Instructions

ACTCOEFF.XLSThis workbook will calculate activities, activity coefficients, and excess Gibbs energies for several activity models. Margules Regular Worksheet using the Margules equation with two adjustable parameters. A spreadsheet to calculate VLE for methanol + benzene using van Laar and Scatchard/Hildbrand theory. A spreadsheet to use with the binary UNIQUAC activity coefficient model. A spreadsheet to use UNIQUAC with up to 5 components. Table of Antoine Coefficients. A spreadsheet to use with the UNIFAC activity coefficient model for VLE for up to 5 components. Database of parameters used by UNIFAC for VLE. Two spreadsheets to use with the UNIFAC activity coefficient model for LLE for up to 5 components. Database of parameters used by UNIFAC for LLE. Liquid + Liquid equilibria: Water + MEK example used in the text.

UNIQUAC UNIQUAC5 ANTOINE UNIFAC (VLE)

aij-UNIFAC (VLE) UNIFAC (LLEa,b)

aij-UNIFAC (LLE) LLE

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

Page 1

81464827.xls Margules Equation GE/RT = x1 x2 ( A21 x1 + A12 x2 ) Margules Parameters A12_ 1.86 Table x1 increment 0.05

A21_ 1.64

x1 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95 1

x2 1 0.95 0.9 0.85 0.8 0.75 0.7 0.65 0.6 0.55 0.5 0.45 0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0

gamma1 6.43 5.26 4.35 3.65 3.11 2.67 2.33 2.05 1.83 1.65 1.51 1.39 1.29 1.21 1.15 1.1 1.06 1.03 1.01 1 1

gamma2 1 1.01 1.02 1.05 1.08 1.13 1.19 1.27 1.36 1.46 1.59 1.74 1.92 2.13 2.38 2.67 3.02 3.42 3.9 4.47 5.14

activity1 0 0.26 0.44 0.55 0.62 0.67 0.7 0.72 0.73 0.74 0.75 0.76 0.77 0.79 0.8 0.82 0.85 0.88 0.91 0.95 1

activity2 1 0.95 0.92 0.89 0.87 0.85 0.83 0.82 0.81 0.81 0.8 0.78 0.77 0.75 0.71 0.67 0.6 0.51 0.39 0.22 0

G(mix) /RT 0 -0.11 -0.16 -0.19 -0.21 -0.22 -0.23 -0.24 -0.25 -0.25 -0.26 -0.26 -0.26 -0.26 -0.25 -0.24 -0.23 -0.21 -0.18 -0.12 0

Page 2

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 (cal/cm3) Antoine Coeff A B C VL (cm3/mol) 1 MeOH 8.08 1582.27 239.73 40 14.5 2 benzene 6.88 1196.76 219.16 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 0.03 0.05 0.09 0.16 0.28 0.33 0.55 0.7 y1 0 0.27 T (C) 80.1 70.67 Calculations based on data T(K) 353.25 343.82 1 0 0.01 0.37 66.44 339.59 0.02 0.46 62.87 336.02 0.04 0.53 60.2 333.35 0.08 0.15 0.56 58.64 331.79 0.18 0.6 58.02 331.17 0.36 0.63 58.1 331.25 0.51

Scatchard-Hildebrand model with zero binary interaction coefficient (x's from above) see plot ----> x1 0 0.03 0.05 0.09 0.16 0.28 0.33 0.55 1 2 P1sat P2sat y1 calc y2 calc T(K) (yi-1)2 4.96 1 760 0 1 353.25 0 4.9 1 635.42 0.19 0.81 347.54 0 4.81 1 952.14 558.01 0.3 0.7 343.54 0 4.63 1.01 793.18 476.14 0.42 0.58 338.79 0 4.19 1.03 624.1 386.43 0.56 0.44 332.77 0 | 3.44 1.09 515.24 326.88 0.66 0.34 328.13 0 3.15 1.14 495.45 315.88 0.68 0.32 327.2 0 2.05 1.62 476.6 305.35 0.71 0.29 326.28

