ACTCOEFF

Instructions

ACTCOEFF.XLS

This workbook will calculate activities, activity coefficients, and excess Gibbs energiesfor 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 willpermit most common calculations.

Copyright 1997-2000, Carl Lira, Richard ElliottFor use with "Introductory Chemical Engineering Thermodynamics" by J.R. Elliott, C.T. Lirawww.egr.msu.edu/~lira/thermtxt.htm

document.xls

Margules Equation

Margules Parameters A12_ A21_1.861 1.6365

Table x1 increment 0.05

x1 x2 gamma1 gamma2 activity1 activity2 G(mix) /RT0 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

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

Regular

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 repeatedfor each composition for each model.Pure Component Data

Antoine Coeff A B C1 MeOH 8.08097 1582.271 239.726 40 14.52 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

0 0.026 0.05 0.088 0.164 0.284209 0.333 0.549 0.699

0 0.267 0.371 0.457 0.526 0.559 0.595 0.633T (C) 80.1 70.67 66.44 62.87 60.2 58.64 58.02 58.1Calculations based on dataT(K) 353.25 343.82 339.59 336.02 333.35 331.79 331.17 331.25

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 ---->

0 0.026 0.05 0.088 0.164 0.284209 0.333 0.549 0.699

4.956911 4.895389 4.806788 4.626503 4.188901 3.44408 3.152024 2.050917 1.506623

1 1.000515 1.001979 1.006504 1.025374 1.092665 1.138907 1.622229 2.731147

1360.424 1106.072 952.1375 793.1757 624.0955 515.2352 495.4532 476.6008 481.2578

759.9965 635.4177 558.0115 476.1449 386.4323 326.8842 315.8845 305.3454 307.9541

0 0.185238 0.3011 0.424905 0.564133 0.663596 0.684263 0.706092 0.666878

1 0.814757 0.698895 0.57509 0.435861 0.336398 0.315739 0.293945 0.333107T(K) 353.2494 347.542 343.5352 338.7874 332.7723 328.1309 327.2006 326.2845 326.5136

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 x1

0.000254 0.2842090 0.973033

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

0 0.026 0.05 0.088 0.164 0.284209 0.333 0.549 0.699

2.996881 2.94956 2.89995 2.812993 2.620077 2.295044 2.163238 1.623682 1.319103

1 1.00035 1.001341 1.004387 1.016992 1.06134 1.091355 1.386062 1.9717

1360.423 1206.105 1097.85 970.3827 809.732 680.2924 650.4601 593.2755 588.0778

759.9959 684.8684 631.3249 567.2759 484.7742 416.5914 400.6269 369.7319 366.9037

0 0.121703 0.209455 0.316068 0.45781 0.583864 0.616532 0.695851 0.713472

0.999995 0.87802 0.790215 0.683717 0.542312 0.416425 0.383723 0.304111 0.286514

The bubble temperatures and vapor compositions at each temperature are computed

VL (cm3/mol) d (cal/cm3

x1

y1

F1

x1

g1

g2

P1sat

P2sat

y1 calc

y2 calc

(Syi-1)2

Dg*xg1*x1g2*x2

x1

g1

g2

P1sat

P2sat

y1 calc

y2 calc

Regular

T(K) 353.2494 349.9045 347.3401 344.037 339.317 334.908 333.7935 331.5318 331.3173

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

For this calculation, experimental azeotrope is taken as x1 = y1 = 0.614, T(C) = 58.3

591.2879 1.28533 1.984748

368.6508 2.061572 1.742401

0 0.026 0.05 0.088 0.164 0.284209 0.333 0.549 0.699

#NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME?

1 #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME?

1360.423 1035.625 885.7867 759.2857 653.4823 605.4583 599.3688 591.8375 593.2068

759.9959 600.202 524.0995 458.4003 402.2488 376.3476 373.0431 368.9498 369.6946


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

Van Laar model with A12 and A21 chosen to match the azeotrope. See plot ---->

P1sat g1 A12

P2sat g2 A21

x1

g1

g2

P1sat

P2sat

y1 calc

y2 calc

(Syi-1)2

First, set this to 331.3 (close to azeotrope T and composition), then adjust kij until cell J48 = 0.

