1.1347844 0.8939538 2.48852
0.6714739 0.2150619 1 1 1
1 0.2402134 1.2701176 1 1
1 1.2198352 1 1 1

Page 23
 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
Note: hidden other functional groups without
P= 86.446 mmHg columns with -> <- editing "aij-UNIFAC (LLE)". That
will be provided in the future.
T(oC)= 25 oC intermediate calcs
Antoine Coefficients (mmHg) log10(Psat)=A-B/(T+C) where T[=] oC
comp1 comp2 comp3 comp4 comp5 Note: MeOH is not a unique group in the citation used to
A 8.07131 7.2806621 develop this sheet.
B 1730.63 1434.2011 T. Magnussen, P. Rasmussen, A. Fredenslund,
C 233.426 246.49905 Ind. Eng. Chem. Process Des. Dev., 1981, 20, 331-339.
Psat[mmHg]23.68641 99.571488 1 1 1
yi 0.26079 0.73763 0.00158 0.00000 0.00000 a phase

1 2 3 comp4 comp5 Table for LLE as described in text.

Water MEK c2-COOH EtOH C5H12 Can be used for binary or ternary.
x 0.830 0.100 0.070 0.000 0.000 Follow text instructions to create macro
gi 1.147 6.414 1.951 1.705 199.114 1 2 3
CH3 1 1 1 2 Ki,old
CH2 1 1 1 3 Ki,new
CH xai,old
ACH xai,new
ACCH2 xbi,old
ACCH3 xbi,new
OH 1
2-Propanol
H2O 1 To avoid having the screen jump to follow the
ACOH cursor during macro execution, just hide ALL
CH3CO 1 of the columns that contain the activity coefficient
CHO calculations before executing the macro.
COOH 1
CH3COO
CH2O
CHCL2
CCL3
ACNH2
S kn k(i)xi 0.830153 0.2995423 0.21 3E-20 5E-20
N groups 1 3 3 3 5

q 1.4000 2.8760 2.6120 2.5880 3.3160

r 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

Page 24
 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= 85.603 mmHg columns with -> <-
T(oC)= 25 oC intermediate calcs
Antoine Coefficients (mmHg) log10(Psat)=A-B/(T+C) where T[=] oC
comp1 comp2 comp3 comp4 comp5
A 8.07131 7.2806621 0 0 0
B 1730.63 1434.2011 0 0 0 b phase
C 233.426 246.49905 0 0 0
P [mmHg]23.68641
sat
99.571488 1 1 1
yi 0.26079 0.73763 0.00158 0.00000 0.00000

comp1 comp2 comp3 comp4 comp5

Water MEK c2-COOH EtOH C5H12
x 0.773 0.139 0.088 0.000 0.000
gi 1.235 4.541 1.535 1.396 104.701
CH3 0 1 1 1 2
CH2 0 1 1 1 3
CH 0 0 0 0 0
ACH 0 0 0 0 0
ACCH2 0 0 0 0 0
ACCH3 0 0 0 0 0
OH 0 0 0 1 0
2-Propano 0 0 0 0 0
H2O 1 0 0 0 0
ACOH 0 0 0 0 0
CH3CO 0 1 0 0 0
CHO 0 0 0 0 0
COOH 0 0 1 0 0
CH3COO 0 0 0 0 0
CH2O 0 0 0 0 0
CHCL2 0 0 0 0 0
CCL3 0 0 0 0 0
ACNH2 0 0 0 0 0
S kn k(i)xi 0.772916 0.417 0.264251 3E-20 5E-20
N groups 1 3 3 3 5

