Beruflich Dokumente
Kultur Dokumente
ACTCOEFF.XLS
This workbook will calculate activities, activity coefficients, and excess Gibbs energies
for several activity models.
Margules
Regular
UNIQUAC
UNIQUAC5
ANTOINE
UNIFAC (VLE)
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
133424545.xls
Margules Equation
GE/RT = x1 x2 ( A21 x1 + A12 x2 )
Margules Parameters
A12_
1.86
Table x1 increment
0.05
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
A21_
1.64
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
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)1/2
VL (cm3/mol)
Antoine Coeff
A
B
C
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
0.78
y1
0
0.27
0.37
0.46
0.53
0.56
0.6
0.63
0.67
T (C)
80.1
70.67
66.44
62.87
60.2
58.64
58.02
58.1
58.47
Calculations based on data
T(K)
353.25 343.82 339.59 336.02 333.35
331.79 331.17 331.25 331.62
1
0
0.01
0.02
0.04
0.08
0.15
0.18
0.36
0.51
0.62
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
0.7
0.78
4.96
4.9
4.81
4.63
4.19
3.44
3.15
2.05
1.51
1.28
1.01
1.03
1.09
1.14
1.62
2.73
4.33
1360.42 1106.07
952.14
793.18
624.1
515.24
495.45
476.6
481.26
471.9
P
P
sat
1
sat
2
y1 calc
y2 calc
T(K)
(yi-1)2
760
635.42
558.01
476.14
386.43
326.88
315.88
305.35
307.95
302.71
0.19
0.3
0.42
0.56
0.66
0.68
0.71
0.67
0.62
1
353.25
0.81
347.54
0.7
343.54
0.58
338.79
0.44
332.77
0.34
328.13
0.32
327.2
0.29
326.28
0.33
326.51
0.38
326.05
0
0
<----- LLE region --->
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
0.33
0.55
0.7
0.78
2.95
2.9
2.81
2.62
2.3
2.16
1.62
1.32
1.18
1.02
1.06
1.09
1.39
1.97
2.69
P1sat
-0.03
970.38
809.73
680.29
650.46
593.28
588.08
588.26
P2sat
760
684.87
631.32
567.28
484.77
416.59
400.63
369.73
366.9
367
y1 calc
0.12
0.21
0.32
0.46
0.58
0.62
0.7
0.71
0.72
1
353.25
0.88
349.9
0.79
347.34
0.68
344.04
0.54
339.32
0.42
334.91
0.38
333.79
0.3
331.53
0.29
331.32
0.28
331.32
y2 calc
T(K)
(yi-1)2
Page 3
Regular
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
These values are calculated from the activitiy coefficient
P2sat
368.65
A21
2.06
1.74
x1
0.03
0.05
0.09
0.16
0.28
0.33
0.55
0.7
0.78
7.28
6.48
5.85
5.01
3.77
2.56
2.24
1.42
1.16
1.08
1.01
1.02
1.06
1.18
1.26
1.8
2.5
3.08
1360.42 1035.63
P1sat
885.79
759.29
653.48
605.46
599.37
591.84
593.21
602.28
P2sat
760
600.2
524.1
458.4
402.25
376.35
373.04
368.95
369.69
374.62
y1 calc
0.23
0.34
0.44
0.53
0.58
0.59
0.61
0.63
0.67
1
353.25
0.77
345.77
0.66
341.64
0.56
337.67
0.47
333.91
0.42
332.03
0.41
331.78
0.39
331.47
0.37
331.53
0.33
331.9
y2 calc
T(K)
(yi-1)2
Page 4
Regular
0.9
0.97
0.76
59.9
0.91
62.7
1
64.7
333.05
335.85
337.85
0.94
0.8
0.97
0.94
360
0.97
0.97
1.07
1.01
1.01
11.65
29.02
29.01
39.8
438.82
515.2
515.06
759.99
284.05
326.86
326.79
458.77
0.56
0.66
0.66
0.44
324.35
0.34
328.13
0.34
328.12
0
|
350
340
T(K)
0.9
320
310
0
337.7 OBJ
0
330
300
0
0.3
0.4
0.5
x-y
0.6
0.7
0.8
0.9
355
0.97
0.97
1.05
350
5.19
9.64
9.63
12.5
345
598.28
668.77
668.69
759.99
372.45
410.43
410.4
458.77
0.74
0.86
0.86
0.26
331.74
0.14
334.48
0.14
334.48
0.2
0.9
T(K)
340
335
330
0
337.7 OBJ
0
0.1
325
320
0
Page 5
T(K)
335
330
Regular
325
First, set this to 331.3 (close to
azeotrope T and composition),
then adjust kij until cell J48 = 0.
