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Instructions

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

Margules Worksheet using the Margules equation with two adjustable parameters.

Regular A spreadsheet to calculate VLE for methanol + benzene


using van Laar and Scatchard/Hildbrand theory.

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

UNIQUAC5 A spreadsheet to use UNIQUAC with up to 5 components.

ANTOINE Table of Antoine Coefficients.

UNIFAC (VLE) A spreadsheet to use with the UNIFAC activity coefficient model
for VLE for up to 5 components.

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

UNIFAC (LLEa,b) Two spreadsheets to use with the UNIFAC activity coefficient model
for LLE for up to 5 components.

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

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

Worksheets are protected. Values in blue may be changed without unlocking the spreadsheet, which will
permit most common calculations.

Copyright 1997-2000, Carl Lira, Richard Elliott


For use with "Introductory Chemical Engineering Thermodynamics" by J.R. Elliott, C.T. Lira
www.egr.msu.edu/~lira/thermtxt.htm

Page1
360601950.xls

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

Page2
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 MeOH 8.08097 1582.271 239.726 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 0.284209 0.333 0.549 0.699
y1 0 0.267 0.371 0.457 0.526 0.559 0.595 0.633
T (C) 80.1 70.67 66.44 62.87 60.2 58.64 58.02 58.1
Calculations based on data
T(K) 353.25 343.82 339.59 336.02 333.35 331.79 331.17 331.25
F1 0 0.011988 0.023364 0.042017 0.081869 0.152887 0.184959 0.356216 0.513517

Scatchard-Hildebrand model with zero binary interaction coefficient (x's from above) see plot ---->
x1 0 0.026 0.05 0.088 0.164 0.284209 0.333 0.549 0.699
g1 4.956911 4.895389 4.806788 4.626503 4.188901 3.44408 3.152024 2.050917 1.506623
g2 1 1.000515 1.001979 1.006504 1.025374 1.092665 1.138907 1.622229 2.731147
P 1
sat
1360.424 1106.072 952.1375 793.1757 624.0955 515.2352 495.4532 476.6008 481.2578
P 2
sat
759.9965 635.4177 558.0115 476.1449 386.4323 326.8842 315.8845 305.3454 307.9541
y1 calc 0 0.185238 0.3011 0.424905 0.564133 0.663596 0.684263 0.706092 0.666878
y2 calc 1 0.814757 0.698895 0.57509 0.435861 0.336398 0.315739 0.293945 0.333107
T(K) 353.2494 347.542 343.5352 338.7874 332.7723 328.1309 327.2006 326.2845 326.5136
(Syi-1)2 2.16E-11 2.48E-11 2.73E-11 3E-11 3.41E-11 3.77E-11 3.58E-12 1.42E-09 2.35E-10
| <----- 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 0.000254 0.284209
g2*x2 0 0.973033

Scatchard-Hildebrand model with binary interaction coefficient kij= -0.0331


x1 0 0.026 0.05 0.088 0.164 0.284209 0.333 0.549 0.699
g1 2.996881 2.94956 2.89995 2.812993 2.620077 2.295044 2.163238 1.623682 1.319103
g2 1 1.00035 1.001341 1.004387 1.016992 1.06134 1.091355 1.386062 1.9717
P 1
sat
1360.423 1206.105 1097.85 970.3827 809.732 680.2924 650.4601 593.2755 588.0778
P 2
sat
759.9959 684.8684 631.3249 567.2759 484.7742 416.5914 400.6269 369.7319 366.9037
y1 calc 0 0.121703 0.209455 0.316068 0.45781 0.583864 0.616532 0.695851 0.713472
y2 calc 0.999995 0.87802 0.790215 0.683717 0.542312 0.416425 0.383723 0.304111 0.286514

Page3
Regular

T(K) 353.2494 349.9045 347.3401 344.037 339.317 334.908 333.7935 331.5318 331.3173
(Syi-1)2 3E-11 7.63E-08 1.09E-07 4.61E-08 1.51E-08 8.36E-08 6.52E-08 1.45E-09 1.84E-10
First, set this to 331.3 (c
azeotrope T and compos
then adjust kij until cell J
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 591.2879 g1 1.28533 A12 1.984748 These values are calculated from the activitiy coe
P2sat 368.6508 g2 2.061572 A21 1.742401 composition values at the azeotrope.

x1 0 0.026 0.05 0.088 0.164 0.284209 0.333 0.549 0.699


g1 #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
g2 1 #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
P 1
sat
1360.423 1035.625 885.7867 759.2857 653.4823 605.4583 599.3688 591.8375 593.2068
P 2
sat
759.9959 600.202 524.0995 458.4003 402.2488 376.3476 373.0431 368.9498 369.6946
y1 calc #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
y2 calc 0.999995 #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
T(K) 353.2494 345.7698 341.6401 337.6738 333.9083 332.0285 331.7813 331.4727 331.529
(Syi-1)2 #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME?