These values are calculated from the activitiy coefficient and composition values at the azeotrope.

J47


H54


Regular

0.782 0.898 0.973033 0.973 1

0.665 0.76 0.907 158.47 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

1.284842 1.072172 1.005708 1.005721 1

4.331675 11.64805 29.02295 29.01087 39.80158

471.905 438.8193 515.2002 515.0633 759.9949

302.7114 284.0489 326.8648 326.7889 458.7727

0.623875 0.555921 0.663379 0.663189 0.999993

0.376121 0.444051 0.336616 0.336805 0326.0516 324.353 328.1293 328.123 337.6976 OBJ

1.94E-11 8.1E-10 2.67E-11 3.54E-11 4.45E-11 3E-09<----- LLE region ---> |

The cross-overs in the above diagram are indicativeof LLE. The points represent experimental data. An interaction parameter is necessary to fit the datawithout predicting LLE.

0.782 0.898 0.973033 0.973 1

1.184253 1.047825 1.003836 1.003845 1

2.688894 5.185622 9.635523 9.632578 12.50164

588.2562 598.28 668.7655 668.6936 759.995

367.0008 372.4518 410.4348 410.3963 458.7727

0.71681 0.740723 0.859509 0.859395 0.999993

0.283063 0.259213 0.140328 0.140442 0

d (cal/cm3)1/2

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1300

310

320

330

340

350

360

x-y

T(K

)

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1320

325

330

335

340

345

350

355

x-y

T(K

)

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

P31

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

Regular

331.3247 331.7369 334.4823 334.4796 337.6976 OBJ

1.59E-08 4E-09 2.67E-08 2.66E-08 4.42E-11 5E-07

0.782 0.898 0.973033 0.973 1

#NAME? #NAME? #NAME? #NAME? 1

#NAME? #NAME? #NAME? #NAME? #NAME?

602.2797 644.9099 716.6531 716.608 759.995

374.6233 397.6455 435.9169 435.893 458.7727

#NAME? #NAME? #NAME? #NAME? 0.999993

#NAME? #NAME? #NAME? #NAME? #NAME?331.8997 333.5814 336.2127 336.2111 337.6976 OBJ

#NAME? #NAME? #NAME? #NAME? #NAME? ###

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1320

325

330

335

340

345

350

355

x-y

T(K

)

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1320

325

330

335

340

345

350

355

x-y

T(K

)

Then, use Solver to adjust B47:O47 to calc bubble T's.



After determining the A12 and A21, the bubble temperatures are calculated across the composition range as before.

P48

Then, use Solver to adjust B47:O47 to calc bubble T's.

P64

After determining the A12 and A21, the bubble temperatures are calculated across the composition range as before.

Regular

The cross-overs in the above diagram are indicativeof LLE. The points represent experimental data. An interaction parameter is necessary to fit the data

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1300

310

320

330

340

350

360

x-y

T(K

)

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1320

325

330

335

340

345

350

355

x-y

T(K

)

Regular

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1320

325

330

335

340

345

350

355

x-y

T(K

)

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1320

325

330

335

340

345

350

355

x-y

T(K

)

UNIQUAC

UNIQUAC Calculation Note: This spreadsheet uses the form of equations that permits the q of the residual part to differ from q of the combinatorial part. (Anderson, T.F., Prausnitz, J.,M., Ind. Eng. Chem. Process Des. Dev. 17, 1978, 552-561). The formulas look a little different because or the use of the intermediate variable 'l', however the equationsare 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

T(C) T(K) tau12 tau21 theta1 theta2 theta'10.000000 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

x1 x2

UNIQUAC

Note: This spreadsheet uses the form of equations that permits the q of the residual part to differ from q of the combinatorial part. (Anderson, T.F., Prausnitz, J.,M., Ind. Eng. Chem. Process Des. Dev. 17, 1978, 552-561). The formulas look a little different because or the use of the intermediate variable 'l', however the equations

theta'2 phi1 phi2 ln(gam1) ln(gam2) gam1 gam21 0 1 ### 0 ### 1

### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### 0.13 0.87 ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###### ### ### ### ### ### ###

0 1 0 0 ### 1 ###

UNIQUAC5

UNIQUAC5This spreadsheet is constructed to calculate activity coefficients for up to 5 componentsusing the UNIQUAC activity coefficient expression. Antoine coeffients are optional.

