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Welcome to XSEOS

Version 12.10.21

XSEOS is an Excel add-in to compute thermodynamic prop


using excess Gibbs free energy models and equations of st
Copyright (C) 2008-12 Marcelo Castier

This program is free software: you can redistribute it and/or modify


it under the terms of the GNU General Public License as published by
the Free Software Foundation, either version 3 of the License, or
(at your option) any later version.

This program is distributed in the hope that it will be useful,


but WITHOUT ANY WARRANTY; without even the implied warranty of
MERCHANTABILITY or FITNESS FOR A PARTICULAR PURPOSE. See the
GNU General Public License for more details.

Please refer to the Worksheet "GNU GPL License" for the license te

Developed by:
Marcelo Castier
Chemical Engineering Program
Texas A & M University at Qatar
PO Box 23874
Doha, Qatar
E-mails: marcelo.castier@qatar.tamu.edu mcastier@gmail.com

Correlations for properties of oil fractions adapted


from Fortran codes written by Geraldo L. Rochocz

Patel-Teja-Valderrama equations implemented and


and tested in collaboration with Ricardo F. Checoni

Electrolattice equations of state implemented and


and tested in collaboration with Ricardo F. Checoni and Andre Zube

Initial development at:


Department of Chemical and Petroleum Engineering
United Arab Emirates University
P.O. Box 17555
Al Ain, United Arab Emirates
hermodynamic properties
and equations of state.

E. See the

ense" for the license text.

castier@gmail.com

econi and Andre Zuber


Physical properties from the Mattedi-Tavares-Castier (MTC) Equation of State

Reference:
Mattedi, S., Tavares, F. W., Castier, M., 2002. High pressure phase equilibrium calculations for hydrocarbon systems
using an equation of state based on the lattice fluid theory. Fluid Phase Equilibria 194, 599607.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Vapor pressure of Nitrogen

R (bar.cm3/(mol.K)) 83.14

Group 1
Vinf (cm3/mol) 20.204
Qa 3.347
B (Kelvin) 9.268
u00 (Kelvin) -152.118
Nitrogen 1 Group description of Nitrogen: 1 N2.

x T (K) P (bar) ln phi liquid


1 70 0.4019300257 -0.0395814312
1 75 0.7792109651 -0.0581658661
1 80 1.3865558109 -0.0807537709
1 85 2.3024551327 -0.1071479413
1 90 3.6131148318 -0.1370690769
1 95 5.4102989185 -0.1701785939
1 100 7.789508293 -0.2061284691
1 105 10.8483338081 -0.2445659058
1 110 14.6852625742 -0.2851586651
1 115 19.3985862545 -0.3275923565
1 120 25.0856959015 -0.3715803627
1 122 27.6547795492 -0.389552831
1 123 29.0053345881 -0.3986096745
1 124 30.4 -0.407687557

35

30

25
Pressure (bar)

20

15

10

0
60 70 80 90 100 110 120 130

Temperature (K)
Pres
10

0
60 70 80 90 100 110 120 130

Temperature (K)

Speed of Sound in Nitrogen

R (bar.cm3/(mol.K)) 83.14

Group 1
Vinf (cm3/mol) 125.32
Qa 40.26
B (Kelvin) 69.90
u00 (Kelvin) - 999.99
Nitrogen 1.00 Group description of Nitrogen: 1 N2.

Molar mass (g/mol) 149.19


Molar mass (kg/mol) 0.15
Ideal gas cp coefficients

Spreadsheet
formula
x Temperature (K) Pespec (bar) cpig (J/(mol.K))
1 283.1495 1.0132 -5.29E+00

1.077097

calculado
2000

1800

1600
Speed of sound (m/s)

1400

1200

1000

800

600

400

200
100 120 140 160 180 200 220 240 260 280

Temperature (K)

Speed of Sound in Oxygen

R (bar.cm3/(mol.K)) 83.14
Group 1
Vinf (cm3/mol) 19.176
Qa 2.841
B (Kelvin) 17.594
u00 (Kelvin) -192.186
Oxygen 1 Group description of Oxygen: 1 O2.

Molar mass (g/mol) 31.999


Molar mass (kg/mol) 0.031999
Ideal gas cp coefficients

Spreadsheet
formula
x Temperature (K) Pespec (bar) cpig (J/(mol.K))
1 150 1.0132 28.466
1 155 1.0132 28.489
1 160 1.0132 28.513
1 165 1.0132 28.537
1 170 1.0132 28.562
1 175 1.0132 28.587
1 180 1.0132 28.613
1 185 1.0132 28.639
1 190 1.0132 28.667
1 195 1.0132 28.694
1 200 1.0132 28.722
1 205 1.0132 28.751
1 210 1.0132 28.781
1 215 1.0132 28.810
1 220 1.0132 28.841
1 225 1.0132 28.872
1 230 1.0132 28.903
1 235 1.0132 28.935
1 240 1.0132 28.968
1 245 1.0132 29.001
1 250 1.0132 29.034
1 255 1.0132 29.068
1 260 1.0132 29.102
1 265 1.0132 29.137
1 270 1.0132 29.172
1 275 1.0132 29.208
1 280 1.0132 29.244
1 285 1.0132 29.281
1 290 1.0132 29.318
1 295 1.0132 29.355
1 300 1.0132 29.393
1 305 1.0132 29.431
1 310 1.0132 29.469
1 315 1.0132 29.508
1 320 1.0132 29.548
1 325 1.0132 29.587
1 330 1.0132 29.627
1 335 1.0132 29.668
1 340 1.0132 29.709
1 345 1.0132 29.750
1 350 1.0132 29.791
1 355 1.0132 29.833
1 360 1.0132 29.875
1 365 1.0132 29.917
1 370 1.0132 29.959
1 375 1.0132 30.002
1 380 1.0132 30.045
1 385 1.0132 30.089
1 390 1.0132 30.132
1 395 1.0132 30.176
1 400 1.0132 30.221