q 1.4000 2.8760 2.6120 2.5880 3.3160

r 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

Page 25
 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) NOTE: Blank cells mean value is unavailable
Main 1 3 4 5 7 8 9 10 11 13 14 15 17 18
Group R Q CH3 CH2 CH ACH ACCH2 ACCH3 OH 2-Propanol H2O ACOH CH3CO CHO COOH CH3COO CH2O CHCL2 CCL3
1 CH3 0.901 0.848 0 0 0 -114.8 -115.7 -115.7 644.6 310.7 1300 2255 472.6 158.1 139.4 972.4 662.1 -243.9 7.5
CH2 0.674 0.54 0 0 0 -114.8 -115.7 -115.7 644.6 310.7 1300 2255 472.6 158.1 139.4 972.4 662.1 -243.9 7.5
CH 0.447 0.228 0 0 0 -114.8 -115.7 -115.7 644.6 310.7 1300 2255 472.6 158.1 139.4 972.4 662.1 -243.9 7.5
3 ACH 0.531 0.4 156.5 156.5 156.5 0 167 167 703.9 577.3 859.4 1649 593.7 362.3 461.8 6 32.14 -231.9
4 ACCH2 1.04 0.66 104.4 104.4 104.4 -146.8 0 0 4000 906.8 5695 292.6 916.7 1218 339.1 5688 213.1 -12.14
ACCH3 1.266 0.968 104.4 104.4 104.4 -146.8 0 0 4000 906.8 5695 292.6 916.7 1218 339.1 5688 213.1 -12.14
5 OH 1 1.2 328.2 328.2 328.2 -9.21 1.27 1.27 0 991.3 28.73 -195.5 67.07 1409 -104 195.6 262.5 272.2 -61.57
7 2-Propanol 3.249 3.124 -131.9 -131.9 -131.9 -252 -273.6 -273.6 -268.8 0 5.89 -153.2 353.8 -338.6 -57.98 487.1 1970 507.8 1544
8 H2O 0.92 1.4 342.4 342.4 342.4 372.8 203.7 203.7 -122.4 104.9 0 344.5 -171.8 -349.9 -465.7 -6.32 64.42 370.7 356.8
9 ACOH 0.895 0.68 -159.8 -159.8 -159.8 -473.2 -470.4 -470.4 -63.15 -547.2 -595.9 0 -825.7 -898.3
10 CH3CO 1.672 1.488 66.56 66.56 66.56 -78.31 -73.87 -73.87 216 -127.6 634.8 -568 0 -37.36 1247 258.7 5.202 -301 12.01
11 CHO 0.998 0.948 146.1 146.1 146.1 -75.3 223.2 223.2 -431.3 231.4 623.7 128 0 0.75 -245.8
13 COOH 1.301 1.224 1744 1744 1744 75.49 147.3 147.3 118.4 349.1 652.3 -101.3 1051 0 -117.6 -96.62 1670 48.15
14 CH3COO 1.903 1.728 -320.1 -320.1 -320.1 114.8 -170 -170 180.6 -152.8 385.9 -337.3 58.84 1090 1417 0 -235.7 108.9 -209.7
15 CH2O 0.918 0.78 1571 1571 1571 52.13 65.69 65.69 137.1 -218.1 212.8 52.38 1402 461.3 0 137.8 -154.3
17 CHCL2 2.061 1.684 27.9 27.9 27.9 669.2 -401.6 740.4 550.6 437.7 -132.9 -197.7 0
18 CCL3 2.64 2.184 21.23 21.23 21.23 288.5 33.61 33.61 418.4 -465.7 793.2 342.2 370.4 176.5 -20.93 0
22 ACNH2 1.06 0.816 175.8 175.8 175.8 -218.9 -15.41 -15.41 529 -239.8 -860.3 857.7 681.4 -216.3

Y
CH3 CH2 CH ACH ACCH2 ACCH3 OH 2-PropanH2O ACOH CH3CO CHO COOH CH3COO CH2O CHCL2 CCL3
CH3 1 1 1 1.4697 1.47412 1.47412 0.115 0.35272 0.0128 0.0005 0.20493 0.588 0.6265 0.038333 0.1085 2.2661 0.9752

Page 26
 aij-UNIFAC (LLE)