1 2 3 4 5Antoine A 8.07131 7.2806621Antoine B 1730.63 1434.2011Antoine C 233.426 246.49905

23.686414 99.571488 1 1 1y 0.2283 0.7717 0.0000 0.0000 0.0000 Unhide columns G-R for LLE iterations.

98.492886

T (K) = 298.15

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 1.187316450.949193 0.7633618 0.0008404 4.26924E-11 1.1873E-11

r 0.92 3.2479 2.2024 3.19 1.43q 1.4 2.876 2.072 2.4 1.43F 0.7048511 0.276213 0.0189359 2.74271E-11 1.2295E-11q 0.8034456 0.1832101 0.0133444 1.54568E-11 9.2097E-12

1.163083 1.5527152

1 2 3 4 51 1 -2.0882 254.15 0 02 345.53 1 -254.13 0 03 -301.02 -4.5537 1 0 04 0 0 0 1 05 0 0 0 0 1

1 2 3 4 51 1 1.0070284 0.4263804 1 1

Enter T, component names, aij's, r, q, and composition values.

Psat (mmHg)

Pcalc (mm Hg)

Phase a

xg

Sixiri Sixiqi

aij matrix (i = row, j=column), enter 0's for unused cells

tij matrix (i = row, j=column)

UNIQUAC5

2 0.313827 1 2.345166 1 13 2.7445744 1.0153904 1 1 14 1 1 1 1 15 1 1 1 1 1

0.0320012 0.6306144 0.4602702 1.677681099 0.30649967

0.8975665 1.0058523 0.7855758 1 1

0.8951377 0.1821441 0.0169867 1.54568E-11 9.2097E-12

1.0858048 0.5028992 2.6587062 1.094268528 1.09426853

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.

ln(gcomb)

Si(qitij)

qj/Si(qitij)

Sj{qjtkj/(Siqitij)}

ln(gresid)

100

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

15 20 60 -15 -26 30 70

84 93 106 98 83 70 120 Source 3 3 3 3 2 2

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

methane ethane propane n-butane n-pentane n-pentane n-hexaneA 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

-182 -143 -108 -78 -50 -50 -25

-158 -84 -35.65 19 58 58 92 Source 5 5 5 5 5 3 5

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

cyclohexan cyclohexane methylcycloh isopentane toluene benzene m-xyleneA ### 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

6.7 7 -3 20 -27 8 29

80.7 81 100 93 111 80 166 Source 1 3 1 3 3 3

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

water acetonitrile Triethylamineacetic acid acetic acid chloroform dichloromethanA 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

1 -27 50 18 118 -10 -44

100 82 95 118 227 60 59 Source 3 3 3 3 3 3 3

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

Source1. 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. Chem, 39, 517(1947).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., Thermodynamics Research Center, Texas A&M University, College Station, TX, 1950-1997.

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

T[oC]

tMin[oC]

tMax[oC]

Psat[mmHg]

tMin[oC]

tMax[oC]

Psat[mmHg]

tMin[oC]

tMax[oC]

Psat[mmHg]

tMin[oC]

tMax[oC]

Psat[mmHg]

1-butanol 2-butanol 1-octanol ethylene glycol7.36366 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 decane6.91058 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-butanone7.00154 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 Naphthalene7.40916 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)

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

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. Chem, 39, 517(1947).2. Fit to data of Handbook of Chemistry and Physics, 56th ed., R.C. Weast, ed., CRC Press, 1974-75, pp D191-D210.

5. TRC Thermodynamic Tables, Hydrocarbons, M. Frenkel, N.M. Gadalla, K.R. Hall, X. Hong, K.N. Marsh, R.C. Wilhoit, eds., Thermodynamics Research Center, Texas A&M University, College Station, TX, 1950-1997.