400

380

360

340
Speed of sound (m/s)

320

300

280

260

240

220

200
100 150 200 250 300 350 400 4

Temperature (K)
for hydrocarbon systems

ln phi vapor difference in ln phi grrtl hrrtl srrl


-0.039581991 5.59863469362654E-07 #NAME? #NAME? #NAME?
-0.0581661015 2.35376454327252E-07 #NAME? #NAME? #NAME?
-0.0807532997 -4.71139838253976E-07 #NAME? #NAME? #NAME?
-0.1071487643 0.000000823 #NAME? #NAME? #NAME?
-0.1370684756 -6.01279992906711E-07 #NAME? #NAME? #NAME?
-0.1701785127 -8.11485811880175E-08 #NAME? #NAME? #NAME?
-0.2061276886 -7.8050447172018E-07 #NAME? #NAME? #NAME?
-0.2445655476 -3.5814848689531E-07 #NAME? #NAME? #NAME?
-0.285157837 -8.2810081991625E-07 #NAME? #NAME? #NAME?
-0.3275914466 -9.0985427192436E-07 #NAME? #NAME? #NAME?
-0.3715796746 -6.8813044151739E-07 #NAME? #NAME? #NAME?
-0.389551874 -0.000000957 #NAME? #NAME? #NAME?
-0.3986094068 -2.6764077176722E-07 #NAME? #NAME? #NAME?
-0.40769555 0.000007993 #NAME? #NAME? #NAME?

6000

5500

5000
Enthalpy of vaporizaton (J/mol)

4500

4000

3500

3000

2500

2000

1500
120 130
1000
60 70 80 90 100 110 120 130
3000

Enthalpy of va
2500

2000

1500
120 130
1000
60 70 80 90 100 110 120 130
Temperature (K)

31.0705845984 -1.36E-02 2.68E-05 -1.53E-06

These 4 columns were calculated with array function mtcsoundspeedv. These columns were calculated u

rho (mol/cm3) dpdrho (bar/(mol/cm3)) cprr (K) dPdT (bar/K) rho (mol/m3)
#NAME? #NAME? #NAME? #NAME? 7219.6146549971

0.00721963

1.077097
240 260 280 300
28.11 -3.680E-06 1.746E-05 -1.065E-08

These 4 columns were calculated with array function mtcsoundspeedv. These columns were calculated u

rho (mol/cm3) dpdrho (bar/(mol/cm3)) cprr (K) dPdT (bar/K) rho (mol/m3)
#NAME? #NAME? #NAME? #NAME? 81.9408633244
#NAME? #NAME? #NAME? #NAME? 79.2224673703
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? 42.0525544636
#NAME? #NAME? #NAME? #NAME? 41.3375644301
#NAME? #NAME? #NAME? #NAME? 40.6465600571
#NAME? #NAME? #NAME? #NAME? 39.9783491376
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? 30.4684070465

400 450
cprrl grrtv hrrtv srrv
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
umns were calculated using spreadsheet formulas

dPdrho (Pa/(mol/m3)) cprr (K) dPdT (Pa/K) cp residual (J/(mol.K)


459889.530444641 70.0514210893 107505.306442865 582.4075149367
Comparison with other calculations and data from the literature.
umns were calculated using spreadsheet formulas

dPdrho (Pa/(mol/m3)) cprr (K) dPdT (Pa/K) cp residual (J/(mol.K)


1225.944333786 0.0828817152 690.2821441883 0.6890785805
1269.2249807283 0.071951796 666.3453424935 0.5982072321
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
2407.6748687656 0.0072647288 350.2691111301 0.060398955
2449.4513461906 0.0068816744 344.2907906674 0.057214241
2491.2181226842 0.0065269524 338.5145311104 0.0542650818
2532.9758521231 0.0061979142 332.9301558921 0.0515294584
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
3325.2248491011 0.002763302 253.5687996625 0.0229740925

Comparison with other calculations and data from the literature.


cprrv hvaporization/(RT) hvaporization(J/mol)
#NAME? 9.5421323526 5553.3301865949
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
cp (J/(mol.K)) cv (J/(mol.K)) gamma=cp/cv sound speed (m/s)
5.77E+02 576.9822173816 1.0002366092 1755.934360911 1.65E-11

sound speed exp (m/s)


1755.94000
cp (J/(mol.K)) cv (J/(mol.K)) gama=cp/cv sound speed (m/s)
29.1554328305 20.4723745385 1.424135377 233.5838485248
29.0874540634 20.4478251076 1.4225206794 237.5365238655
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
29.377974905 21.0215777049 1.3975152254 324.2716569034
29.4121743473 21.0577940458 1.3967357779 326.9816149462
29.4470110818 21.094510042 1.3959561527 329.6655476344
29.4824551022 21.1317077362 1.3951761718 332.3241072285
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
30.2435020925 21.9118504027 1.3802349659 378.7205036076
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It is common to report UNIQUAC binary interaction param
In this case, use R=1 in the spreadsheet; otherwise use u

methanol(1)+water(2)
R T(K)
1 333.15
r 1.4311 0.92
q 1.432 1.4
Binary interactions 0 -213.6961399
358.550089 0

The first five columns are experimental data for the mixture.

x1exp x2exp ge/RT


0 1 -7.771561E-16
0.1686 0.8314 0.1043990948
0.2167 0.7833 0.1218441457
0.3039 0.6961 0.1428062734
0.3681 0.6319 0.1506464987
0.4461 0.5539 0.1527209407
0.5282 0.4718 0.1471587404
0.6044 0.3956 0.1357249984
0.6804 0.3196 0.1189501625
0.7255 0.2745 0.1066737659
0.7776 0.2224 0.0904897355
1 0 1.5898394E-16
binary interaction parameters as a12/R, a21/R, etc in Kelvin.
dsheet; otherwise use units compatible with the aij values.

a for the mixture.

Energia livre de ativao


0.18
0.16
0.14
0.12
0.1
0.08
0.06
0.04
0.02
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
-0.02
Notes and comments

Literature references:

Some of the models implemented in XSEOS are relatively new and are not discussed in textbooks.
In such cases, references to scientific journals are provided.

Other models implemented in XSEOS are commonly used by the oil/gas/chemical industry and are discussed in ma
Given that XSEOS is primarily intended for education and access to scientific journals may not be immediate for all
reference to a textbook was preferred in these cases. In the case of the most popular models, many textbooks actu
but a single reference is provided, as example.

Version history:

7.11.29:
(a) fixed r and q values of methanol in the UNIQUAC sheet.

8.01.17:
(a) fixed function rkp (previously called srkp by mistake)
(b) included Margules model.
(c) included reference to the MTC equation of state

8.01.29:
(a) included function eosresidual to compute gr/(RT),.hr/(RT), sr/R, and cpr/R given T,v,x.
(b) included specific functions for each EOS that interface the function eosresidual.