320
Then, use Solver to adjust
B47:O47 to calc bubble T's.
0.1
0.97
0.97
355
1.02
350
4.22
5.26
5.26
5.71
345
644.91
716.65
716.61
759.99
340
397.65
435.92
435.89
458.77
0.77
0.92
0.92
330
0.23
333.58
0.08
336.21
0.08
336.21
0
337.7 OBJ
325
T(K)
0.9
335
320
0.2
0.3
0.4
0.5
x-y
Page 6
0.6
0.7
0.8
0.9
.7
Regular
0.8
0.9
7 0.8 0.9
1
Page 7
Regular
7 0.8 0.9
0.8
0.9
Page 8
UNIQUAC
UNIQUAC Calculation
Note: This spreadsheet uses the form of equations that permits the q of the residual part to
of the combinatorial part. (Anderson, T.F., Prausnitz, J.,M., Ind. Eng. Chem. Process Des. D
The formulas look a little different because or the use of the intermediate variable 'l', howev
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
Page 9
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
UNIQUAC
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) ln(gam2)
1.96
0
1.71
0.01
1.49
0.02
1.29
0.05
1.12
0.09
0.97
0.13
0.83
0.19
0.71
0.24
0.6
0.31
0.5
0.38
0.41
0.46
0.33
0.55
0.26
0.64
0.2
0.74
0.15
0.85
0.11
0.97
0.07
1.1
0.04
1.24
0.02
1.39
0
1.55
0
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
Page 10
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
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) =
298.15 Phase
1
Name
x
1.00E-11
1.00E-11
Water
2
MEK
Acetic
1.07
0.95
7.72
0.76
0.08
0
4.27
0
1.19
0
0.92
1.4
0.7
0.8
3.25
2.88
0.28
0.18
2.2
2.07
0.02
0.01
3.19
2.4
0
0
1.43
1.43
0
0
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
4
0
0
0
1
0
5
0
0
0
0
1
4
1
1
1
5
1
1
1
r
q
ixiri
2
1.01
1
1.02
3
0.43
2.35
1
Page 11
UNIQUAC5
4
5
1
1
1
1
1
1
1
1
1
1
ln(comb)
i(iij)
0.03
0.63
0.46
1.68
0.31
0.9
1.01
0.79
j/i(iij)
0.9
0.18
0.02
1.09
0.03
0.5
1.41
2.66
-2.94
1.09
-0.23
1.09
-0.13
j{jkj/(iiij)}
ln(resid)
ZOOM in to see subscripts clearly, the i's and j's look the same when the font is small.
Page 12
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
A
B
C
tMin[oC]
tMax[oC]
Source
Psat[mmHg]
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
### 92966.74 30665.09 11108.55
4423.1
4443.62
1844.31
A
B
C
tMin[oC]
tMax[oC]
Source
Psat[mmHg]
cyclohexane
cyclohexane 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
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
o-xylene
7
1476.39
213.87
63
145
3
198.49
dichoromethane
tetrachloromethane
1,2-dichloroethane
Benzyl chloride
nitroethaneBiphenyl 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
ong, K.N. 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.
comp1
8.88
2010.33
252.64
694.02
comp2
8.07
1730.63
233.43
359.89
0.58963
0.41037
comp3
comp4
8.11
1592.86
226.18
824.46
comp5
6.88
1075.78
233.21
2790.14
0.00000 0.00000
0.00000
SubGroup
comp1
comp2
comp3
comp4
comp5
IPA
Water
C2-COOH
EtOH
C5H12
xi
0.500
0.500
0.000
0.000
0.000
1.267
1.700
0.980
1.107
12.607
CH3
2
3
9
10
11
12
14
15
CH2
CH
ACH
AC
ACCH3
ACCH2
OH
CH3OH
16
H2O
17
ACOH
18
CH3CO
20
CHO
21
CH3COO
29
CH2NH2
36
ACNH2
42
COOH
49
CCL2
51
CCL3
99
CON(CH2)2
2
1
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)".