3-pentanone7.23064

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 View…Comment…to show or hide them.

P= 745.5159 mmHg

80.37

comp1 comp2 comp3 comp4 comp5

A 8.87829 8.07131 8.1122 6.87632

B 2010.33 1730.63 1592.864 1075.78

C 252.636 233.426 226.184 233.205

694.019617 359.887203 824.4594 2790.1374

0.58963 0.41037 0.00000 0.00000 0.00000

Table 2. Component Structure Information and Activity Coefficient Calculation.comp1 comp2 comp3 comp4 comp5

IPA Water C2-COOH EtOH C5H12

0.500 0.500 0.000 0.000 0.000

SubGroup 1.267 1.700 0.980 1.107 12.607

1 CH3 2 1 1 2

2 CH2 1 1 3

3 CH 1

9 ACH

10 AC

11 ACCH3

12 ACCH2

14 OH 1 1

15 CH3OH

16 H2O 1

17 ACOH

18 CH3CO

20 CHO

21 CH3COO

29 CH2NH2

36 ACNH2

42 COOH 1

49 CCL2

51 CCL3

99 CON(CH2)2

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

0.6905 0.3095 0.0000 0.0000 0.0000

0.7793 0.2207 0.0000 0.0000 0.0000

0.0042 0.0994 0.1625 0.0152 0.2233

1.3197 0.0000 1.1812 1.0915 0.0000

1.5520 0.4313 0.9983 1.1784 2.3110

T(oC)= oC

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

Psat[mmHg]

yi

xi

gi

Sknk(i)xi

qi

Fi

lngC

lngRo

lngR

Enter Antoine constants or vapor pressures if you want bubble P and vapor phase concentrations calculated automatically.

As distributed, this cell has a formula to calculate the bubble pressure.

Vapor phase mole fractions calculated automatically.

Liquid phase mole fractions. Enter a very small number like 1E-20 or smaller for absent compounds - don't use zero.

Enter the number of occurences of a chemical structure in this table for each component. Residual group interaction parameters are not available for all groups, and are treated as zero if unavailable. Check Table 1 on sheet "aij-UNIFAC (VLE)".

The sub-groups available in this table may be changed in this column by changing the SubGroup number. If you change a sub-group here, be sure to edit the component structure information in the table. Available subgroups and subgroup numbers are in Table 2 of sheet "aij-UNIFAC (VLE)".

Note that columns H:AS are hidden. They contain intermediate calculations. Unprotect the sheet and unhide them to see the calculations.

C9

As distributed, this cell has a formula to calculate the bubble pressure.

G13

Enter Antoine constants or vapor pressures if you want bubble P and vapor phase concentrations calculated automatically.

G17

Vapor phase mole fractions calculated automatically.

G21

Liquid phase mole fractions. Enter a very small number like 1E-20 or smaller for absent compounds - don't use zero.

A23

The sub-groups available in this table may be changed in this column by changing the SubGroup number. If you change a sub-group here, be sure to edit the component structure information in the table. Available subgroups and subgroup numbers are in Table 2 of sheet "aij-UNIFAC (VLE)".

G23

Enter the number of occurences of a chemical structure in this table for each component. Residual group interaction parameters are not available for all groups, and are treated as zero if unavailable. Check Table 1 on sheet "aij-UNIFAC (VLE)".

G45

Note that columns H:AS are hidden. They contain intermediate calculations. Unprotect the sheet and unhide them to see the calculations.

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 unprotectthe 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 476.42 -35.36 0 38.81 74.15 524.1 787.6 270.6 526.1 182.63 -11.12 3.446 0 167 636.1 637.3 903.8 1329 25.774 -69.7 -113.6 -146.8 0 803.2 603.2 5695 884.9 -52.15 156.4 457 89.6 25.82 0 -137.1 353.5 -259.7 846 16.51 -12.52 -50 -44.5 249.1 0 -181 -101.7 23.397 300 496.1 362.3 377.6 -229.1 289.6 0 324.5 -195.48 275.8 217.5 25.34 244.2 -451.6 -265.2 -601.8 0 -356.19 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 12811 114.8 132.1 85.84 -170 245.4 249.6 200.8 -36.72 372.214 -30.48 1.163 -44.85 296.4 -242.8 -481.7 -330.417 1139 2000 247.5 762.8 -17.4 -118.1 -341.6 -253.1 -450.320 315.3 1264 62.32 89.96 -151 339.8 -66.17 -11 -297.822 34.1 -23.5 121.3 140.8 527.6 669.9 708.7 82.8623 36.7 51.06 228.5 69.9 742.1 649.1 826.8 552.146 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 newsub-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 Q1 1 CH3 0.9011 0.8482 1 CH2 0.6744 0.54