0.7 1.51 2.73

1360.42 1106.07

481.26 307.95 0.67 0.33 326.51

0 0

This table permits calculation of LLE if it exists as above in column G and M (LLE explained in Chap 12) *x LLE x1 1*x1 0 0.28 2*x2 0 0.97 Scatchard-Hildebrand model with binary interaction coefficient kij= x1 0 0.03 0.05 0.09 0.16 0.28 1 3 2.95 2.9 2.81 2.62 2.3 2 P1sat P2sat y1 calc y2 calc 1 760 0 1 1 684.87 0.12 0.88 1 631.32 0.21 0.79 1 970.38 567.28 0.32 0.68 1.02 809.73 484.77 0.46 0.54 1.06 680.29 416.59 0.58 0.42 1360.42 1206.11 1097.85 -0.03 0.33 2.16 1.09 650.46 400.63 0.62 0.38 0.55 1.62 1.39 593.28 369.73 0.7 0.3 0.7 1.32 1.97 588.08 366.9 0.71 0.29

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Regular T(K) (yi-1)2 353.25 0 349.9 0 347.34 0 344.04 0 339.32 0 334.91 0 333.79 0 331.53 0 331.32 0

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 1 A12 591.29 1.29 1.98 P2sat x1 1 2 P1sat P2sat y1 calc y2 calc T(K) (yi-1)2 368.65 0 7.28 1 760 0 1 353.25 0 0.03 6.48 1 600.2 0.23 0.77 345.77 0 2 0.05 5.85 1.01 885.79 524.1 0.34 0.66 341.64 0 2.06 0.09 5.01 1.02 759.29 458.4 0.44 0.56 337.67 0 0.16 3.77 1.06 653.48 402.25 0.53 0.47 333.91 0 A21 0.28 2.56 1.18 605.46 376.35 0.58 0.42 332.03 0 1.74 0.33 2.24 1.26 599.37 373.04 0.59 0.41 331.78 0

First, set this to 331.3 azeotrope T and comp then adjust kij until ce 0.

These values are calculated from the activi coefficient and composition values at the a

0.55 1.42 1.8 591.84 368.95 0.61 0.39 331.47 0

0.7 1.16 2.5 593.21 369.69 0.63 0.37 331.53 0

1360.42 1035.63

Page 4

Regular

(cal/cm3)1/2

0.78 0.67 58.47 331.62 0.62

0.9 0.76 59.9 333.05 0.8

0.97

0.97 0.91 62.7 335.85

1 1 64.7 337.85 1

0.94

0.94

3600.78 1.28 4.33 471.9 302.71 0.62 0.38 326.05 0 0.9 1.07 11.65 438.82 284.05 0.56 0.44 324.35 0 0.97 1.01 29.02 515.2 326.86 0.66 0.34 328.13 0 | 0.97 1.01 29.01 515.06 326.79 0.66 0.34 328.12 0 1 1 39.8 759.99 458.77 1 0 337.7 OBJ 0 0

350 340

T(K)

330 320 310 300 -0.2 0 0.2 0.4 x-y 0.6

E region --->

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

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.

0.78 1.18 2.69 588.26 367 0.72 0.28

0.9 1.05 5.19 598.28 372.45 0.74 0.26

0.97 1 9.64 668.77 410.43 0.86 0.14

0.97 1 9.63 668.69 410.4 0.86 0.14

1 1 12.5 759.99

355 350 345 340

T(K)Page 5

458.77 1 0

335 330 325 320 -0.2 0 0.2 0.4 x-y 0.6

0

345 340

T(K)

Regular 331.32 0 331.74 0 334.48 0 334.48 0 337.7 OBJ 0 0

335 330 325 320 -0.2 0 0.2 0.4 x-y 0.6

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

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

0

values are calculated from the activitiy cient and composition values at the azeotrope.

0.78 1.08 3.08 602.28 374.62 0.67 0.33 331.9 0

0.9 1.02 4.22 644.91 397.65 0.77 0.23 333.58 0

0.97 1 5.26 716.65 435.92 0.92 0.08 336.21 0

0.97 1 5.26 716.61 435.89 0.92 0.08 336.21 0

1 1 5.71 458.77 1 0 337.7 OBJ 0 0T(K)

355 350 345 340 335 330 325 320 -0.2 0 0.2 0.4 x-y 0.6

759.99

0

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

Page 6

Regular

.2

0.4 x-y

0.6

0.8

1

bove diagram are indicative sent experimental data. r is necessary to fit the data