kk(i)xi
0.5
N groups
3.1240
1.4000
2.6120
2.5880
3.3160
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
lnC
0.0042
0.0994
0.1625
0.0152
0.2233
lnRo
1.3197
0.0000
1.1812
1.0915
0.0000
lnR
1.5520
0.4313
0.9983
1.1784
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
8
1
0
86.02
61.13
76.5
986.5
697.2
1318
1333
2
-35.36
0
38.81
74.15
524.1
787.6
270.6
526.1
3
-11.12
3.45
0
167
636.1
637.3
903.8
1329
4
-69.7
-113.6
-146.8
0
803.2
603.2
5695
884.9
5
156.4
457
89.6
25.82
0
-137.1
353.5
-259.7
6
16.51
-12.52
-50
-44.5
249.1
0
-181
-101.7
7
300
496.1
362.3
377.6
-229.1
289.6
0
324.5
8
275.8
217.5
25.34
244.2
-451.6
-265.2
-601.8
0
9
26.76
42.92
140.1
365.8
164.5
108.7
472.5
-133.1
10
505.7
56.3
23.39
106
529
-340.2
480.8
-155.6
11
114.8
132.1
85.84
-170
245.4
249.6
200.8
-36.72
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
-253.1
20
315.3
1264
62.32
89.96
-151
339.8
-66.17
-11
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
MainGroup
1
2
3
4
R
1 CH3
1 CH2
1 CH
1C
Q
0.9
0.67
0.45
0.22
0.85
0.54
0.23
0
Page 17
9
476.4
182.6
25.77
-52.1
84
23.39
-195.4
-356.1
0
128
372.2
10
677
448.8
347.3
586.6
-203.6
306.4
-116
-271.1
-37.36
0
185.1
-450.3
-297.8
82.86
552.1
-165.5
190.6
242.8
aij-UNIFAC (VLE)
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
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
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
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
Page 18
aij-UNIFAC (VLE)
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
0
-15.07
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
22
53.76
58.55
-144.4
-111
65.28
-102.5
370.4
23
24.9
-13.99
-231.9
-80.25
-98.12
-139.4
353.7
-130.3
67.52
108.9
-354.6
-483.7
-209.7
-396
0
543.3
504.2
-70.25
-111
-44.7
0
-84.53
39.63
0
0
46
380.9
200.2
-382.7
835.6
-322.3
80.37 C
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
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
CH3
CH3
1
CH2
1
CH
1
Page 19
aij-UNIFAC (VLE)
ACH
AC
ACCH3
ACCH2
OH
CH3OH
H2O
ACOH
CH3CO
CHO
CH3COO
CH2NH2
ACNH2
COOH
CCL2
CCL3
CON(CH2)2
Page 20
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
aij-UNIFAC (VLE)
ers to be used in the calculations for the selected groups as indicated on sheet "UNIFAC (VLE)".
you want to reprogram. Change values in Tables 1 and 2 unless you want to reprogram.