Page4
Regular

d (cal/cm3)1/2

0.782 0.898 0.973033 0.973 1


0.665 0.76 0.907 1
58.47 59.9 62.7 64.7

331.62 333.05 335.85 337.85


0.619848 0.800071 0.942532 0.942464 1

0.782 0.898 0.973033 0.973 1 360


350
T(K)

1.284842 1.072172 1.005708 1.005721 1


4.331675 11.64805 29.02295 29.01087 39.80158 340
471.905 438.8193 515.2002 515.0633 759.9949 330
302.7114 284.0489 326.8648 326.7889 458.7727 320
0.623875 0.555921 0.663379 0.663189 0.999993 310
0.376121 0.444051 0.336616 0.336805 0 300
326.0516 324.353 328.1293 328.123 337.6976 OBJ
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
1.94E-11 8.1E-10 2.67E-11 3.54E-11 4.45E-11 3E-09 x-y
E region ---> |

Bubble temperatures can be found The cross-overs in the above diagram are indicative
across the composition range using
Solver by setting this to zero and
of LLE. The points represent experimental data.
adjusting B30:O30 An interaction parameter is necessary to fit the data
without predicting LLE.

0.782 0.898 0.973033 0.973 1


355
1.184253 1.047825 1.003836 1.003845 1
350
2.688894 5.185622 9.635523 9.632578 12.50164
T(K)

345
588.2562 598.28 668.7655 668.6936 759.995
367.0008 372.4518 410.4348 410.3963 458.7727 340
0.71681 0.740723 0.859509 0.859395 0.999993 335
0.283063 0.259213 0.140328 0.140442 0 330
325
320
Page5
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
x-y
T(K
345
340
Regular
335
330
331.3247 331.7369 334.4823 334.4796 337.6976 OBJ 325
1.59E-08 4E-09 2.67E-08 2.66E-08 4.42E-11 5E-07
320
First, set this to 331.3 (close to
Then, use Solver to adjust
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
azeotrope T and composition), x-y
B47:O47 to calc bubble T's.
then adjust kij until cell J48 = 0.

values are calculated from the activitiy coefficient and


sition values at the azeotrope.

0.782 0.898 0.973033 0.973 1


355
#NAME? #NAME? #NAME? #NAME? 1
350
#NAME? #NAME? #NAME? #NAME? #NAME?

T(K)
345
602.2797 644.9099 716.6531 716.608 759.995 340
374.6233 397.6455 435.9169 435.893 458.7727 335
#NAME? #NAME? #NAME? #NAME? 0.999993 330
#NAME? #NAME? #NAME? #NAME? #NAME? 325
331.8997 333.5814 336.2127 336.2111 337.6976 OBJ 320
#NAME? #NAME? #NAME? #NAME? #NAME? ### 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
x-y

After determining the A12 and A21, the bubble


temperatures are calculated across the composition
range as before.

Page6
Regular

3 0.4 0.5 0.6 0.7 0.8 0.9 1


x-y

bove diagram are indicative


sent experimental data.
r is necessary to fit the data

Page7
.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x-y
Regular

.3 0.4 0.5 0.6 0.7 0.8 0.9 1


x-y

3 0.4 0.5 0.6 0.7 0.8 0.9 1


x-y

Page8
UNIQUAC

UNIQUAC Calculation Note: This spreadsheet uses the form of equations that permits the q of the residual par
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', 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 ### -32.78 529.57
(2) Benzene 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


0.000000 1 90 363.15 ### ### 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 ### ### ### ### ###
0.300000 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

Page9
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 phi1 phi2 ln(gam1) ln(gam2) gam1 gam2


1 0 1 ### 0 ### 1
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### 0.13 0.87 ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
### ### ### ### ### ### ###
0 1 0 0 ### 1 ###

Page10
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 7.2806621
Antoine B 1730.63 1434.2011
Antoine C 233.426 246.49905
P (mmHg)
sat
23.686414 99.571488 1 1 1
y 0.2283 0.7717 0.0000 0.0000 0.0000 Unhide columns G-R for LLE iterations.
Pcalc (mm Hg) 98.492886
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 1.0652077 7.7175272 0.0840355 4.269243444 1.18731645
xg 0.949193 0.7633618 0.0008404 4.26924E-11 1.1873E-11

r 0.92 3.2479 2.2024 3.19 1.43


q 1.4 2.876 2.072 2.4 1.43
F 0.7048511 0.276213 0.0189359 2.74271E-11 1.2295E-11
q 0.8034456 0.1832101 0.0133444 1.54568E-11 9.2097E-12
Sixiri 1.163083 Sixiqi 1.5527152
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
1 1 1.0070284 0.4263804 1 1