0.2

0.4 x-y

0.6

0.8

1

Page 7

Regular

0.2

0.4 x-y

0.6

0.8

1

.2

0.4 x-y

0.6

0.8

1

Page 8

UNIQUAC UNIQUAC Calculation

Note: This spreadsheet uses the form of equations that permits the q of the residual part of the combinatorial part. (Anderson, T.F., Prausnitz, J.,M., Ind. Eng. Chem. Process De 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 -1.22 -32.78 529.57 (2) Benzene 3.19 2.4 2.4 1.76 2.72 Table x1 increment 0.05 x1 0.000000 0.050000 0.100000 0.150000 0.200000 0.250000 0.300000 0.350000 0.400000 0.450000 0.500000 0.550000 0.600000 0.650000 0.700000 0.750000 0.800000 0.850000 0.900000 0.950000 1.000000 x2 1 0.95 0.9 0.85 0.8 0.75 0.7 0.65 0.6 0.55 0.5 0.45 0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0 T(C) 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 90 T(K) 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 363.15 tau12 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 1.09 tau21 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 0.23 theta1 0 0.03 0.06 0.1 0.13 0.17 0.2 0.24 0.28 0.33 0.37 0.42 0.47 0.53 0.58 0.64 0.7 0.77 0.84 0.92 1 theta2 1 0.97 0.94 0.9 0.87 0.83 0.8 0.76 0.72 0.67 0.63 0.58 0.53 0.47 0.42 0.36 0.3 0.23 0.16 0.08 0 theta'1 0 0.03 0.06 0.1 0.13 0.17 0.2 0.24 0.28 0.33 0.37 0.42 0.47 0.53 0.58 0.64 0.7 0.77 0.84 0.92 1

Page 9

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 1 0.97 0.94 0.9 0.87 0.83 0.8 0.76 0.72 0.67 0.63 0.58 0.53 0.47 0.42 0.36 0.3 0.23 0.16 0.08 0

phi1 0 0.02 0.05 0.07 0.1 0.13 0.16 0.19 0.23 0.27 0.31 0.35 0.4 0.45 0.51 0.57 0.64 0.72 0.8 0.89 1

phi2 1 0.98 0.95 0.93 0.9 0.87 0.84 0.81 0.77 0.73 0.69 0.65 0.6 0.55 0.49 0.43 0.36 0.28 0.2 0.11 0

ln(gam1) 1.96 1.71 1.49 1.29 1.12 0.97 0.83 0.71 0.6 0.5 0.41 0.33 0.26 0.2 0.15 0.11 0.07 0.04 0.02 0 0

ln(gam2) 0 0.01 0.02 0.05 0.09 0.13 0.19 0.24 0.31 0.38 0.46 0.55 0.64 0.74 0.85 0.97 1.1 1.24 1.39 1.55 1.73

gam1 7.12 5.53 4.44 3.65 3.07 2.63 2.29 2.03 1.82 1.65 1.51 1.4 1.3 1.23 1.16 1.11 1.07 1.04 1.02 1 1

gam2 1 1.01 1.02 1.05 1.09 1.14 1.2 1.28 1.36 1.47 1.59 1.73 1.9 2.1 2.35 2.64 3 3.45 4.01 4.72 5.65

Page 10

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 8.07 7.28 Antoine B 1730.63 1434.2 Antoine C 233.43 246.5 Psat (mmHg) 23.69 99.57 1 1 1 y 0.2283 0.7717 0.0000 0.0000 0.0000 Unhide columns G-R for LLE iterations. Pcalc (mm Hg) 98.49 T (K) = Name x x r q ixiri 298.15 Phase 1 Water 8.91E-01 1.07 0.95 0.92 1.4 0.7 0.8 MEK 9.89E-02 7.72 0.76 3.25 2.88 0.28 0.18 2 Acetic 1.00E-02 0.08 0 2.2 2.07 0.02 0.01 1.00E-11 4.27 0 3.19 2.4 0 0 1.00E-11 1.19 0 1.43 1.43 0 0 3 4 5

1.16 ixiqi 1.55 aij matrix (i = row, j=column), enter 0's for unused cells 1 2 3 1 1 -2.09 254.15 2 345.53 1 -254.13 3 -301.02 -4.55 1 4 0 0 0 5 0 0 0 ij matrix (i = row, j=column) 1 1 1 2 1.01 3 0.43