8.04.24
(a) uses a less tight convergence criterion in the EOS root-finding procedure to reduce numerical crashes.
(b) fixed a comment about isenthalpic expansion in the SRK worksheet.

8.05.20
(a) included a version of the Peng-Robinson EOS with a quadratic mixing rule for the b-parameter.
(b) included the following methods to predict Tc, Pc, acentric factor, and molar mass of oil fractions
b.1: Whitson interpolation functions
b.2: Kesler-Lee correlations
b.3: Edminster correlation for acentric factor

8.09.22
(a) enhanced compatibility with Excel 2007.

9.04.01
(a) included several methods to predict critical temperature, critical pressure, and acentric factor of oil fractions
9.11.17
(a) included the parachor, Miqueu, and Danesh methods to predict surface tension
(b) included functions to compute liquid or vapor molar volume with each equation of state

10.03.22
(a) the surface tension examples were moved to a separate file because they were slowing down all spreadsheet calc

10.05.12
(a) corrected the temperature used to compute the properties of stream III in the adiabatic mixing example of the UNIQ

10.10.04
(a) included an extended Peng-Robinson model for confined fluids.
This required several code changes to include the optional argument "extracells" in several Subs and Functions.

10.10.11
(a) included an option to compute EOS properties with the root that gives the lowest value of the molar Gibbs energy a

11.10.13
(a) included the Patel-Teja-Valderrama and the electrolattice equations of state

11.11.13
(a) The van der Waals, Redlich-Kwong, Peng-Robinson, Soave-Redlich-Kwong, Stryjek-Vera equations of state were r
They now return the residual entropy divided by R.
Acknowledgements to Dema Almasri and Mary Katebah (TAMUQ students) and Dr. Aaron Scurto (University of Kan

12.04.20
(a) Two versions of the electrolattice equation of state were implemented: with ions of equal diameter and of unequal d

12.10.21
(a) Removed DLL calls forgotten inside the package after some experimental runs.
Acknowledgements to Dr. Ali Khalaf Al-matar, Chemical Engineering Department, University of Jordan, for spotting
Calculation of activity coefficients and excess properties in binary mixtures using the 2-, 3-

Reference:
Reid, R.C., J.M. Prausnitz, and B.E. Poling
The Properties of Gases and Liquids
4th ed., McGraw-Hill, New York, 1987.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Comments about the Margules model:

(1) Unlike other models in XSEOS, the Margules model is implemented for binary mixtures only;
(2) To use Margules 2-suffix formula, set the values of B and C to zero;
(3) To use Margules 3-suffix formula, set the value of C to zero;
(4) Acitivity coefficients were derived from the following form of the Margules molar excess Gibbs free energy (Reid et al., 1987

g E x1 x2

RT RT

A B x1 x2 C x1 x2
2

methyl ethyl ketone(1)+toluene(2)
Example taken from Smith, J.M., H.C. van Ness, and M.M. Abbott, Introduction to Chemical Engineering Thermodynam

Comment: Smith, van Ness, and Abbott write the Margules equation in a form different from the one above. There
cannot be used directly and must be converted to the above representation. The values of parameters

Universal gas constant and temperature

R (J/(mol.K)) 8.314
T (K) 323.15

Model parameters
A 765.7007
B -233.74
C 0
These 2 columns were calculated These two columns were calculated
with array function margules. with spreadsheet formulas.
x1 x2 lngama(1) lngama(2) gama(1)
0 1 #NAME? #NAME? 1.4506329813
0.05 0.95 #NAME? #NAME? #NAME?
0.1 0.9 #NAME? #NAME? #NAME?
0.15 0.85 #NAME? #NAME? #NAME?
0.2 0.8 #NAME? #NAME? #NAME?
0.25 0.75 #NAME? #NAME? #NAME?
0.3 0.7 #NAME? #NAME? #NAME?
0.35 0.65 #NAME? #NAME? #NAME?
0.4 0.6 #NAME? #NAME? #NAME?
0.45 0.55 #NAME? #NAME? #NAME?
0.5 0.5 #NAME? #NAME? #NAME?
0.55 0.45 #NAME? #NAME? #NAME?
0.6 0.4 #NAME? #NAME? #NAME?
0.65 0.35 #NAME? #NAME? #NAME?
0.7 0.3 #NAME? #NAME? #NAME?
0.75 0.25 #NAME? #NAME? #NAME?
0.8 0.2 #NAME? #NAME? #NAME?
0.85 0.15 #NAME? #NAME? #NAME?
0.9 0.1 #NAME? #NAME? #NAME?
0.95 0.05 #NAME? #NAME? #NAME?
1 0 #NAME? #NAME? #NAME?

The values highlighted with a pink background are the activity coefficients of methyl ethyl ketone(1) and toluene(2) at
They are in perfect agreement with the values reported by Smith, van Ness, and Abbott.
inary mixtures using the 2-, 3- or 4-suffix Margules model

xcess Gibbs free energy (Reid et al., 1987):

to Chemical Engineering Thermodynamics, 6th ed.,McGraw-Hill, page 424.

rm different from the one above. Therefore, the parameters they provide
presentation. The values of parameters A and B below represent these conversions.

wo columns were calculated These 4 columns were calculated


readsheet formulas. with array function margulesxs.
gama(2) ge/(RT) he/(RT) se/R cpe/R
1 #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?

methyl ethyl ketone(1) and toluene(2) at infinite dilution.