aij-UNIFAC (VLE)

3 1 CH 0.4469 0.2284 1 C 0.2195 05 2 CH2=CH 1.3454 1.1766 2 CH=CH 1.1167 0.8677 2 CH2=C 1.1173 0.9888 2 CH=C 0.8886 0.676

70 2 C=C 0.6605 0.4859 3 ACH 0.5313 0.4

10 3 AC 0.3652 0.1211 4 ACCH3 1.2663 0.96812 4 ACCH2 1.0396 0.6613 4 ACCH 0.8121 0.34814 5 OH 1 1.215 6 CH3OH 1.4311 1.43216 7 H2O 0.92 1.417 8 ACOH 0.8952 0.6818 9 CH3CO 1.6724 1.48819 9 CH2CO 1.4457 1.1820 10 CHO 0.998 0.94821 11 CH3COO 1.9031 1.72822 11 CH2COO 1.6764 1.4229 14 CH2NH2 1.3692 1.23636 17 ACNH2 1.06 0.81642 20 COOH 1.3013 1.22449 22 CCL2 1.8016 1.44851 23 CCL3 2.6401 2.18499 46 CON(CH2)2 2.4054 1.812

aij-UNIFAC (VLE)

Table 3. Interaction Parameters to be used in the calculations for the selected groups as indicated 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.

T= 80.37

Sub Main10 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

aij-UNIFAC (VLE)

Table 3. Interaction Parameters to be used in the calculations for the selected groups as indicated 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.

C

1 1 1 3 3 4 4R Q CH3 CH2 CH ACH AC ACCH3 ACCH2

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

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

CH3 CH2 CH ACH AC ACCH3 ACCH2 OH CH3OHCH3 1 1 1 0.841206523 0.841206523 0.805417009 0.805417009 0.061390087 0.139155168

aij (i=column, j=row)

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

Y

aij-UNIFAC (VLE)

CH2 1 1 1 0.841206523 0.841206523 0.805417009 0.805417009 0.061390087 0.139155168CH 1 1 1 0.841206523 0.841206523 0.805417009 0.805417009 0.061390087 0.139155168ACH 1.031955019 1.031955019 1.031955019 1 1 0.623509084 0.623509084 0.165409274 0.164848755AC 1.031955019 1.031955019 1.031955019 1 1 0.623509084 0.623509084 0.165409274 0.164848755ACCH3 1.217938884 1.217938884 1.217938884 1.514752894 1.514752894 1 1 0.103105016 0.181541975ACCH2 1.217938884 1.217938884 1.217938884 1.514752894 1.514752894 1 1 0.103105016 0.181541975OH 0.642487586 0.642487586 0.642487586 0.776117768 0.776117768 0.929566541 0.929566541 1 1.473755618CH3OH 0.954372004 0.954372004 0.954372004 1.151925297 1.151925297 1.134142541 1.134142541 0.494292543 1H2O 0.428010187 0.428010187 0.428010187 0.358855336 0.358855336 0.343655713 0.343655713 1.91181654 0.44078861ACOH 0.458335477 0.458335477 0.458335477 0.930829539 0.930829539 0.501191437 0.501191437 3.587438128 2.117359348CH3CO 0.927098132 0.927098132 0.927098132 0.672804779 0.672804779 0.355320043 0.355320043 0.627934003 0.735298259CHO 0.239196307 0.239196307 0.239196307 0.935978138 0.935978138 0.740935581 0.740935581 0.223939518 2.617767335CH3COO 0.722719497 0.722719497 0.722719497 0.784416526 0.784416526 1.617493982 1.617493982 0.49949306 0.493593936CH2NH2 1.090044588 1.090044588 1.090044588 1.135265947 1.135265947 0.432391011 0.432391011 1.987359692 3.906266397ACNH2 0.039879902 0.039879902 0.039879902 0.496534738 0.496534738 0.115587438 0.115587438 1.050450669 1.39663922COOH 0.409881451 0.409881451 0.409881451 0.838379659 0.838379659 0.775327827 0.775327827 1.532856266 0.382437394CCL2 0.908047604 0.908047604 0.908047604 0.709552623 0.709552623 0.671473885 0.671473885 0.224828116 0.150327009CCL3 0.90139377 0.90139377 0.90139377 0.523951246 0.523951246 0.820594887 0.820594887 0.122557616 0.159437154CON(CH2)2 0.923930359 0.923930359 0.923930359 1 1 1 1 0.327335873 1