4 0 0 0 1 0

5 0 0 0 0 1

4 1

5 1

Page 11

UNIQUAC5 2 3 4 5 ln(comb) i(iij) j/i(iij) j{jkj/(iiij)} ln(resid) 0.31 2.74 1 1 0.03 0.9 0.9 1.09 0.03 1 1.02 1 1 0.63 1.01 0.18 0.5 1.41 2.35 1 1 1 0.46 0.79 0.02 2.66 -2.94 1 1 1 1 1.68 1 0 1.09 -0.23 1 1 1 1 0.31 1 0 1.09 -0.13

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

Page 12

Antoine coefficients for: log10(Psat[mmHg])=A-B/(T[oC]+C) T[oC] 100

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

methanol ethanol 1-propanol 1-propanol 2-propanol 1-butanol 1-butanol 8.08 8.11 7.74 8.38 8.88 7.81 7.75 1582.27 1592.86 1437.69 1788.02 2010.33 1522.56 1506.07 239.73 226.18 198.46 227.44 252.64 191.95 191.59 15 20 60 -15 -26 30 70 84 93 106 98 83 70 120 3 3 3 3 2 2 2651.42 1693.83 845.66 828.54 1504.62 393.68 387.53 methane ethane propane n-butane n-pentane n-pentane n-hexane 6.64 6.83 6.8 6.81 6.85 6.88 6.88 395.74 663.72 804 935.77 1064.84 1075.78 1171.17 266.68 256.68 247.04 238.79 232.01 233.21 224.41 -182 -143 -108 -78 -50 -50 -25 -158 -84 -35.65 19 58 58 92 5 5 5 5 5 3 5 366903.01 92966.74 30665.09 11108.55 4423.1 4443.62 1844.31

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

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

cyclohexanecyclohexane methylcyclohexane isopentane toluene benzene m-xylene 7.26 6.85 7.12 8.11 6.95 6.88 7.01 1434.15 1206.47 1444.59 1592.86 1342.31 1196.76 1462.27 246.72 223.14 240.18 226.18 219.19 219.16 215.11 6.7 7 -3 20 -27 8 29 80.7 81 100 93 111 80 166 1 3 1 3 3 3 1344.1 1311.69 740.63 1693.83 556.5 1349.47 233.67 water acetonitrile Triethylamineacetic acid acetic acid chloroform dichloromethane 7.34 5.86 8.02 8.27 6.95 7.08 1482.29 695.67 1936.01 2258.22 1170.97 1138.91 250.52 144.83 258.45 300.97 226.23 231.45 -27 50 18 118 -10 -44 82 95 118 227 60 59 3 3 3 3 3 3 1291.41 1040.85 416.83 431.97 2318.91 4407.13

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

8.07 1730.63 233.43 1 100 3 760.09

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 7.36 7.2 8.37 7.25 1305.2 1157 2170.24 1448.57 173.43 168.28 205.92 134.12 89 72 55 80 126 107 150 200 3 3 1 1 389.21 773.81 18.7 11.6 hexane 6.91 1189.64 226.28 -30 170 3 1838.69 n-heptane heptane n-octane n-nonane n-decane decane 6.9 6.89 6.92 6.94 6.94 7.44 1264.9 1264.37 1351.99 1431.82 1495.17 1843.12 216.54 216.64 209.16 202.11 193.86 230.22 -2 -3 19 39 58 17 123 127 152 178 203 174 5 3 5 5 5 3 795.79 795.75 351.16 158.32 71.71 72.2

o-xylene 7 1476.39 213.87 63 145 3 198.49

p-xylene acetone acetone acrolein ethyl acetate 1,4-dioxane 2-butanone 2-butanone 6.99 7.63 7.12 7.07 7.1 7.43 7.28 7.06 1453.43 1566.69 1210.6 1204.95 1244.95 1554.68 1434.2 1261.34 215.31 273.42 229.66 235.35 217.88 240.34 246.5 221.97 27 57 -13 -65 16 20 -6.5 43 166 205 55 53 76 105 80 88 3 3 3 3 3 3 1 3 240.44 2727.54 2785.68 2977.13 1532.45 730.29 1385.3 1399.53

dichoromethane tetrachloromethane 1,2-dichloroethane chloride Benzyl nitroethane Biphenyl Naphthalene 7.41 6.84 7.03 7.6 7.19 13.54 8.62 1325.94 1177.91 1271.25 1961.47 1446.51 4993.37 2165.72 252.62 220.58 222.93 236.51 220.79 296.07 198.28 -40 -20 -31 22 1.5 20 20 40 77 99 180 94 40 40 3 3 3 1 1 solid 4(solid) 4455.24 1467.49 1226.42 58.66 484.67 8.48 23