Calculation of activity coefficients and excess properties using Regular Solution Theory

Reference:
Reid, R.C., J.M. Prausnitz, and B.E. Poling
The Properties of Gases and Liquids
4th ed., McGraw-Hill, New York, 1987.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Universal gas constant and temperature

R (J/(mol.K)) 8.314
T (K) 344

Model parameters

v(cm3/mol) delta (J/cm3)^(1/2)


n-pentane 116 14.5
n-octane 164 15.3

These 2 columns were calculated These two columns were calculated


with array function regsol. with spreadsheet formulas.
x(n-pentane) x(n-octane) lngama(n-pentane) lngama(n-octane) gama(n-pentane)
0 1 #NAME? #NAME? 1.0262977371
0.02 0.98 #NAME? #NAME? 1.0255452372
0.04 0.96 #NAME? #NAME? #NAME?
0.06 0.94 #NAME? #NAME? #NAME?
0.08 0.92 #NAME? #NAME? #NAME?
0.1 0.9 #NAME? #NAME? #NAME?
0.12 0.88 #NAME? #NAME? #NAME?
0.14 0.86 #NAME? #NAME? #NAME?
0.16 0.84 #NAME? #NAME? #NAME?
0.18 0.82 #NAME? #NAME? #NAME?
0.2 0.8 #NAME? #NAME? #NAME?
0.22 0.78 #NAME? #NAME? #NAME?
0.24 0.76 #NAME? #NAME? #NAME?
0.26 0.74 #NAME? #NAME? #NAME?
0.28 0.72 #NAME? #NAME? #NAME?
0.3 0.7 #NAME? #NAME? #NAME?
0.32 0.68 #NAME? #NAME? #NAME?
0.34 0.66 #NAME? #NAME? #NAME?
0.36 0.64 #NAME? #NAME? #NAME?
0.38 0.62 #NAME? #NAME? #NAME?
0.4 0.6 #NAME? #NAME? #NAME?
0.42 0.58 #NAME? #NAME? #NAME?
0.44 0.56 #NAME? #NAME? #NAME?
0.46 0.54 #NAME? #NAME? #NAME?
0.48 0.52 #NAME? #NAME? #NAME?
0.5 0.5 #NAME? #NAME? #NAME?
0.52 0.48 #NAME? #NAME? #NAME?
0.54 0.46 #NAME? #NAME? 1.0077784834
0.56 0.44 #NAME? #NAME? #NAME?
0.58 0.42 #NAME? #NAME? #NAME?
0.6 0.4 #NAME? #NAME? #NAME?
0.62 0.38 #NAME? #NAME? #NAME?
0.64 0.36 #NAME? #NAME? #NAME?
0.66 0.34 #NAME? #NAME? #NAME?
0.68 0.32 #NAME? #NAME? #NAME?
0.7 0.3 #NAME? #NAME? #NAME?
0.72 0.28 #NAME? #NAME? #NAME?
0.74 0.26 #NAME? #NAME? #NAME?
0.76 0.24 #NAME? #NAME? #NAME?
0.78 0.22 #NAME? #NAME? #NAME?
0.8 0.2 #NAME? #NAME? #NAME?
0.82 0.18 #NAME? #NAME? 1.0014571476
0.84 0.16 #NAME? #NAME? #NAME?
0.86 0.14 #NAME? #NAME? #NAME?
0.88 0.12 #NAME? #NAME? #NAME?
0.9 0.1 #NAME? #NAME? #NAME?
0.92 0.08 #NAME? #NAME? #NAME?
0.94 0.06 #NAME? #NAME? #NAME?
0.96 0.04 #NAME? #NAME? #NAME?
L o g a r ith m o f a c tiv ity c o e ffic ie n t

0.98 0.02 #NAME? #NAME? #NAME?


1 0 #NAME? #NAME? #NAME?

12

10

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Mole fraction n-pentane

12

10
RT)
12

10

ge/(RT)
8

0
0 0.1 0.2 0.3 0.4 0.5 0.6
Mole fraction of n-pentane
using Regular Solution Theory

wo columns were calculated These 4 columns were calculated with array function regsolxs.
eadsheet formulas.
gama(n-octane) ge/(RT) he/(RT) se/R cpe/R
1 #NAME? #NAME? #NAME? #NAME?
1.000007431 #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
1.0075812071 #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
1.0216039775 #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?

n-pentane
n-octane

0.5 0.6 0.7 0.8 0.9 1


fraction n-pentane
0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fraction of n-pentane
Calculation of activity coefficients and excess properties using the Flory-Huggins model

Reference:
Reid, R.C., J.M. Prausnitz, and B.E. Poling
The Properties of Gases and Liquids
4th ed., McGraw-Hill, New York, 1987.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

R (cal/(mol.K)) T(K)
1.987 344
Size parameter 1 5
Chi parameter (symmetrical matrix) 0 0.1
0.1 0

These 2 columns were calculated


with array function fh.
x1 x2 lngama(1) lngama(2)
0 1 #NAME? #NAME?
0.02 0.98 #NAME? #NAME?
0.04 0.96 #NAME? #NAME?
0.06 0.94 #NAME? #NAME?
0.08 0.92 #NAME? #NAME?
0.1 0.9 #NAME? #NAME?
0.12 0.88 #NAME? #NAME?
0.14 0.86 #NAME? #NAME?
0.16 0.84 #NAME? #NAME?
0.18 0.82 #NAME? #NAME?
0.2 0.8 #NAME? #NAME?
0.22 0.78 #NAME? #NAME?
0.24 0.76 #NAME? #NAME?
0.26 0.74 #NAME? #NAME?
0.28 0.72 #NAME? #NAME?
0.3 0.7 #NAME? #NAME?
0.32 0.68 #NAME? #NAME?
0.34 0.66 #NAME? #NAME?
0.36 0.64 #NAME? #NAME?
0.38 0.62 #NAME? #NAME?
0.4 0.6 #NAME? #NAME?
0.42 0.58 #NAME? #NAME?
0.44 0.56 #NAME? #NAME?
0.46 0.54 #NAME? #NAME?
0.48 0.52 #NAME? #NAME?
0.5 0.5 #NAME? #NAME?
0.52 0.48 #NAME? #NAME?
0.54 0.46 #NAME? #NAME?
0.56 0.44 #NAME? #NAME?
0.58 0.42 #NAME? #NAME?
0.6 0.4 #NAME? #NAME?
0.62 0.38 #NAME? #NAME?
0.64 0.36 #NAME? #NAME?
0.66 0.34 #NAME? #NAME?
0.68 0.32 #NAME? #NAME?
0.7 0.3 #NAME? #NAME?
0.72 0.28 #NAME? #NAME?
0.74 0.26 #NAME? #NAME?
0.76 0.24 #NAME? #NAME?
0.78 0.22 #NAME? #NAME?
0.8 0.2 #NAME? #NAME?
0.82 0.18 #NAME? #NAME?
0.84 0.16 #NAME? #NAME?
0.86 0.14 #NAME? #NAME?
0.88 0.12 #NAME? #NAME?
0.9 0.1 #NAME? #NAME?
0.92 0.08 #NAME? #NAME?
0.94 0.06 #NAME? #NAME?
0.96 0.04 #NAME? #NAME?
L o g a rith m o f a c tiv ity c o e ffic ie n t

0.98 0.02 #NAME? #NAME?