Page11
UNIQUAC5

2 0.313827 1 2.345166 1 1
3 2.7445744 1.0153904 1 1 1
4 1 1 1 1 1
5 1 1 1 1 1

ln(gcomb) 0.0320012 0.6306144 0.4602702 1.677681099 0.30649967


Si(qitij) 0.8975665 1.0058523 0.7855758 1 1
qj/Si(qitij) 0.8951377 0.1821441 0.0169867 1.54568E-11 9.2097E-12
Sj{qjtkj/(Siqitij)} 1.0858048 0.5028992 2.6587062 1.094268528 1.09426853
ln(gresid
) 0.0311687 1.4128796 -2.936786 -0.22624447 -0.13480399

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

Page12
Antoine coefficients for: log10(Psat[mmHg])=A-B/(T[oC]+C)
T[oC] 200

methanol ethanol 1-propanol 1-propanol 2-propanol 1-butanol 1-butanol


A 8.08097 8.1122 7.74416 8.37895 8.87829 7.81028 7.75328
B 1582.271 1592.864 1437.686 1788.02 2010.33 1522.56 1506.07
C 239.726 226.184 198.463 227.438 252.636 191.95 191.593
tMin[oC] 15 20 60 -15 -26 30 70
tMax[oC] 84 93 106 98 83 70 120
Source 3 3 3 3 2 2
Psat[mmHg] ### ### ### ### ### ### ###

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
tMin[oC] -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] ### ### ### ### ### ### ###

cyclohexanecyclohexane methylcycloh isopentane toluene benzene m-xylene


A ### 6.85146 7.1161 8.1122 6.95087 6.87987 7.00909
B ### 1206.47 1444.59 1592.864 1342.31 1196.76 1462.266
C ### 223.136 240.184 226.184 219.187 219.161 215.11
tMin[oC] 6.7 7 -3 20 -27 8 29
tMax[oC] 80.7 81 100 93 111 80 166
Source 1 3 1 3 3 3
Psat[mmHg] ### ### ### ### ### ### ###

water acetonitrile Triethylamine acetic acid acetic acid chloroform dichloromethan


A 8.07131 7.33986 5.85879 8.021 8.26735 6.95465 7.0803
B 1730.63 1482.29 695.666 1936.01 2258.222 1170.966 1138.91
C 233.426 250.523 144.832 258.451 300.97 226.232 231.45
tMin[oC] 1 -27 50 18 118 -10 -44
tMax[oC] 100 82 95 118 227 60 59
Source 3 3 3 3 3 3 3
Psat[mmHg] ### ### ### ### ### ### ###

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 ### ###
1305.198 1157 ### ###
173.427 168.279 ### ###
89 72 55 80
126 107 150 200
3 3 1 1
### ### ### ###

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
### ### ### ### ### ### ###

o-xylene p-xylene acetone acetone acrolein ethyl acetat 1,4-dioxane 2-butanone 2-butanone
7.00154 6.99053 7.6313 7.11714 7.06691 7.10179 7.43155 ### 7.06356
1476.393 1453.43 1566.69 1210.595 1204.95 1244.95 1554.679 ### 1261.339
213.872 215.31 273.419 229.664 235.35 217.881 240.337 ### 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
### ### ### ### ### ### ### ### ###

dichoromethatetrachloro 1,2-dichlor Benzyl chlornitroethane Biphenyl Naphthalene


7.40916 6.84093 7.0253 ### ### 13.5354 8.62233
1325.938 1177.91 1271.254 ### ### 4993.37 2165.72
252.616 220.576 222.927 ### ### 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)
### ### ### ### ### ### ###

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
7.23064
1477.021
237.517
36
102
3
###
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.