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 7.23 1477.02 237.52 36 102 3 715.32

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.

has a formula to calculate P= 745.52 mmHg the bubble pressure. 80.37 oC T(oC)= sat Table 1. Antoine Coefficients (mmHg) log10(P )=A-B/(T+C) where T[=] oC A B C Psat[mmHg] yi comp1 8.88 2010.33 252.64 694.02 0.58963 comp1 IPA xi SubGroup 1 2 3 9 10 11 12 14 15 16 17 18 20 21 29 36 42 49 51 99 i CH3 CH2 CH ACH AC ACCH3 ACCH2 OH CH3OH H2O ACOH CH3CO CHO CH3COO CH2NH2 ACNH2 COOH CCL2 CCL3 CON(CH2)2 kk(i)xi N groups 2 4 0.5 1 0 3 0 3 0 5 Note that columns H:AS are hidden. They contain intermediate calculations. Unprotect the sheet and unhide them to see the calculations. 1 0.500 1.267 2 1 comp2 8.07 1730.63 233.43 359.89 0.41037 comp2 Water 0.500 1.700 comp3 comp4 8.11 1592.86 226.18 824.46 0.00000 comp4 EtOH 0.000 1.107 1 1 comp5 6.88 1075.78 233.21 2790.14 0.00000 comp5 C5H12 0.000 12.607 2 3 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)". Liquid phase mole fractions. Enter a very small number like 1E20 or smaller for absent compounds - don't use zero. Enter Antoine constants or vapor pressures if you want bubble P and vapor phase concentrations calculated automatically. Vapor phase mole fractions calculated automatically.

As distributed, this cell

0.00000 comp3 C2-COOH 0.000 0.980 1 1

Table 2. Component Structure Information and Activity Coefficient Calculation.

1 1

1

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)".

q r i i lnC lnRo lnR

3.1240 3.2491 0.6905 0.7793 0.0042 1.3197 1.5520

1.4000 0.9200 0.3095 0.2207 0.0994 0.0000 0.4313

2.6120 2.8768 0.0000 0.0000 0.1625 1.1812 0.9983

2.5880 2.5755 0.0000 0.0000 0.0152 1.0915 1.1784

3.3160 3.8254 0.0000 0.0000 0.2233 0.0000 2.3110

Page 16

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 1 0 86.02 61.13 76.5 986.5 697.2 1318 2 -35.36 0 38.81 74.15 524.1 787.6 270.6 3 -11.12 3.45 0 167 636.1 637.3 903.8 4 -69.7 -113.6 -146.8 0 803.2 603.2 5695 5 156.4 457 89.6 25.82 0 -137.1 353.5 6 16.51 -12.52 -50 -44.5 249.1 0 -181 7 300 496.1 362.3 377.6 -229.1 289.6 0 8 275.8 217.5 25.34 244.2 -451.6 -265.2 -601.8 9 26.76 42.92 140.1 365.8 164.5 108.7 472.5 10 505.7 56.3 23.39 106 529 -340.2 480.8 11 114.8 132.1 85.84 -170 245.4 249.6 200.8 14 -30.48 1.16 -44.85 296.4 -242.8 -481.7 -330.4 17 1139 2000 247.5 762.8 -17.4 -118.1 -341.6 20 315.3 1264 62.32 89.96 -151 339.8 -66.17 22 34.1 -23.5 121.3 140.8 527.6 669.9 708.7 23 36.7 51.06 228.5 69.9 742.1 649.1 826.8 46 27.97 9.76 394.8 -509.3

8 1333 526.1 1329 884.9 -259.7 -101.7 324.5 0 -133.1 -155.6 -36.72 -253.1 -11

9 476.4 182.6 25.77 -52.1 84 23.39 -195.4 -356.1 0 128 372.2 -450.3 -297.8 82.86 552.1