1 0 #NAME? #NAME?

12

10

0
0 0.1 0.2 0.3 0.4 0.5
Mole fraction of comp
2

0
0 0.1 0.2 0.3 0.4 0.5
Mole fraction of comp

12

10

ge/(RT)
8

0
0 0.1 0.2 0.3 0.4 0.5 0.6
Mole fraction of compone
-Huggins model

ecifications.

These two columns were calculated These 4 columns were calculated with array function fhxs.
with spreadsheet formulas.
gama(1) gama(2) ge/(RT) he/(RT) se/R cpe/R
0.4919206222 1 #NAME? #NAME? #NAME? #NAME?
0.4978920868 0.9998774891 #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?

Component 1
Component 2

0.4 0.5 0.6 0.7 0.8 0.9 1


Mole fraction of component 1
0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fraction of component 1

0.4 0.5 0.6 0.7 0.8 0.9 1


ole fraction of component 1
Calculation of activity coefficients and excess properties using the Wilson model

Reference:
Reid, R.C., J.M. Prausnitz, and B.E. Poling
The Properties of Gases and Liquids
4th ed., McGraw-Hill, New York, 1987.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Acetone(1)+Water(2)
R (cal/(mol.K)) T(K)
1.987 344
V (cm3/mol) 74.05 18.07
Binary interactions (cal/mol) 0 291.27
1448.01 0

These 2 columns were calculated


with array function wilson.
x1 x2 lngama(1)
0 1 #NAME?
0.02 0.98 #NAME?
0.04 0.96 #NAME?
0.06 0.94 #NAME?
0.08 0.92 #NAME?
0.1 0.9 #NAME?
0.12 0.88 #NAME?
0.14 0.86 #NAME?
0.16 0.84 #NAME?
0.18 0.82 #NAME?
0.2 0.8 #NAME?
0.22 0.78 #NAME?
0.24 0.76 #NAME?
0.26 0.74 #NAME?
0.28 0.72 #NAME?
0.3 0.7 #NAME?
0.32 0.68 #NAME?
0.34 0.66 #NAME?
0.36 0.64 #NAME?
0.38 0.62 #NAME?
0.4 0.6 #NAME?
0.42 0.58 #NAME?
0.44 0.56 #NAME?
0.46 0.54 #NAME?
0.48 0.52 #NAME?
0.5 0.5 #NAME?
0.52 0.48 #NAME?
0.54 0.46 #NAME?
0.56 0.44 #NAME?
0.58 0.42 #NAME?
0.6 0.4 #NAME?
0.62 0.38 #NAME?
0.64 0.36 #NAME?
0.66 0.34 #NAME?
0.68 0.32 #NAME?
0.7 0.3 #NAME?
0.72 0.28 #NAME?
0.74 0.26 #NAME?
0.76 0.24 #NAME?
0.78 0.22 #NAME?
0.8 0.2 #NAME?
0.82 0.18 #NAME?
0.84 0.16 #NAME?
0.86 0.14 #NAME?
0.88 0.12 #NAME?
0.9 0.1 #NAME?
0.92 0.08 #NAME?
0.94 0.06 #NAME?
0.96 0.04 #NAME?
0.98 0.02 #NAME?
1 0 #NAME?

Parameter fitting in the Wilson model from vapor-liquid equilibrium data using Excel Solver

Modified version of problem 12.1: Smith, van Ness, and Abbott, Introduction to Chemical Engineering Thermodynamic

Objective:
Fit the binary interaction parameters of the Wilson model using experimental vapor-liquid equilibrium data minimizing the summ

methanol(1)+water(2)
R (cal/(mol.K)) T(K)
1.987 333.15
Molar volume (cm3/mol) 40.73 18.07
Binary interactions 0 200
600 0

The first five columns are experimental data for the mixture.

x1exp x2exp y1exp


0 1 0
0.1686 0.8314 0.5714
0.2167 0.7833 0.6268
0.3039 0.6961 0.6943
0.3681 0.6319 0.7345
0.4461 0.5539 0.7742
0.5282 0.4718 0.8085
0.6044 0.3956 0.8383
0.6804 0.3196 0.8733
0.7255 0.2745 0.8922
0.7776 0.2224 0.9141
1 0 1
g the Wilson model

one are problem specifications.

ls are results of calculations.

e 2 columns were calculated These two columns were calculated These 4 columns were calculated with array function wilso
array function wilson. with spreadsheet formulas.
lngama(2) gama(1) gama(2) ge/(RT) he/(RT)
#NAME? 10.4224359009 1 #NAME? #NAME?
#NAME? 8.4573411015 1.0020636842 #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? 1.0581773475 2.8032722819 #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? 1 4.704841713 #NAME? #NAME?

brium data using Excel Solver

Chemical Engineering Thermodynamics, 6th edition, Mc-Graw-Hill, 2001 (reference to the data points available there).

uid equilibrium data minimizing the summation of the squared difference between experimental and calculated pressures.

Pure component vapor pressures


P1sat 84.562
P2sat 19.953

ntal data for the mixture. These 2 columns were calculated These final columns were calculated wit
with array function wilson.
y2exp Pexp(kPa) lngama1 lngama2 gama1
1 19.953 #NAME? #NAME? 3.3342976779
0.4286 39.223 #NAME? #NAME? #NAME?
0.3732 42.984 #NAME? #NAME? #NAME?
0.3057 48.852 #NAME? #NAME? #NAME?
0.2655 52.784 #NAME? #NAME? #NAME?
0.2258 56.652 #NAME? #NAME? #NAME?
0.1915 60.614 #NAME? #NAME? #NAME?
0.1617 63.998 #NAME? #NAME? #NAME?
0.1267 67.924 #NAME? #NAME? #NAME?
0.1078 70.229 #NAME? #NAME? #NAME?
0.0859 72.832 #NAME? #NAME? #NAME?
0 84.562 #NAME? #NAME? #NAME?
calculated with array function wilsonxs.

se/R cpe/R
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?

oints available there).

lculated pressures.

final columns were calculated with spreadsheet formulas.

gama2 Pcalc(kPa) deltaP deltaP^2 y1calc y2calc


1 19.953 0 0 0 1
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
Objective function: Sum(deltaP^2) 210.599400559