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
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
CH
1
1
1
ACH
1
1
1
AC
0.84
0.84
0.84
ACCH3
0.84
0.84
0.84
ACCH2
0.81
0.81
0.81
OH
0.81
0.81
0.81
Page 21
CH3OH
0.06
0.06
0.06
H2O
0.14
0.14
0.14
ACOH
0.02
0.02
0.02
CH3CO
0.02
0.02
0.02
0.26
0.26
0.26
aij-UNIFAC (VLE)
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
1.03
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
1.51
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
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
0.62
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
0.62
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
Page 22
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
0.16
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
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
0.08
0.08
2.08
1.33
0.4
1
1.46
1.55
1.11
1
2.05
1.03
1
1
1
0.93
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
aij-UNIFAC (VLE)
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
CHO
0.15
0.15
0.15
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
CH3COO
CH2NH2
ACNH2
COOH
CCL2
0.52
0.33
0.07
0.15
0.52
0.33
0.07
0.15
0.52
0.33
0.07
0.15
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
CCL3
0.86
0.86
0.86
Page 23
0.93
0.93
0.93
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
CON(CH2)2
0.34
0.34
0.34
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
aij-UNIFAC (VLE)
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
0.98
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
0.63
0.63
0.95
0.95
0.98
0.36
0.87
1
1
1
1
1
1.04
1
1
1
1
0.16
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
0.22
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
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
Page 24
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
1
1
1
1
2.95
1
0.09
1
1
1
1
1
1
2.49
1
1
1
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
functional groups without editing "aijUNIFAC (LLE)". That will be provided
in the future.
Note: hidden
<P=
86.45 mmHg columns with ->
intermediate calcs
T(oC)=
25 oC
Antoine Coefficients (mmHg) log10(Psat)=A-B/(T+C) where T[=] oC
A
B
C
Psat[mmHg]
yi
x
i
comp1
8.07
1730.63
233.43
23.69
comp2
7.28
1434.2
246.5
99.57
0.26079
0.73763
comp3
comp4
comp5
0.00158 0.00000
0.00000
phase
comp4
comp5
Water
MEK
c2-COOH
EtOH
C5H12
0.830
0.100
0.070
0.000
0.000
1.147
6.414
1.951
1.705
199.114
CH3
Ki,old
CH2
Ki,new
CH
xi,old
ACH
xi,new
ACCH2
xi,old
ACCH3
OH
2-Propanol
H2O
xi,new
1
1
ACOH
CH3CO
CHO
COOH
CH3COO
CH2O
CHCL2
CCL3
ACNH2
kk(i)xi
0.83
0.3
0.21
1.4000
2.8760
2.6120
2.5880
3.3160
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
lnC
0.0606
0.4430
0.3795
0.0676
0.4747
lnRo
0.0000
0.8719