aij-UNIFAC (VLE)

5 6 7 8 9 10 11 14 17 20OH CH3OH H2O ACOH CH3CO CHO CH3COO CH2NH2 ACNH2 COOH

986.5 697.2 1318 1333 476.4 677 232.1 391.5 920.7 663.5986.5 697.2 1318 1333 476.4 677 232.1 391.5 920.7 663.5986.5 697.2 1318 1333 476.4 677 232.1 391.5 920.7 663.5636.1 637.3 903.8 1329 25.77 347.3 5.994 161.7 648.2 537.4636.1 637.3 903.8 1329 25.77 347.3 5.994 161.7 648.2 537.4803.2 603.2 5695 884.9 -52.1 586.6 5688 19.02 664.2 872.3803.2 603.2 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 199249.1 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 0 119.9 408.9164.5 108.7 472.5 -133.1 0 -37.36 -213.7 0 6201 669.4

529 -340.2 480.8 -155.6 128 0 -110.3 0 0 497.5245.4 249.6 200.8 -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 0 140.8 543.3742.1 649.1 826.8 0 552.1 242.8 176.5 0 0 504.2394.8 0 -509.3 0 0 0 0 0 0 -70.25

H2O ACOH CH3CO CHO CH3COO CH2NH2 ACNH2 COOH CCL2 CCL30.024035604 0.023037097 0.259865795 0.147337998 0.518642768 0.330405759 0.073949059 0.15307326 0.858927635 0.931988794

aij-UNIFAC (VLE)

0.024035604 0.023037097 0.259865795 0.147337998 0.518642768 0.330405759 0.073949059 0.15307326 0.858927635 0.9319887940.024035604 0.023037097 0.259865795 0.147337998 0.518642768 0.330405759 0.073949059 0.15307326 0.858927635 0.931988794

0.07757005 0.023299236 0.929698024 0.374409365 0.983187737 0.632927205 0.15984357 0.218681203 1.504504267 1.927018910.07757005 0.023299236 0.929698024 0.374409365 0.983187737 0.632927205 0.15984357 0.218681203 1.504504267 1.92701891

1.00872E-07 0.081829983 1.158788394 0.190269829 1.02889E-07 0.947619939 0.152770461 0.084799128 1.368869292 1.2548332751.00872E-07 0.081829983 1.158788394 0.190269829 1.02889E-07 0.947619939 0.152770461 0.084799128 1.368869292 1.2548332750.367900254 2.084672781 0.788509898 1.778770071 0.751276897 0.975850797 1.159739363 0.56954917 0.831389267 1.3198940681.668614537 1.33332818 0.935978138 0.42033136 1.030788046 0.36191357 0.25027084 1.770737707 1.336348859 1.483375126

1 0.399352301 1.737985808 1.388367416 0.813729765 0.870841875 0.502611161 1.040661223 0.350726571 0.3676921785.48659703 1 2.7381925 2.152993109 3.565182366 1 0.712368145 0.314537149 1 1