Hint: use Solver to minimize the objective function cell


changing the two cells that correspond to the binary
interaction parameters of the Wilson model.
Calculation of activity coefficients and excess properties using the TK-Wilson model

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

R (cal/(mol.K)) T(K)
1.987 344
V (cm3/mol) 74.05 18.07 Parameters for a hypothetical mixture
Binary interactions (cal/mol) 0 291.27
1448.01 0

These 2 columns were calculated


with array function tkwilson.
x1 x2 lngama(1) lngama(2)
0 1 #NAME? #NAME?
0.02 0.98 #NAME? #NAME?
0.04 0.96 #NAME? #NAME?
0.06 0.94 #NAME? #NAME?
0.08 0.92 #NAME? #NAME?
0.1 0.9 #NAME? #NAME?
0.12 0.88 #NAME? #NAME?
0.14 0.86 #NAME? #NAME?
0.16 0.84 #NAME? #NAME?
0.18 0.82 #NAME? #NAME?
0.2 0.8 #NAME? #NAME?
0.22 0.78 #NAME? #NAME?
0.24 0.76 #NAME? #NAME?
0.26 0.74 #NAME? #NAME?
0.28 0.72 #NAME? #NAME?
0.3 0.7 #NAME? #NAME?
0.32 0.68 #NAME? #NAME?
0.34 0.66 #NAME? #NAME?
0.36 0.64 #NAME? #NAME?
0.38 0.62 #NAME? #NAME?
0.4 0.6 #NAME? #NAME?
0.42 0.58 #NAME? #NAME?
0.44 0.56 #NAME? #NAME?
0.46 0.54 #NAME? #NAME?
0.48 0.52 #NAME? #NAME?
0.5 0.5 #NAME? #NAME?
0.52 0.48 #NAME? #NAME?
0.54 0.46 #NAME? #NAME?
0.56 0.44 #NAME? #NAME?
0.58 0.42 #NAME? #NAME?
0.6 0.4 #NAME? #NAME?
0.62 0.38 #NAME? #NAME?
0.64 0.36 #NAME? #NAME?
0.66 0.34 #NAME? #NAME?
0.68 0.32 #NAME? #NAME?
0.7 0.3 #NAME? #NAME?
0.72 0.28 #NAME? #NAME?
0.74 0.26 #NAME? #NAME?
0.76 0.24 #NAME? #NAME?
0.78 0.22 #NAME? #NAME?
0.8 0.2 #NAME? #NAME?
0.82 0.18 #NAME? #NAME?
0.84 0.16 #NAME? #NAME?
0.86 0.14 #NAME? #NAME?
0.88 0.12 #NAME? #NAME?
0.9 0.1 #NAME? #NAME?
0.92 0.08 #NAME? #NAME?
0.94 0.06 #NAME? #NAME?
0.96 0.04 #NAME? #NAME?
0.98 0.02 #NAME? #NAME?
1 0 #NAME? #NAME?
he TK-Wilson model

m specifications.

calculations.

eters for a hypothetical mixture

These two columns were calculated These 4 columns were calculated with array function tkwilsonxs.
with spreadsheet formulas.
gama(1) gama(2) ge/(RT) he/(RT) se/R
56.3411825569 1 #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
ay function tkwilsonxs.

cpe/R
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
Calculation of activity coefficients and excess properties using the NRTL model

Reference:
Reid, R.C., J.M. Prausnitz, and B.E. Poling
The Properties of Gases and Liquids
4th ed., McGraw-Hill, New York, 1987.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

R (cal/(mol.K)) T(K)
1.987 333.15
alfa 0.3 0.3
0.3 0.3
Binary interactions (cal/mol) 0 -270.3
840.8 0

These 2 columns were calculated


with array function nrtl.
x1 x2 lngamma(1)
0 1 #NAME?
0.02 0.98 #NAME?
0.04 0.96 #NAME?
0.06 0.94 #NAME?
0.08 0.92 #NAME?
0.1 0.9 #NAME?
0.12 0.88 #NAME?
0.14 0.86 #NAME?
0.16 0.84 #NAME?
0.18 0.82 #NAME?
0.2 0.8 #NAME?
0.22 0.78 #NAME?
0.24 0.76 #NAME?
0.26 0.74 #NAME?
0.28 0.72 #NAME?
0.3 0.7 #NAME?
0.32 0.68 #NAME?
0.34 0.66 #NAME?
0.36 0.64 #NAME?
0.38 0.62 #NAME?
0.4 0.6 #NAME?
0.42 0.58 #NAME?
0.44 0.56 #NAME?
0.46 0.54 #NAME?
0.48 0.52 #NAME?
0.5 0.5 #NAME?
0.52 0.48 #NAME?
0.54 0.46 #NAME?
0.56 0.44 #NAME?
0.58 0.42 #NAME?
0.6 0.4 #NAME?
0.62 0.38 #NAME?
0.64 0.36 #NAME?
0.66 0.34 #NAME?
0.68 0.32 #NAME?
0.7 0.3 #NAME?
0.72 0.28 #NAME?
0.74 0.26 #NAME?
0.76 0.24 #NAME?
0.78 0.22 #NAME?
0.8 0.2 #NAME?
0.82 0.18 #NAME?
0.84 0.16 #NAME?
0.86 0.14 #NAME?
0.88 0.12 #NAME?
0.9 0.1 #NAME?
0.92 0.08 #NAME?
0.94 0.06 #NAME?
0.96 0.04 #NAME?
0.98 0.02 #NAME?
1 0 #NAME?
T h e rm o d y n a m ic p ro p e rty

12

10

0
0 0.1 0.2 0.3 0.
M

Parameter fitting in the NRTL model from isothermal vapor-liquid equilibrium data using

Modified version of problem 12.1: Smith, van Ness, and Abbott, Introduction to Chemical Engineering Thermodyna

Objective:
Fit the binary interaction parameters of the NRTL model using experimental vapor-liquid equilibrium data minimizing the su

methanol(1)+water(2)
R (cal/(mol.K)) T(K)
1.987 333.15
alfa 0.3 0.3
0.3 0.3
Binary interactions (cal/mol) 0 -100
100 0

The first five columns are experimental data for the mixture.