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 1 2 MainGroup 1 CH3 1 CH2 R 0.9 0.67 Q 0.85 0.54

Page 17

aij-UNIFAC (VLE) 3 4 5 6 7 8 70 9 10 11 12 13 14 15 16 17 18 19 20 21 22 29 36 42 49 51 99 1 CH 1C 2 CH2=CH 2 CH=CH 2 CH2=C 2 CH=C 2 C=C 3 ACH 3 AC 4 ACCH3 4 ACCH2 4 ACCH 5 OH 6 CH3OH 7 H2O 8 ACOH 9 CH3CO 9 CH2CO 10 CHO 11 CH3COO 11 CH2COO 14 CH2NH2 17 ACNH2 20 COOH 22 CCL2 23 CCL3 46 CON(CH2)2 0.45 0.22 1.35 1.12 1.12 0.89 0.66 0.53 0.37 1.27 1.04 0.81 1 1.43 0.92 0.9 1.67 1.45 1 1.9 1.68 1.37 1.06 1.3 1.8 2.64 2.41 0.23 0 1.18 0.87 0.99 0.68 0.49 0.4 0.12 0.97 0.66 0.35 1.2 1.43 1.4 0.68 1.49 1.18 0.95 1.73 1.42 1.24 0.82 1.22 1.45 2.18 1.81

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aij-UNIFAC (VLE)

Table 3. Interaction Parameters to be u Do not edit this table unless you want T= 80.37

10 677 448.8 347.3 586.6 -203.6 306.4 -116 -271.1 -37.36 0 185.1

11 232.1 37.85 5.99 5688 101.1 -10.72 72.87 -449.4 -213.7 -110.3 0 -294.8 -256.3 -133 176.5

14 391.5 240.9 161.7 19.02 8.64 359.3 48.89

17 920.7 749.3 648.2 664.2 -52.39 489.7 243.2 119.9 6201 475.5 -200.7 0 493.8 140.8

20 663.5 318.9 537.4 872.3 199 -202 -14.09 408.9 669.4 497.5 660.2 -396 0 543.3 504.2 -70.25

22 53.76 58.55 -144.4 -111 65.28 -102.5 370.4 -130.3 67.52 108.9 -111 -44.7 0 -84.53

23 24.9 -13.99 -231.9 -80.25 -98.12 -139.4 353.7 -354.6 -483.7 -209.7

46 380.9 200.2

-382.7 835.6

0 -15.07

-165.5 190.6 242.8

39.63 0 0

-322.3

0

Sub Main Group Group 1 1 2 1 3 1 9 3 10 3 11 4 12 4 14 5 15 6 16 7 17 8 18 9 20 10 21 11 29 14 36 17 42 20 49 22 51 23 99 46

Page 19

aij-UNIFAC (VLE)

Page 20

aij-UNIFAC (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 Q CH3 CH2 0.85 0 0 0.54 0 0 0.23 0 0 0.4 -11.12 -11.12 0.12 -11.12 -11.12 0.97 -69.7 -69.7 0.66 -69.7 -69.7 1.2 156.4 156.4 1.43 16.51 16.51 1.4 300 300 0.68 275.8 275.8 1.49 26.76 26.76 0.95 505.7 505.7 1.73 114.8 114.8 1.24 -30.48 -30.48 0.82 1139 1139 1.22 315.3 315.3 1.45 34.1 34.1 2.18 36.7 36.7 1.81 27.97 27.97 1 CH 0 0 0 -11.12 -11.12 -69.7 -69.7 156.4 16.51 300 275.8 26.76 505.7 114.8 -30.48 1139 315.3 34.1 36.7 27.97 3 ACH 61.13 61.13 61.13 0 0 -146.8 -146.8 89.6 -50 362.3 25.34 140.1 23.39 85.84 -44.85 247.5 62.32 121.3 228.5 0 3 AC 61.13 61.13 61.13 0 0 -146.8 -146.8 89.6 -50 362.3 25.34 140.1 23.39 85.84 -44.85 247.5 62.32 121.3 228.5 0 4 ACCH3 76.5 76.5 76.5 167 167 0 0 25.82 -44.5 377.6 244.2 365.8 106 -170 296.4 762.8 89.96 140.8 69.9 0 4 ACCH2 76.5 76.5 76.5 167 167 0 0 25.82 -44.5 377.6 244.2 365.8 106 -170 296.4 762.8 89.96 140.8 69.9 0