1.1448
1.2862
0.0000
lnR
0.0761
2.2874
1.4339
1.7522
4.8192
N groups
Page 25
UNIFAC (LLEb)
Note: hidden
<P=
85.6 mmHg columns with ->
intermediate calcs
T(oC)=
25 oC
Antoine Coefficients (mmHg) log10(Psat)=A-B/(T+C) where T[=] oC
A
B
C
Psat[mmHg]
yi
x
i
CH3
CH2
CH
ACH
ACCH2
ACCH3
OH
2-Propanol
H2O
comp1
8.07
1730.63
233.43
23.69
0.26079
comp2
7.28
1434.2
246.5
99.57
0.73763
comp3
comp4
0
0
0
1
comp5
0
0
0
1
0.00158 0.00000
0
0
0
1
0.00000
comp1
comp2
comp3
comp4
comp5
Water
MEK
c2-COOH
EtOH
C5H12
0.773
0.139
0.088
0.000
0.000
1.235
0
0
0
0
0
0
0
0
1
4.541
1
1
0
0
0
0
0
0
0
1.535
1
1
0
0
0
0
0
0
0
1.396
1
1
0
0
0
0
1
0
0
104.701
2
3
0
0
0
0
0
0
0
ACOH
CH3CO
CHO
COOH
CH3COO
CH2O
CHCL2
CCL3
ACNH2
0.77
0.42
0.26
1.4000
2.8760
2.6120
2.5880
3.3160
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
lnC
0.0909
0.3122
0.2677
0.0150
0.3208
lnRo
0.0000
0.8719
1.1448
1.2862
0.0000
lnR
0.1204
2.0730
1.3059
1.6049
4.3303
kk(i)xi
N groups
phase
Page 26
aij-UNIFAC (LLE)
1
R
CH3
0
CH2
0
CH
3
ACH
4
ACCH2
0
ACCH3
OH 2-Propanol H2O
9
ACOH
10
CH3CO
11
CHO
13
14
15
1 CH3
0.9
0.85
-114.8
-115.7
-115.7 644.6
310.7
1300
2255
472.6 158.1
139.4
972.4
662.1
CH2
0.67
0.54
-114.8
-115.7
-115.7 644.6
310.7
1300
2255
472.6 158.1
139.4
972.4
662.1
CH
0.45
0.23
3 ACH
4 ACCH2
ACCH3
5 OH
7 2-Propanol
8 H2O
9 ACOH
10 CH3CO
11 CHO
13 COOH
14 CH3COO
15 CH2O
17 CHCL2
18 CCL3
22 ACNH2
-114.8
-115.7
-115.7 644.6
310.7
1300
2255
472.6 158.1
139.4
972.4
662.1
0.53
0.4 156.5
156.5
156.5
167
167 703.9
577.3
859.4
1649
593.7 362.3
461.8
32.14
1.04
0.66 104.4
104.4
104.4
-146.8
5695
292.6
916.7
1218
339.1
5688
213.1
1.27
0.97 104.4
104.4
104.4
-146.8
1.2 328.2
328.2
328.2
-9.21
-131.9
-252
-273.6
3.25
0.92
1.4 342.4
0.9
4000
906.8
4000
906.8
5695
292.6
916.7
1218
339.1
5688
213.1
1.27
1.27
991.3
28.73 -195.5
67.07
1409
-104
195.6
262.5
-273.6 -268.8
5.89 -153.2
487.1
1970
-6.32
64.42
342.4
342.4
372.8
203.7
203.7 -122.4
104.9
344.5
-159.8
-473.2
-470.4
-470.4 -63.15
-547.2
-595.9
-78.31
-73.87
-73.87
216
-127.6
634.8
-568
1.67
1.49 66.56
66.56
66.56
-898.3
0 -37.36
1247
258.7
-245.8
5.2
0.95 146.1
146.1
146.1
-75.3
223.2
223.2 -431.3
231.4
623.7
128
0.75
1.3
1.22
1744
1744
75.49
147.3
147.3 118.4
349.1
652.3
-101.3
1051
-117.6 -96.62
1.9
-320.1
114.8
-170
-170 180.6
-152.8
385.9 -337.3
58.84
1090
1417
0 -235.7
52.13
65.69
65.69 137.1
-218.1
212.8
52.38
1402
669.2
-401.6
740.4
550.6
437.7
-132.9 -197.7
33.61 418.4
-465.7
793.2
-825.7
370.4
-898.3 -20.93
857.7
681.4
1744
0.92
0.78
1571
1571
1571
2.06
1.68
27.9
27.9
27.9
2.64
2.18 21.23
21.23
21.23
288.5
33.61
1.06
0.82 175.8
175.8
175.8
-218.9
-15.41
-15.41
529
-239.8 -860.3
461.3
CH3
CH2
CH
ACH
ACCH2 ACCH3
OH
2-Propanol
H2O
ACOH CH3CO
CHO
CH3
1.47
1.47
1.47
0.12
0.35
0.01
0.2
0.59