x1exp x2exp y1exp


0 1 0
0.1686 0.8314 0.5714
0.2167 0.7833 0.6268
0.3039 0.6961 0.6943
0.3681 0.6319 0.7345
0.4461 0.5539 0.7742
0.5282 0.4718 0.8085
0.6044 0.3956 0.8383
0.6804 0.3196 0.8733
0.7255 0.2745 0.8922
0.7776 0.2224 0.9141
1 0 1
Pressure (kPa)

90
80
70
60
50
40
30
20
10
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Mole fraction of methanol

Parameter fitting in the NRTL model from isobaric vapor-liquid equilibrium data using Ex
Objective:
Fit the binary interaction parameters of the NRTL model using experimental vapor-liquid equilibrium data minimizing the su

Experimental data
Radhamma, M. , Cheng-Ting Hsieh, P. Venkatesu, M. V. Prabhakara Rao, Ming-Jer Lee, and Ho-mu Lin
Isobaric VaporLiquid Equilibrium for Dimethylsulfoxide with Chloroethanes and Chloroethenes
J. Chem. Eng. Data 2008, 53, 374377

1,2-DCE DMSO
C1 85.45 49.37
C2 -6920.4 -7620.6
C3 0 0
C4 0 0
C5 -10.65 -4.63
C6 9.140E-06 4.380E-07
C7 2 2

R (using R=1 is equivalent to fitting the interaction parameters/R, w


1

1,2-DCE (1) DMSO (2)


alfa 0 0.3
0.3 0
Binary interactions (cal/mol) 0 -110.316
91.082 0

P experimental (kPa) 95.3

Experimental Experimental Experimental


x1 x2 T (K)
0 1 460.95
0.0748 0.9252 436
0.1307 0.8693 423
0.3107 0.6893 395
0.4286 0.5714 383
0.5197 0.4803 376
0.6433 0.3567 369
0.844 0.156 360
0.9253 0.0747 357
1 0 355.05

470

450

430
mperature (K)

410
470

450

430

Temperature (K)
410

390

370

350
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
x1
using the NRTL model

e are problem specifications.

are results of calculations.

Parameters for methanol(1)+water(2)

columns were calculated These two columns were calculated These 4 columns were calculated with array function nr
ay function nrtl. with spreadsheet formulas.
lngamma(2) gamma(1) gamma(2) ge/(RT) he/(RT)
#NAME? 2.2447872816 1 #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?

0.2 0.3 0.4 fraction0.5


Mole of methanol0.6 0.7 0.8 0.9

or-liquid equilibrium data using Excel Solver

n to Chemical Engineering Thermodynamics, 6th edition, Mc-Graw-Hill, 2001 (reference to the data points available there).
or-liquid equilibrium data minimizing the summation of the squared difference between experimental and calculated pressures.

P1sat 84.562
P2sat 19.953

al data for the mixture. These 2 columns were calculated These final columns were calculated
with array function nrtl.
y2exp Pexp(kPa) lngamma1 lngamma2 gamma1
1 19.953 #NAME? #NAME? 0.993020825
0.4286 39.223 #NAME? #NAME? #NAME?
0.3732 42.984 #NAME? #NAME? #NAME?
0.3057 48.852 #NAME? #NAME? #NAME?
0.2655 52.784 #NAME? #NAME? #NAME?
0.2258 56.652 #NAME? #NAME? #NAME?
0.1915 60.614 #NAME? #NAME? #NAME?
0.1617 63.998 #NAME? #NAME? #NAME?
0.1267 67.924 #NAME? #NAME? #NAME?
0.1078 70.229 #NAME? #NAME? #NAME?
0.0859 72.832 #NAME? #NAME? #NAME?
0 84.562 #NAME? #NAME? #NAME?

Observe the difference between experim


calculated values before and after param
Experimental
Calculated

3 0.4 0.5 0.6 0.7 0.8 0.9 1


Mole fraction of methanol

quid equilibrium data using Excel Solver


or-liquid equilibrium data minimizing the summation of the squared difference between experimental and calculated temperatures.

Jer Lee, and Ho-mu Lin


Chloroethenes

T in Kelvin; saturation pressure in kPa

1,2-DCE: 1,2-dichloroethane
DMSO: dimethylsulfoxide

nt to fitting the interaction parameters/R, with unit in Kelvin)

Calculated Calculated Calculated Calculated Calculated


T (K) Psat1 (kPa) Psat2 (kPa) ln (gamma1) ln (gamma2)
461.85 1182.242 95.300 #NAME? #NAME?
436.42 732.562 46.897 #NAME? #NAME?
422.66 551.870 30.644 #NAME? #NAME?
394.60 290.378 11.572 #NAME? #NAME?
383.23 217.315 7.441 #NAME? #NAME?
376.44 181.069 5.634 #NAME? #NAME?
369.06 147.179 4.108 #NAME? #NAME?
359.99 112.614 2.733 #NAME? #NAME?
357.04 102.850 2.381 #NAME? #NAME?
354.60 95.300 2.120 #NAME? #NAME?

Experimental
Calculated
With the fitted parameters, the experimental and
Experimental
calculated values are undistinguishable in the
Calculated
phase diagram.

0.3 0.4 0.5 0.6 0.7 0.8 0.9 1


x1
e calculated with array function nrtlxs.

se/R cpe/R
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?

ge/(RT)
he/(RT)
se/R

0.8 0.9 1

e data points available there).


and calculated pressures.

se final columns were calculated with spreadsheet formulas.

gamma2 Pcalc(kPa) deltaP deltaP^2 y1calc y2calc


1 19.953 0 0 0 1
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
Objective function: Sum(deltaP^2) 494.2866227913

Hint: use Solver to minimize the objective function cell


changing the two cells that correspond to the binary
interaction parameters of the NRTL model.

erve the difference between experimental and


ulated values before and after parameter fitting.
and calculated temperatures.

Calculated Calculated Calculated


gamma1 gamma2 P (kPa) delta T (delta T)^2 delta P
0.94234 1.00000 95.30 0.8972 0.80493 0.0000
#NAME? #NAME? #NAME? 0.4234 0.17928 #NAME?
#NAME? #NAME? #NAME? -0.3436 0.11803 #NAME?
#NAME? #NAME? #NAME? -0.3958 0.15663 #NAME?
#NAME? #NAME? #NAME? 0.2320 0.05380 #NAME?
#NAME? #NAME? #NAME? 0.4422 0.19556 #NAME?
#NAME? #NAME? #NAME? 0.0556 0.00309 #NAME?
#NAME? #NAME? #NAME? -0.0079 0.00006 #NAME?
#NAME? #NAME? #NAME? 0.0370 0.00137 #NAME?
#NAME? #NAME? #NAME? -0.4539 0.20601 #NAME?