R CH3 CH2 CH ACH AC ACCH3 ACCH2 OH CH3OH H2O ACOH CH3CO CHO CH3COO CH2NH2 ACNH2 COOH CCL2 CCL3 CON(CH2)2 0.9 0.67 0.45 0.53 0.37 1.27 1.04 1 1.43 0.92 0.9 1.67 1 1.9 1.37 1.06 1.3 1.8 2.64 2.41

Table 4. Matrix of 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. CH3 CH2 CH ACH AC ACCH3 ACCH2 OH CH3 1 1 1 0.84 0.84 0.81 0.81

CH3OH 0.06 0.14

Page 21

aij-UNIFAC (VLE) CH2 CH ACH AC ACCH3 ACCH2 OH CH3OH H2O ACOH CH3CO CHO CH3COO CH2NH2 ACNH2 COOH CCL2 CCL3 CON(CH2)2 1 1 1.03 1.03 1.22 1.22 0.64 0.95 0.43 0.46 0.93 0.24 0.72 1.09 0.04 0.41 0.91 0.9 0.92 1 1 1.03 1.03 1.22 1.22 0.64 0.95 0.43 0.46 0.93 0.24 0.72 1.09 0.04 0.41 0.91 0.9 0.92 1 1 1.03 1.03 1.22 1.22 0.64 0.95 0.43 0.46 0.93 0.24 0.72 1.09 0.04 0.41 0.91 0.9 0.92 0.84 0.84 1 1 1.51 1.51 0.78 1.15 0.36 0.93 0.67 0.94 0.78 1.14 0.5 0.84 0.71 0.52 1 0.84 0.84 1 1 1.51 1.51 0.78 1.15 0.36 0.93 0.67 0.94 0.78 1.14 0.5 0.84 0.71 0.52 1 0.81 0.81 0.62 0.62 1 1 0.93 1.13 0.34 0.5 0.36 0.74 1.62 0.43 0.12 0.78 0.67 0.82 1 0.81 0.81 0.62 0.62 1 1 0.93 1.13 0.34 0.5 0.36 0.74 1.62 0.43 0.12 0.78 0.67 0.82 1 0.06 0.06 0.17 0.17 0.1 0.1 1 0.49 1.91 3.59 0.63 0.22 0.5 1.99 1.05 1.53 0.22 0.12 0.33 0.14 0.14 0.16 0.16 0.18 0.18 1.47 1 0.44 2.12 0.74 2.62 0.49 3.91 1.4 0.38 0.15 0.16 1

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aij-UNIFAC (VLE)

5 OH 986.5 986.5 986.5 636.1 636.1 803.2 803.2 0 249.1 -229.1 -451.6 164.5 529 245.4 -242.8 -17.4 -151 527.6 742.1 394.8

6 CH3OH 697.2 697.2 697.2 637.3 637.3 603.2 603.2 -137.1 0 289.6 -265.2 108.7 -340.2 249.6 -481.7 -118.1 339.8 669.9 649.1 0