CH2 1 1 1 1.4697 1.47412 1.47412 0.115 0.35272 0.0128 0.0005 0.20493 0.588 0.6265 0.038333 0.1085 2.2661 0.9752
CH 1 1 1 1.4697 1.47412 1.47412 0.115 0.35272 0.0128 0.0005 0.20493 0.588 0.6265 0.038333 0.1085 2.2661 0.9752
ACH 0.592 0.5916 0.59161 1 0.57114 0.57114 0.094 0.14424 0.056 0.004 0.13652 0.297 0.2125 0.980077 0.8978 1 2.1767
ACCH2 0.705 0.7046 0.70458 1.6362 1 1 1E-06 0.04777 5E-09 0.3748 0.04621 0.017 0.3207 5.18E-09 0.4893 1 1.0416
ACCH3 0.705 0.7046 0.70458 1.6362 1 1 1E-06 0.04777 5E-09 0.3748 0.04621 0.017 0.3207 5.18E-09 0.4893 1 1.0416
OH 0.333 0.3326 0.33261 1.0314 0.99575 0.99575 1 0.03598 0.9081 1.9265 0.79855 0.009 1.4174 0.518899 0.4146 0.4013 1.2294
2-Propanol 1.556 1.5564 1.55643 2.3285 2.50342 2.50342 2.463 1 0.9804 1.6717 0.30524 3.113 1.2147 0.195198 0.0014 0.1821 0.0056
H2O 0.317 0.3171 0.31714 0.2864 0.50499 0.50499 1.508 0.7034 1 0.3149 1.7793 3.234 4.7682 1.021424 0.8057 0.2884 0.3022
ACOH 1.709 1.7091 1.70911 4.8896 4.84394 4.84394 1.236 6.26713 7.3791 1 15.9492 1 1 20.34658 1 1 1
CH3CO 0.8 0.7999 0.79992 1.3004 1.28115 1.28115 0.485 1.53414 0.1189 6.72 1 1.133 0.0153 0.419923 0.9827 2.7444 0.9605
CHO 0.613 0.6126 0.61261 1.2873 0.47302 0.47302 4.249 0.46019 0.1235 1 0.65096 1 0.9975 2.280551 1 1 1
COOH 0.003 0.0029 0.00288 0.7763 0.61015 0.61015 0.672 0.31009 0.1122 1 1.40461 0.029 1 1.483542 1.3827 0.0037 0.8509
CH3COO 2.926 2.926 2.92595 0.6804 1.76859 1.76859 0.546 1.66945 0.2741 3.0997 0.8209 0.026 0.0086 1 2.2046 0.694 2.0205
CH2O 0.005 0.0051 0.00515 0.8396 0.80226 0.80226 0.631 2.07822 0.4898 1 0.83888 1 0.0091 0.212841 1 0.6299 1.6779
CHCL2 0.911 0.9107 0.91067 1 1 1 0.106 3.84577 0.0835 1 0.15775 1 0.2304 1.561659 1.9408 1 1
CCL3 0.931 0.9313 0.93127 0.38 0.89339 0.89339 0.246 4.76818 0.0699 1 0.31735 1 0.2887 0.553229 1.0727 1 1
ACNH2 0.555 0.5545 0.55453 2.0838 1.05304 1.05304 0.17 1 2.2351 17.912 0.05632 1 0.1017 1 1 1 2.0657

Page 27
 aij-UNIFAC (LLE)

22
ACNH2
902.2 CH3
902.2 CH2
902.2 CH
1.64 ACH
689.6 ACCH2
689.6 ACCH3
-348.2 OH
2-Propanol
-109.8 H2O
-851.6 ACOH
1010 CH3CO
CHO
942.2 COOH
CH3COO
CH2O
CHCL2
-75.5 CCL3
0 ACNH2

ACNH2
0.04851

Page 28
 aij-UNIFAC (LLE)

0.04851
0.04851
0.99451
0.09897
0.09897
3.21513
1
1.44523
17.3967
0.03379
1
0.04242
1
1
1
1.28818
1

Page 29
 ### added NRTL and NRTL5 (CTL)
3/30/2018 fix bugs in UNIFAC LLE. Fix errors in aij for groups aij (18,10), aij (18,14).
Fix UNIFAC (LLEa) and UNIFAC (LLEb) to extend formulas in rows 51 and 51 through row 41.
through row 41.
 LLE

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

Summary of calculations for Example in Textbook
x1 DGmix/RT gw gmek gw*xw gmek*xmek Coexistence calculation
0.00 0 ### 1 0 1 @x1~0.35
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

0
Gm/RT

-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 0.80 0.90 1.00

xw

1.2

0.8
xigi

0.6

0.4
Page 32
0.2
 1

0.8 LLE

xigi 0.6

0.4

0.2

0
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

xw

Page 33