0.262748482 1.457174385 1 1.111466171 1.830322108 1 2.41077E-08 0.150539774 1.445678648 2.726598850.256651484 1.552932112 0.696231634 1 1.366161494 1 1 0.244809383 0.82613801 3.9284282940.566656596 1.109455832 0.348945333 0.59238927 1 1 0.260528211 0.154508841 0.73488239 1.8097291432.546196274 1 1 1 1 1 1.764238127 1 1 12.628154698 2.046114279 3.574270259 1 2.302278011 1.043550063 1 3.065353609 1.368869292 11.205837927 1.031604789 2.321898465 1.597035187 2.064719419 1 0.247385054 1 1.134784351 0.8939538260.134701288 1 0.79105672 0.583244307 1.456762253 1 0.671473885 0.215061854 1 10.096446732 1 0.209774505 0.503180176 0.606976903 1 1 0.240213383 1.270117641 1

4.22345703 1 1 1 1 1 1 1.219835206 1 1

aij-UNIFAC (VLE)

22 23 46CCL2 CCL3 CON(CH2)2

53.76 24.9 380.9 CH353.76 24.9 380.9 CH253.76 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 CH3OH370.4 353.7 835.6 H2O

0 0 0 ACOH-130.3 -354.6 0 CH3CO67.52 -483.7 0 CHO108.9 -209.7 0 CH3COO

0 0 0 CH2NH2-111 0 0 ACNH2

-44.7 39.63 -322.3 COOH0 0 0 CCL2

-84.53 0 0 CCL30 0 0 CON(CH2)2

CON(CH2)20.340462719

aij-UNIFAC (VLE)

0.3404627190.340462719

1111

2.9521723791

0.094075565111111

2.488520021111

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.

Note: hidden P= 86.4464 mmHg columns with -> <-T(oC)= 25 intermediate calcs

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.

23.686414 99.5714883 1 1 1

0.26079 0.73763 0.00158 0.00000 0.00000

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

1.147 6.414 1.951 1.705 199.114 1 2 3

CH3 1 1 1 2

CH2 1 1 1 3

CH

ACH

ACCH2

ACCH3

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

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

0.7120 0.1759 0.1120 0.0000 0.0000

0.5923 0.2515 0.1562 0.0000 0.0000

0.0606 0.4430 0.3795 0.0676 0.4747

0.0000 0.8719 1.1448 1.2862 0.0000

0.0761 2.2874 1.4339 1.7522 4.8192

oC

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

Psat[mmHg]yi a phase

gi

Ki,old

Ki,new

xai,old

xai,new

xbi,old

xbi,new

Sknk(i)xi

qi

Fi

lngC

lngRo

lngR

This sheet does not yet have the cabability for specification of other functional groups without editing "aij-UNIFAC (LLE)". That will be provided in the future.

AU8

This sheet does not yet have the cabability for specification of other functional groups without editing "aij-UNIFAC (LLE)". That will be provided in the future.

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)= 25 intermediate calcs

comp1 comp2 comp3 comp4 comp5A 8.07131 7.28066211 0 0 0B 1730.63 1434.20107 0 0 0C 233.426 246.499046 0 0 0

23.686414 99.5714883 1 1 10.26079 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 0.0001.235 4.541 1.535 1.396 104.701

CH3 0 1 1 1 2CH2 0 1 1 1 3CH 0 0 0 0 0ACH 0 0 0 0 0ACCH2 0 0 0 0 0ACCH3 0 0 0 0 0OH 0 0 0 1 02-Propanol 0 0 0 0 0H2O 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

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

0.6321 0.2335 0.1344 0.0000 0.0000

0.5022 0.3188 0.1790 0.0000 0.0000

0.0909 0.3122 0.2677 0.0150 0.3208

0.0000 0.8719 1.1448 1.2862 0.0000

0.1204 2.0730 1.3059 1.6049 4.3303

oC

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

b phase

Psat[mmHg]

yi

gi

Sknk(i)xi

qi

Fi

lngC

lngRo

lngR

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.