7 H2O 1318 1318 1318 903.8 903.8 5695 5695 353.5 -181 0 -601.8 472.5 480.8 200.8 -330.4 -341.6 -66.17 708.7 826.8 -509.3

8 ACOH 1333 1333 1333 1329 1329 884.9 884.9 -259.7 -101.7 324.5 0 -133.1 -155.6 -36.72 0 -253.1 -11 0 0 0

9 CH3CO 476.4 476.4 476.4 25.77 25.77 -52.1 -52.1 84 23.39 -195.4 -356.1 0 128 372.2 0 -450.3 -297.8 82.86 552.1 0

10 CHO 677 677 677 347.3 347.3 586.6 586.6 -203.6 306.4 -116 -271.1 -37.36 0 185.1 0 0 -165.5 190.6 242.8 0

11 CH3COO 232.1 232.1 232.1 5.99 5.99 5688 5688 101.1 -10.72 72.87 -449.4 -213.7 -110.3 0 0 -294.8 -256.3 -133 176.5 0

14 CH2NH2 391.5 391.5 391.5 161.7 161.7 19.02 19.02 8.64 359.3 48.89 0 0 0 0 0 -15.07 0 0 0 0

17 ACNH2 920.7 920.7 920.7 648.2 648.2 664.2 664.2 -52.39 489.7 243.2 119.9 6201 0 475.5 -200.7 0 493.8 140.8 0 0

20 COOH 663.5 663.5 663.5 537.4 537.4 872.3 872.3 199 -202 -14.09 408.9 669.4 497.5 660.2 0 -396 0 543.3 504.2 -70.25

H2O 0.02

ACOH 0.02

CH3CO 0.26

CHO 0.15

CH3COO CH2NH2 ACNH2 COOH 0.52 0.33 0.07

CCL2 0.15 0.86

CCL3 0.93

Page 23

aij-UNIFAC (VLE) 0.02 0.02 0.08 0.08 0 0 0.37 1.67 1 5.49 0.26 0.26 0.57 2.55 2.63 1.21 0.13 0.1 4.22 0.02 0.02 0.02 0.02 0.08 0.08 2.08 1.33 0.4 1 1.46 1.55 1.11 1 2.05 1.03 1 1 1 0.26 0.26 0.93 0.93 1.16 1.16 0.79 0.94 1.74 2.74 1 0.7 0.35 1 3.57 2.32 0.79 0.21 1 0.15 0.15 0.37 0.37 0.19 0.19 1.78 0.42 1.39 2.15 1.11 1 0.59 1 1 1.6 0.58 0.5 1 0.52 0.52 0.98 0.98 0 0 0.75 1.03 0.81 3.57 1.83 1.37 1 1 2.3 2.06 1.46 0.61 1 0.33 0.33 0.63 0.63 0.95 0.95 0.98 0.36 0.87 1 1 1 1 1 1.04 1 1 1 1 0.07 0.07 0.16 0.16 0.15 0.15 1.16 0.25 0.5 0.71 0 1 0.26 1.76 1 0.25 0.67 1 1 0.15 0.15 0.22 0.22 0.08 0.08 0.57 1.77 1.04 0.31 0.15 0.24 0.15 1 3.07 1 0.22 0.24 1.22 0.86 0.86 1.5 1.5 1.37 1.37 0.83 1.34 0.35 1 1.45 0.83 0.73 1 1.37 1.13 1 1.27 1 0.93 0.93 1.93 1.93 1.25 1.25 1.32 1.48 0.37 1 2.73 3.93 1.81 1 1 0.89 1 1 1

Page 24

aij-UNIFAC (VLE)

22 CCL2 53.76 53.76 53.76 -144.4 -144.4 -111 -111 65.28 -102.5 370.4 0 -130.3 67.52 108.9 0 -111 -44.7 0 -84.53 0

23 46 CCL3 CON(CH2)2 24.9 380.9 CH3 24.9 380.9 CH2 24.9 380.9 CH -231.9 0 ACH -231.9 0 AC -80.25 0 ACCH3 -80.25 0 ACCH2 -98.12 -382.7 OH -139.4 0 CH3OH 353.7 835.6 H2O 0 0 ACOH -354.6 0 CH3CO -483.7 0 CHO -209.7 0 CH3COO 0 0 CH2NH2 0 0 ACNH2 39.63 -322.3 COOH 0 0 CCL2 0 0 CCL3 0 0 CON(CH2)2

CON(CH2)2 0.34

Page 25

aij-UNIFAC (VLE) 0.34 0.34 1 1 1 1 2.95 1 0.09 1 1 1 1 1 1 2.49 1 1 1

Page 26

UNIFAC (LLEa)

Liquid-liquid calculation using UNIFAC LLE. Sheet for first liquid phase. See also "UNIFAC (LLEb)". Instructions: Type the temperature of interest in centigrade. Then enter the number of occurences of each functional group in each component. If you have less than 5 components, type a samll number like 1E-20 for the mole fractions of the absent components. If you want the pressure to be computed automatically, you must enter the Antoine coefficients of the components. To use different functional groups than those provided, follow the instructions on the aij-UNIFAC sheet.

P= T(oC)=

86.45 mmHg 25 oCcomp1 8.07 1730.63 233.43 23.69 0.26079 1 Water comp2 7.28 1434.2 246.5 99.57 0.73763 2 MEK 0.100 6.414 1 1

Note: hidden columns with -> intermediate calcscomp3 comp4 comp5