Pethanol 742.3559
Pwater 599.8698
1342.226
As distributed, this cell has a
P= 1342.226 mmHg formula to calculate the
bubble pressure.
T(oC)= 100.3119 oC
Table 1. Antoine Coefficients (mmHg) log10(Psat)=A-B/(T+C) where T[=] oC
comp1 comp2 comp3 comp4 comp5
A 8.1122 8.07131 8.1122 6.87632 Enter Antoine constants or
vapor pressures if you want
B 1592.864 1730.63 1592.864 1075.78
bubble P and vapor phase
C 226.184 233.426 226.184 233.205 concentrations calculated
Psat[mmHg] 1712.12202 768.622473 1712.122 4474.6173 automatically.
yi 0.55308 0.44692 0.00000 0.00000 0.00000
Table 2. Component Structure Information and Activity Coefficient Calculation. Vapor phase mole fractions
comp1 comp2 comp3 comp4 comp5 calculated automatically.
methanol water C2-COOH EtOH C5H12
xi 0.300 0.700 0.000 0.000 0.000 Liquid phase mole fractions. Enter a very small number like 1E-20 or
gi smaller for absent compounds - don't use zero.
SubGroup 1.445 1.115 2.332 2.176 112.093
1 CH3 1 1 1 2
2 CH2 1 1 3 Enter the number of occurences of a chemical structure in this
3 CH table for each component. Residual group interaction
9 ACH parameters are not available for all groups, and are treated as
10 AC 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 changed in
15 CH3OH this column by changing the SubGroup number. If you
16 H2O 1 change a sub-group here, be sure to edit the component
structure information in the table. Available subgroups and
17 ACOH subgroup numbers are in Table 2 of sheet "aij-UNIFAC
18 CH3CO (VLE)".
20 CHO
21 CH3COO
29 CH2NH2
36 ACNH2
42 COOH 1
49 CCL2
51 CCL3
99 CON(CH2)2
Sknk(i)xi 0.6 0.7 3E-20 3E-20 5E-20
N groups 2 1 3 3 5
Note that columns H:AS are hidden.
They contain intermediate calculations.
q 2.0480 1.4000 2.6120 2.5880 3.3160
Unprotect the sheet and unhide them to
r 1.9011 0.9200 2.8768 2.5755 3.8254 see the calculations.
qi 0.3853 0.6147 0.0000 0.0000 0.0000
Fi 0.4697 0.5303 0.0000 0.0000 0.0000
lngC 0.0971 0.0374 0.5020 0.1379 0.6466
lngRo 0.7722 0.0000 1.1444 1.0670 0.0000
lngR 1.0435 0.0714 1.4891 1.7067 4.0727

Page16
aijUNIFAC(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
1 0 86.02 61.13 76.5 986.5 697.2 1318 1333 476.4
2 -35.36 0 38.81 74.15 524.1 787.6 270.6 526.1 182.6
3 -11.12 3.446 0 167 636.1 637.3 903.8 1329 25.77
4 -69.7 -113.6 -146.8 0 803.2 603.2 5695 884.9 -52.1
5 156.4 457 89.6 25.82 0 -137.1 353.5 -259.7 84
6 16.51 -12.52 -50 -44.5 249.1 0 -181 -101.7 23.39
7 300 496.1 362.3 377.6 -229.1 289.6 0 324.5 -195.4
8 275.8 217.5 25.34 244.2 -451.6 -265.2 -601.8 0 -356.1
9 26.76 42.92 140.1 365.8 164.5 108.7 472.5 -133.1 0
10 505.7 56.3 23.39 106 529 -340.2 480.8 -155.6 128
11 114.8 132.1 85.84 -170 245.4 249.6 200.8 -36.72 372.2
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
20 315.3 1264 62.32 89.96 -151 339.8 -66.17 -11 -297.8
22 34.1 -23.5 121.3 140.8 527.6 669.9 708.7 82.86
23 36.7 51.06 228.5 69.9 742.1 649.1 826.8 552.1
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

Page17
aijUNIFAC(VLE)

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

Page18
aijUNIFAC(VLE)

Table 3. Interaction Parameters to be


Do not edit this table unless you want

T= 100.31

Sub Main
10 11 14 17 20 22 23 46 Group Group
677 232.1 391.5 920.7 663.5 53.76 24.9 380.9 1 1
448.8 37.85 240.9 749.3 318.9 58.55 -13.99 200.2 2 1
347.3 5.994 161.7 648.2 537.4 -144.4 -231.9 3 1
586.6 5688 19.02 664.2 872.3 -111 -80.25 9 3
-203.6 101.1 8.642 -52.39 199 65.28 -98.12 -382.7 10 3
306.4 -10.72 359.3 489.7 -202 -102.5 -139.4 11 4
-116 72.87 48.89 243.2 -14.09 370.4 353.7 835.6 12 4
-271.1 -449.4 119.9 408.9 14 5
-37.36 -213.7 6201 669.4 -130.3 -354.6 15 6
0 -110.3 497.5 67.52 -483.7 16 7
185.1 0 475.5 660.2 108.9 -209.7 17 8
0 -200.7 18 9
-294.8 -15.07 0 -396 -111 20 10
-165.5 -256.3 493.8 0 -44.7 39.63 -322.3 21 11
190.6 -133 140.8 543.3 0 0 29 14
242.8 176.5 504.2 -84.53 0 36 17
-70.25 0 42 20
49 22
51 23
99 46