For a new main group, carefully replace all entries for the row and column associated with the new group. You must unprotectthe sheet, and then change only the values in blue. Parameters from T. Magnussen, P. Rasmussen, A. Fredenslund, T= 25 C

NOTE: Blank cells mean value is unavailableMain 1 3 4 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

CH3 CH2 CH ACH ACCH2 ACCH3 OH 2-PropanoH2O ACOH CH3CO CHO COOH

CH3 1 1 1 1.46967 1.474118 1.4741178 0.1151 0.352716 0.01278 0.00052 0.204926 0.5884 0.62654

If you want to use a different subgroup, you may just change the R and Q parameters, and leave the aijmatrix.

Ind. Eng. Chem. Process Des. Dev., 1981, 20, 331-339.

aij (i=column, j=row)

Y

aij-UNIFAC (LLE)

CH2 1 1 1 1.46967 1.474118 1.4741178 0.1151 0.352716 0.01278 0.00052 0.204926 0.5884 0.62654

CH 1 1 1 1.46967 1.474118 1.4741178 0.1151 0.352716 0.01278 0.00052 0.204926 0.5884 0.62654

ACH 0.5916 0.59161 0.591612 1 0.57114 0.5711401 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 0.047767 5.1E-09 0.37479 0.046207 0.0168 0.32067

ACCH3 0.7046 0.70458 0.704576 1.63619 1 1 1E-06 0.047767 5.1E-09 0.37479 0.046207 0.0168 0.32067

OH 0.3326 0.33261 0.332609 1.03137 0.995749 0.9957495 1 0.035978 0.90814 1.92651 0.798553 0.0089 1.41739

2-Propanol 1.5564 1.55643 1.55643 2.32847 2.503423 2.5034228 2.4634 1 0.98044 1.67169 0.305242 3.1133 1.21466

H2O 0.3171 0.31714 0.317139 0.2864 0.504992 0.5049918 1.5076 0.703395 1 0.31491 1.7793 3.2335 4.76818

ACOH 1.7091 1.70911 1.709108 4.88965 4.843944 4.8439443 1.2359 6.267125 7.37915 1 15.94924 1 1

CH3CO 0.7999 0.79992 0.79992 1.30038 1.281154 1.2811539 0.4846 1.534144 0.11894 6.71995 1 1.1335 0.01526

CHO 0.6126 0.61261 0.612613 1.28731 0.473021 0.4730205 4.2486 0.460188 0.12345 1 0.650955 1 0.99749

COOH 0.0029 0.00288 0.002882 0.77632 0.610152 0.6101523 0.6723 0.310092 0.11216 1 1.404613 0.0294 1

CH3COO 2.926 2.92595 2.925954 0.68042 1.76859 1.7685903 0.5457 1.669449 0.27409 3.09971 0.820903 0.0258 0.00863

CH2O 0.0051 0.00515 0.005148 0.83959 0.802258 0.8022577 0.6314 2.078218 0.48981 1 0.838884 1 0.00907

CHCL2 0.9107 0.91067 0.910668 1 1 1 0.106 3.845767 0.08347 1 0.157754 1 0.23037

CCL3 0.9313 0.93127 0.93127 0.37998 0.893393 0.8933932 0.2458 4.768184 0.06992 1 15.94924 1 0.28871

ACNH2 0.5545 0.55453 0.554529 2.0838 1.053044 1.0530444 0.1696 1 2.23512 17.9118 0.056318 1 0.10173

aij-UNIFAC (LLE)

Parameters from T. Magnussen, P. Rasmussen, A. 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

aij-UNIFAC (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

LLE

Water(1)+mek(2) at 298K by UNIFAC (cf Arce, JCEDat,40:226)Summary of calculations for Example in Textbook

x1 Coexistence calculation0.00 0 ### 1 0 1 @x1~0.350.05 ### ### ### ### ###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

DGmix/RT gw gmek gw*xw gmek*xmek

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00-0.09 -0.08 -0.07 -0.06 -0.05 -0.04 -0.03 -0.02 -0.01

0

xw

Gm/RT

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.000

0.2

0.4

0.6

0.8

1

1.2

xw

xigi

LLE

0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.000

0.2

0.4

0.6

0.8

1

1.2

xw

xigi

LLE

Coexistence calculation

ACTCOEFF

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