0.63
0.04
0.11
CH2
1.47
1.47
1.47
0.12
0.35
0.01
0.2
0.59
0.63
0.04
0.11
Page 27
aij-UNIFAC (LLE)
CH
ACH
ACCH2
ACCH3
1.47
1.47
1.47
0.12
0.35
0.01
0.2
0.59
0.63
0.04
0.11
0.59
0.59
0.59
0.57
0.57
0.09
0.14
0.06
0.14
0.3
0.21
0.98
0.9
0.7
0.7
0.7
1.64
0.05
0.37
0.05
0.02
0.32
0.49
0.7
0.7
0.7
1.64
0.05
0.37
0.05
0.02
0.32
0.49
OH
0.33
0.33
0.33
1.03
0.04
0.91
1.93
0.8
0.01
1.42
0.52
0.41
2-Propanol
1.56
1.56
1.56
2.33
2.5
2.5
2.46
0.98
1.67
0.31
3.11
1.21
0.2
H2O
0.32
0.32
0.32
0.29
0.5
0.5
1.51
0.7
0.31
1.78
3.23
4.77
1.02
0.81
ACOH
1.71
1.71
1.71
4.89
4.84
4.84
1.24
6.27
7.38
15.95
20.35
0.8
0.8
0.8
1.3
1.28
1.28
0.48
1.53
0.12
6.72
1.13
0.02
0.42
0.98
0.61
0.61
0.61
1.29
0.47
0.47
4.25
0.46
0.12
0.65
2.28
0.78
0.61
0.61
0.67
0.31
0.11
1.4
0.03
1.48
1.38
CH3COO
2.93
2.93
2.93
0.68
1.77
1.77
0.55
1.67
0.27
3.1
0.82
0.03
0.01
2.2
CH2O
0.01
0.01
0.01
0.84
0.8
0.8
0.63
2.08
0.49
0.84
0.01
0.21
CHCL2
0.91
0.91
0.91
0.11
3.85
0.08
0.16
0.23
1.56
1.94
CCL3
0.93
0.93
0.93
0.38
0.89
0.89
0.25
4.77
0.07
15.95
0.29
20.35
1.07
ACNH2
0.55
0.55
0.55
2.08
1.05
1.05
0.17
2.24
17.91
0.06
0.1
CH3CO
CHO
COOH
Page 28
aij-UNIFAC (LLE)
17
18
CHCL2 CCL3
22
ACNH2
-243.9
7.5
902.2 CH3
-243.9
7.5
902.2 CH2
7.5
902.2 CH
-243.9
-231.9
-12.14
-12.14
272.2 -61.57
507.8
1544
370.7
356.8
1.64 ACH
689.6 ACCH2
689.6 ACCH3
-348.2 OH
2-Propanol
-109.8 H2O
-851.6 ACOH
-301
12.01
1010 CH3CO
1670
48.15
942.2 COOH
CHO
108.9 -209.7
CH3COO
137.8 -154.3
CH2O
CHCL2
0
-75.5 CCL3
-216.3
CHCL2 CCL3
0 ACNH2
ACNH2
2.27
0.98
0.05
2.27
0.98
0.05
Page 29
aij-UNIFAC (LLE)
2.27
0.98
0.05
2.18
0.99
1.04
0.1
1.04
0.1
0.4
1.23
3.22
0.18
0.01
0.29
0.3
1.45
17.4
2.74
0.96
0.03
0.85
0.04
0.69
2.02
0.63
1.68
1.29
2.07
Page 30
LLE
Water(1)+mek(2) at 298K by UNIFAC (cf Arce, JCEDat,40:226)
Summary of calculations for Example in Textbook
w
mek
w*xw
mek*xmek
x1 Gmix/RT
0.00
0 23.55
1
0
1
0.05
-0.06 12.21
1.02
0.61
0.97
0.10
-0.07
7.89
1.05
0.79
0.95
0.15
-0.08
5.75
1.1
0.86
0.93
0.20
-0.08
4.52
1.16
0.9
0.93
0.25
-0.08
3.73
1.22
0.93
0.92
0.30
-0.08
3.18
1.3
0.95
0.91
0.35
-0.08
2.78
1.39
0.97
0.9
0.40
-0.07
2.47
1.49
0.99
0.89
0.45
-0.07
2.22
1.61
1
0.89
0.50
-0.06
2.01
1.76
1.01
0.88
0.55
-0.05
1.84
1.95
1.01
0.88
0.60
-0.05
1.68
2.19
1.01
0.88
0.65
-0.04
1.55
2.51
1.01
0.88
0.70
-0.03
1.43
2.97
1
0.89
0.75
-0.03
1.32
3.66
0.99
0.91
0.80
-0.03
1.23
4.74
0.98
0.95
0.85
-0.03
1.14
6.64
0.97
1
0.90
-0.03
1.07 10.36
0.97
1.04
0.95
-0.03
1.02 19.09
0.97
0.95
1.00
0
1 45.76
1
0
Coexistence calculation
@x1~0.35
Gm/RT
-0.05
-0.1
-0.15
-0.2
-0.25
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
xw
1.2
1
xigi
0.8
0.6
0.4
0.2
Page 31
0.80
0.90
1.00
0.8
xigi
LLE
0.6
0.4
0.2
0
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
xw
Page 32
0.80
0.90
1.00