Page19
aijUNIFAC(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
aij (i=column, j=row)
1 1 1 3 3 4 4
R Q CH3 CH2 CH ACH AC ACCH3 ACCH2
CH3 0.9011 0.848 0 0 0 61.13 61.13 76.5 76.5
CH2 0.6744 0.54 0 0 0 61.13 61.13 76.5 76.5
CH 0.4469 0.228 0 0 0 61.13 61.13 76.5 76.5
ACH 0.5313 0.4 -11.12 -11.12 -11.12 0 0 167 167
AC 0.3652 0.12 -11.12 -11.12 -11.12 0 0 167 167
ACCH3 1.2663 0.968 -69.7 -69.7 -69.7 -146.8 -146.8 0 0
ACCH2 1.0396 0.66 -69.7 -69.7 -69.7 -146.8 -146.8 0 0
OH 1 1.2 156.4 156.4 156.4 89.6 89.6 25.82 25.82
CH3OH 1.4311 1.432 16.51 16.51 16.51 -50 -50 -44.5 -44.5
H2O 0.92 1.4 300 300 300 362.3 362.3 377.6 377.6
ACOH 0.8952 0.68 275.8 275.8 275.8 25.34 25.34 244.2 244.2
CH3CO 1.6724 1.488 26.76 26.76 26.76 140.1 140.1 365.8 365.8
CHO 0.998 0.948 505.7 505.7 505.7 23.39 23.39 106 106
CH3COO 1.9031 1.728 114.8 114.8 114.8 85.84 85.84 -170 -170
CH2NH2 1.3692 1.236 -30.48 -30.48 -30.48 -44.85 -44.85 296.4 296.4
ACNH2 1.06 0.816 1139 1139 1139 247.5 247.5 762.8 762.8
COOH 1.3013 1.224 315.3 315.3 315.3 62.32 62.32 89.96 89.96
CCL2 1.8016 1.448 34.1 34.1 34.1 121.3 121.3 140.8 140.8
CCL3 2.6401 2.184 36.7 36.7 36.7 228.5 228.5 69.9 69.9
CON(CH2)2 2.4054 1.812 27.97 27.97 27.97 0 0 0 0

Table 4. Matrix of Y 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.
Y
CH3 CH2 CH ACH AC ACCH3 ACCH2 OH CH3OH
CH3 1 1 1 0.849009654 0.849009654 0.81477751 0.81477751 0.071254211 0.154608785

Page20
aijUNIFAC(VLE)

CH2 1 1 1 0.849009654 0.849009654 0.81477751 0.81477751 0.071254211 0.154608785


CH 1 1 1 0.849009654 0.849009654 0.81477751 0.81477751 0.071254211 0.154608785
ACH 1.030223186 1.030223186 1.030223186 1 1 0.639436802 0.639436802 0.182090233 0.181506084
AC 1.030223186 1.030223186 1.030223186 1 1 0.639436802 0.639436802 0.182090233 0.181506084
ACCH3 1.205183912 1.205183912 1.205183912 1.481535374 1.481535374 1 1 0.116404023 0.198859198
ACCH2 1.205183912 1.205183912 1.205183912 1.481535374 1.481535374 1 1 0.116404023 0.198859198
OH 0.65784601 0.65784601 0.65784601 0.786692834 0.786692834 0.933198904 0.933198904 1 1.443550587
CH3OH 0.956754936 0.956754936 0.956754936 1.143258458 1.143258458 1.126544979 1.126544979 0.513244714 1
H2O 0.447850912 0.447850912 0.447850912 0.379040409 0.379040409 0.363825654 0.363825654 1.846790984 0.46049774
ACOH 0.477832146 0.477832146 0.477832146 0.934399089 0.934399089 0.520023103 0.520023103 3.350891975 2.034220464
CH3CO 0.930853005 0.930853005 0.930853005 0.68719395 0.68719395 0.375504722 0.375504722 0.64373163 0.747470444
CHO 0.2581828 0.2581828 0.2581828 0.939290736 0.939290736 0.752893978 0.752893978 0.242567161 2.48664995
CH3COO 0.735360681 0.735360681 0.735360681 0.794653233 0.794653233 1.576489337 1.576489337 0.518354857 0.512558029
CH2NH2 1.08503773 1.08503773 1.08503773 1.127601247 1.127601247 0.452188862 0.452188862 1.915796244 3.632146607
ACNH2 0.047366364 0.047366364 0.047366364 0.515448294 0.515448294 0.129702601 0.129702601 1.047693523 1.371946344
COOH 0.42987409 0.42987409 0.42987409 0.846308673 0.846308673 0.785934864 0.785934864 1.498290953 0.40257843
CCL2 0.91273668 0.91273668 0.91273668 0.722672669 0.722672669 0.685907111 0.685907111 0.243478182 0.166333996
CCL3 0.906404376 0.906404376 0.906404376 0.542350428 0.542350428 0.829304643 0.829304643 0.13709464 0.175860823
CON(CH2)2 0.927841962 0.927841962 0.927841962 1 1 1 1 0.347449457 1

Page21
aijUNIFAC(VLE)

5 6 7 8 9 10 11 14 17 20
OH CH3OH H2O ACOH CH3CO CHO CH3COO CH2NH2 ACNH2 COOH
986.5 697.2 1318 1333 476.4 677 232.1 391.5 920.7 663.5
986.5 697.2 1318 1333 476.4 677 232.1 391.5 920.7 663.5
986.5 697.2 1318 1333 476.4 677 232.1 391.5 920.7 663.5
636.1 637.3 903.8 1329 25.77 347.3 5.994 161.7 648.2 537.4
636.1 637.3 903.8 1329 25.77 347.3 5.994 161.7 648.2 537.4
803.2 603.2 5695 884.9 -52.1 586.6 5688 19.02 664.2 872.3
803.2 603.2 5695 884.9 -52.1 586.6 5688 19.02 664.2 872.3
0 -137.1 353.5 -259.7 84 -203.6 101.1 8.642 -52.39 199
249.1 0 -181 -101.7 23.39 306.4 -10.72 359.3 489.7 -202
-229.1 289.6 0 324.5 -195.4 -116 72.87 48.89 243.2 -14.09
-451.6 -265.2 -601.8 0 -356.1 -271.1 -449.4 0 119.9 408.9
164.5 108.7 472.5 -133.1 0 -37.36 -213.7 0 6201 669.4
529 -340.2 480.8 -155.6 128 0 -110.3 0 0 497.5
245.4 249.6 200.8 -36.72 372.2 185.1 0 0 475.5 660.2
-242.8 -481.7 -330.4 0 0 0 0 0 -200.7 0
-17.4 -118.1 -341.6 -253.1 -450.3 0 -294.8 -15.07 0 -396
-151 339.8 -66.17 -11 -297.8 -165.5 -256.3 0 493.8 0
527.6 669.9 708.7 0 82.86 190.6 -133 0 140.8 543.3
742.1 649.1 826.8 0 552.1 242.8 176.5 0 0 504.2
394.8 0 -509.3 0 0 0 0 0 0 -70.25

H2O ACOH CH3CO CHO CH3COO CH2NH2 ACNH2 COOH CCL2 CCL3
0.029330064 0.028175374 0.279254345 0.163201638 0.537147537 0.350533209 0.084982323 0.169209019 0.865930659 0.935500615

Page22
aijUNIFAC(VLE)

0.029330064 0.028175374 0.279254345 0.163201638 0.537147537 0.350533209 0.084982323 0.169209019 0.865930659 0.935500615
0.029330064 0.028175374 0.279254345 0.163201638 0.537147537 0.350533209 0.084982323 0.169209019 0.865930659 0.935500615
0.088916306 0.028478771 0.933323851 0.39457434 0.98407828 0.648576093 0.176285139 0.237172179 1.472045023 1.860689185
0.088916306 0.028478771 0.933323851 0.39457434 0.98407828 0.648576093 0.176285139 0.237172179 1.472045023 1.860689185
2.38424E-07 0.093531953 1.149705181 0.207897674 2.42935E-07 0.950346242 0.168892159 0.096741407 1.346110211 1.239714836
2.38424E-07 0.093531953 1.149705181 0.207897674 2.42935E-07 0.950346242 0.168892159 0.096741407 1.346110211 1.239714836
0.388077917 2.004481869 0.798578051 1.724900666 0.762837399 0.977125434 1.150598295 0.586928498 0.839627475 1.300476819
1.623614087 1.313003114 0.939290736 0.440241497 1.029120346 0.382097483 0.269484333 1.717526586 1.315818739 1.452468261
1 0.41941378 1.687440252 1.364253451 0.822735654 0.877296473 0.521417409 1.038448823 0.370907927 0.387870145
5.00986789 1 2.594804125 2.066612542 3.33121047 1 0.725386843 0.334576096 1 1
0.282185831 1.428171801 1 1.105211799 1.772185845 1 6.15076E-08 0.166556838 1.417504238 2.584403062
0.275983571 1.516859808 0.709823343 1 1.343589486 1 1 0.263914342 0.834606517 3.651650016
0.584106444 1.103319424 0.369124538 0.609185204 1 1 0.279928127 0.170710817 0.747070258 1.753305962
2.422246552 1 1 1 1 1 1.711558365 1 1 1
2.495989172 1.969368869 3.339247983 1 2.202011168 1.041177391 1 2.887379237 1.346110211 1
1.193846057 1.02989221 2.219771048 1.557607536 1.986315866 1 0.266542017 1 1.127148439 0.899320991
0.149920475 1 0.801019452 0.600279428 1.427789438 1 0.685907111 0.233454743 1 1
0.109275757 1 0.228018079 0.521976177 0.623376157 1 1 0.25922187 1.254004114 1
3.910741332 1 1 1 1 1 1 1.206960102 1 1

Page23
aijUNIFAC(VLE)

22 23 46
CCL2 CCL3 CON(CH2)2
53.76 24.9 380.9 CH3
53.76 24.9 380.9 CH2
53.76 24.9 380.9 CH
-144.4 -231.9 0 ACH
-144.4 -231.9 0 AC
-111 -80.25 0 ACCH3
-111 -80.25 0 ACCH2
65.28 -98.12 -382.7 OH
-102.5 -139.4 0 CH3OH
370.4 353.7 835.6 H2O
0 0 0 ACOH
-130.3 -354.6 0 CH3CO
67.52 -483.7 0 CHO
108.9 -209.7 0 CH3COO
0 0 0 CH2NH2
-111 0 0 ACNH2
-44.7 39.63 -322.3 COOH
0 0 0 CCL2
-84.53 0 0 CCL3
0 0 0 CON(CH2)2

CON(CH2)2
0.360624964

Page24
aijUNIFAC(VLE)

0.360624964
0.360624964
1
1
1
1
2.786361192
1
0.106730957
1
1
1
1
1
1
2.370276168
1
1
1

Page25
UNIFAC(LLEa)

Liquid-liquid calculation using UNIFAC LLE. Sheet for first liquid phase. See also "UNIFAC (LLEb)".
Instructions: Type the temperature of interest in centigrade. Then enter the number
of occurences of each functional group in each component. If you have less than 5
components, type a samll number like 1E-20 for the mole fractions of the absent components. If you want
the pressure to be computed automatically, you must enter the Antoine coefficients of
the components. To use different functional groups than those provided,
follow the instructions on the aij-UNIFAC sheet.
This sheet does not yet have the
cabability for specification of other
Note: hidden functional groups without editing "aij-
UNIFAC (LLE)". That will be provided in
P= 86.4464 mmHg columns with -> <- 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 7.28066211 develop this sheet.
B 1730.63 1434.20107 T. Magnussen, P. Rasmussen, A. Fredenslund,
C 233.426 246.499046 Ind. Eng. Chem. Process Des. Dev., 1981, 20, 331-339.
P [mmHg] 23.686414
sat
99.5714883 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
Sknk(i)xi 0.8301526 0.29954229 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

Page26
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= 85.6032 mmHg columns with -> <-
T(oC)= ### oC intermediate calcs
Antoine Coefficients (mmHg) log10(Psat)=A-B/(T+C) where T[=] oC
comp1 comp2 comp3 comp4 comp5
A 8.07131 7.28066211 0 0 0
B 1730.63 1434.20107 0 0 0 b phase
C 233.426 246.499046 0 0 0
Psat[mmHg] 23.686414 99.5714883 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-Propanol 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
Sknk(i)xi 0.7729163 0.41700003 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

Page27
aijUNIFAC(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 0 0 3 4 0 5 7 8 9 10 11 13
Group R Q CH3 CH2 CH ACH ACCH2 ACCH3 OH 2-Propanol H2O ACOH CH3CO CHO COOH
1 CH3 0.9011 0.848 0 0 0 -114.8 -115.7 -115.7 644.6 310.7 1300 2255 472.6 158.1 139.4
CH2 0.6744 0.54 0 0 0 -114.8 -115.7 -115.7 644.6 310.7 1300 2255 472.6 158.1 139.4
CH 0.4469 0.228 0 0 0 -114.8 -115.7 -115.7 644.6 310.7 1300 2255 472.6 158.1 139.4
3 ACH 0.5313 0.4 156.5 156.5 156.5 0 167 167 703.9 577.3 859.4 1649 593.7 362.3 461.8
4 ACCH2 1.0396 0.66 104.4 104.4 104.4 -146.8 0 0 4000 906.8 5695 292.6 916.7 1218 339.1
ACCH3 1.2663 0.968 104.4 104.4 104.4 -146.8 0 0 4000 906.8 5695 292.6 916.7 1218 339.1
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
7 2-Propanol 3.2491 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
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
9 ACOH 0.8952 0.68 -159.8 -159.8 -159.8 -473.2 -470.4 -470.4 -63.15 -547.2 -595.9 0 -825.7
10 CH3CO 1.6724 1.488 66.56 66.56 66.56 -78.31 -73.87 -73.87 216 -127.6 634.8 -568 0 -37.36 1247
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
13 COOH 1.3013 1.224 1744 1744 1744 75.49 147.3 147.3 118.4 349.1 652.3 -101.3 1051 0
14 CH3COO 1.9031 1.728 -320.1 -320.1 -320.1 114.8 -170 -170 180.6 -152.8 385.9 -337.3 58.84 1090 1417
15 CH2O 0.9183 0.78 1571 1571 1571 52.13 65.69 65.69 137.1 -218.1 212.8 52.38 1402
17 CHCL2 2.0606 1.684 27.9 27.9 27.9 669.2 -401.6 740.4 550.6 437.7
18 CCL3 2.6401 2.184 21.23 21.23 21.23 288.5 33.61 33.61 418.4 -465.7 793.2 -825.7 370.4
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

Y
CH3 CH2 CH ACH ACCH2 ACCH3 OH 2-PropanoH2O ACOH CH3CO CHO COOH
CH3 1 1 1 1.46967 1.47412 1.474118 0.1151 0.35272 0.01278 0.00052 0.204926 0.5884 0.62654

Page28
aijUNIFAC(LLE)

CH2 1 1 1 1.46967 1.47412 1.474118 0.1151 0.35272 0.01278 0.00052 0.204926 0.5884 0.62654
CH 1 1 1 1.46967 1.47412 1.474118 0.1151 0.35272 0.01278 0.00052 0.204926 0.5884 0.62654
ACH 0.5916 0.59161 0.591612 1 0.57114 0.57114 0.0943 0.14424 0.056 0.00396 0.136521 0.2967 0.21248
ACCH2 0.7046 0.70458 0.704576 1.63619 1 1 1E-06 0.04777 5E-09 0.37479 0.046207 0.0168 0.32067
ACCH3 0.7046 0.70458 0.704576 1.63619 1 1 1E-06 0.04777 5E-09 0.37479 0.046207 0.0168 0.32067
OH 0.3326 0.33261 0.332609 1.03137 0.99575 0.995749 1 0.03598 0.90814 1.92651 0.798553 0.0089 1.41739
2-Propanol 1.5564 1.55643 1.55643 2.32847 2.50342 2.503423 2.4634 1 0.98044 1.67169 0.305242 3.1133 1.21466
H2O 0.3171 0.31714 0.317139 0.2864 0.50499 0.504992 1.5076 0.7034 1 0.31491 1.7793 3.2335 4.76818
ACOH 1.7091 1.70911 1.709108 4.88965 4.84394 4.843944 1.2359 6.26713 7.37915 1 15.94924 1 1
CH3CO 0.7999 0.79992 0.79992 1.30038 1.28115 1.281154 0.4846 1.53414 0.11894 6.71995 1 1.1335 0.01526
CHO 0.6126 0.61261 0.612613 1.28731 0.47302 0.473021 4.2486 0.46019 0.12345 1 0.650955 1 0.99749
COOH 0.0029 0.00288 0.002882 0.77632 0.61015 0.610152 0.6723 0.31009 0.11216 1 1.404613 0.0294 1
CH3COO 2.926 2.92595 2.925954 0.68042 1.76859 1.76859 0.5457 1.66945 0.27409 3.09971 0.820903 0.0258 0.00863
CH2O 0.0051 0.00515 0.005148 0.83959 0.80226 0.802258 0.6314 2.07822 0.48981 1 0.838884 1 0.00907
CHCL2 0.9107 0.91067 0.910668 1 1 1 0.106 3.84577 0.08347 1 0.157754 1 0.23037
CCL3 0.9313 0.93127 0.93127 0.37998 0.89339 0.893393 0.2458 4.76818 0.06992 1 15.94924 1 0.28871
ACNH2 0.5545 0.55453 0.554529 2.0838 1.05304 1.053044 0.1696 1 2.23512 17.9118 0.056318 1 0.10173

Page29
aijUNIFAC(LLE)

Fredenslund,

14 15 17 18 22
CH3COO CH2O CHCL2 CCL3 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
6 32.14 -231.9 1.64 ACH
5688 213.1 -12.14 689.6 ACCH2
5688 213.1 -12.14 689.6 ACCH3
195.6 262.5 272.2 -61.57 -348.2 OH
487.1 1970 507.8 1544 2-Propanol
-6.32 64.42 370.7 356.8 -109.8 H2O
-898.3 -851.6 ACOH
258.7 5.202 -301 12.01 1010 CH3CO
-245.8 CHO
-117.6 -96.62 1670 48.15 942.2 COOH
0 -235.7 108.9 -209.7 CH3COO
461.3 0 137.8 -154.3 CH2O
-132.9 -197.7 0 CHCL2
-898.3 -20.93 0 -75.5 CCL3
-216.3 0 ACNH2

CH3COO CH2O CHCL2 CCL3 ACNH2


0.0383329 0.10853 2.26606 0.97516 0.04851

Page30
aijUNIFAC(LLE)

0.0383329 0.10853 2.26606 0.97516 0.04851


0.0383329 0.10853 2.26606 0.97516 0.04851
0.980077 0.89781 1 2.17667 0.994515
5.184E-09 0.48932 1 1.04156 0.098971
5.184E-09 0.48932 1 1.04156 0.098971
0.5188992 0.4146 0.40133 1.22938 3.215132
0.1951979 0.00135 0.18211 0.00564 1
1.0214236 0.80568 0.28842 0.30219 1.445234
20.346583 1 1 1 17.3967
0.4199229 0.9827 2.74439 0.96052 0.033791
2.2805514 1 1 1 1
1.4835418 1.38274 0.00369 0.85087 0.042419
1 2.20459 0.69402 2.02048 1
0.2128414 1 0.62991 1.67787 1
1.5616591 1.94078 1 1 1
20.346583 1.07272 1 1 1.288177
1 1 1 2.06571 1

Page31
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
-0.01
Gm/RT

-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
Page32
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

Page33
LLE

e calculation

Page34