Sum((delta^2)) 1.718777
Use Solver to minimize this cell by chan
In the minimization,impose the constraint th
cells (grey cells) should be equal to zero.
ers, the experimental and
ndistinguishable in the
inimize this cell by changing the blue cells
on,impose the constraint that all the deltaP
should be equal to zero.
Calculation of activity coefficients and excess properties using the UNIQUAC model

Reference:
Reid, R.C., J.M. Prausnitz, and B.E. Poling
The Properties of Gases and Liquids
4th ed., McGraw-Hill, New York, 1987.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Liquid-liquid equilibrium of the ternary mixture acetonitrile(1)+benzene(2)+n-heptane(3)

R T(K)
1 318.49
r 1.87 3.19 5.17
q 1.72 2.4 4.4
Binary interactions 0 60.28 23.71
89.57 0 -135.9
545.8 245.4 0

x1 x2 x3 lngama(1)
0.1311 0.033 0.8359 #NAME?
0.9118717313 0.0197423977 0.068385871 #NAME?

Parameter fitting in the UNIQUAC model from vapor-liquid equilibrium data using Excel So

Modified version of problem 12.1: Smith, van Ness, and Abbott, Introduction to Chemical Engineering Thermodynamic

Objective:
Fit the binary interaction parameters of the UNIQUAC model using experimental vapor-liquid equilibrium data minimizing the su

methanol(1)+water(2)
R T(K) P1sat
1 333.15 P2sat
r 1.4311 0.92
q 1.432 1.4
Binary interactions 0 -213.6961399482 It is common to report UNIQUAC
358.550089419 0 In this case, use R=1 in the sprea

The first five columns are experimental data for the mixture.

x1exp x2exp y1exp y2exp


0 1 0 1
0.1686 0.8314 0.5714 0.4286
0.2167 0.7833 0.6268 0.3732
0.3039 0.6961 0.6943 0.3057
0.3681 0.6319 0.7345 0.2655
0.4461 0.5539 0.7742 0.2258
0.5282 0.4718 0.8085 0.1915
0.6044 0.3956 0.8383 0.1617
0.6804 0.3196 0.8733 0.1267
0.7255 0.2745 0.8922 0.1078
0.7776 0.2224 0.9141 0.0859
1 0 1 0

Isothermal flash calculation by direct minimization of the system's Gibbs free energy

A 10 mol/s stream of a mixture of methanol(1)+water(2), with mole fractions of 0.67 and 0.33, respectively,
is fed to a continuous separation vessel (flash) that operates at 333.15 K and 60 kPa.
Determine the flowrates and compositions in the liquid and vapor output streams from the separation vessel. Assum
(1) ideal vapor phase behavior;
(2) activity coefficient given by the UNIQUAC model with the parameters provided;
(3) Poynting factors and saturated liquid fugacity corrections are negligible.

methanol(1)+water(2)
R T(K) P1sat (kPa)
1 333.15 P2sat (kPa)
r 1.4311 0.92 P (kPa)
q 1.432 1.4
Binary interactions 0 -213.6961399482 It is common to report UNIQUAC
358.550089419 0 In this case, use R=1 in the sprea

Spreadsheet Spreadsheet
formula formula
Methanol Water Total Mole fraction (1)
Feed flow (mol/s) 6.7 3.3 10 0.67
Liquid out (mol/s) 2.3855038251 2.2433653032 4.6288691283 0.5153534824
Vapor out (mol/s) 4.3144961749 1.0566346968 5.3711308717 0.8032751906

Hints:
Liquid out flow to be calculated using Solver.
Vapor out is the feed flow minus the liquid out flow.

Isothermal mixing of two liquid streams

Comment: since all streams are at the same temperature, the pure component heat capacities cancel in the energy balance (tr

methanol(1)+water(2)
R T(K)
1 333.15
r 1.4311 0.92
q 1.432 1.4
Binary interactions 0 -213.6961399482 It is common to report UNIQUAC
358.550089419 0 In this case, use R=1 in the sprea

These 4 columns were calculat

x1 x2 Ge/(RT)
stream I 0.2 0.8 #NAME?
stream II 0.6 0.4 #NAME?
stream III 0.4 0.6 #NAME?

Heat load (J/s) -108.31

Adiabatic mixing of two liquid streams


methanol(1)+water(2)
R T(K)
1 333.15
r 1.4311 0.92
q 1.432 1.4
Binary interactions 0 -213.6961399482 It is common to report UNIQUAC
358.550089419 0 In this case, use R=1 in the sprea

These 4 columns were calculat

x1 x2 ge/(RT)
stream I 0.2 0.8 #NAME?
stream II 0.6 0.4 #NAME?
stream III 0.4 0.6 #NAME?

Reference T (K) 333.15


H(I) (J/s) -162.6709938407
H(II) (J/s) -275.1355112999

(H(I)+H(II)) (J/s) -437.8065051406

Temperature (III) (K) 330


H(III) (J/s) -1042.2335275071

(H(III)-(H(I)+H(II))) (J/s) -604.4270223666 Use Solver to zero this cell, by


changing the temperature of stream III.

Liquid-liquid equilibrium in the system sulfolane(1) + benzene (2) + n-heptane (3)

Original reference
Letcher, T.M., G.G. Redhi, S.E. Radloff, U. Domanska
Liquid-Liquid Equilibria of the Ternary Mixtures with Sulfolane at 303.15 K
J. Chem. Eng. Data 1996, 41, 634-638

sulfolane (1) benzene (2) n-heptane (3)


Molar volume (cm3/mol) 95.26 89.4 147.4
l (bulk factor) 1 1 0

Z (coordination number) 10

R (J/(mol.K)) T(K)
8.314 303.15

sulfolane (1) benzene (2) n-heptane (3)


r 2.7893 2.6177 4.3160
q 2.2314 2.0942 3.6528
Binary interactions 0 1926.46 717.84
(J/mol) 688.69 0 -277.39
12884.36 1926.77 0

Experimental Experimental
n-heptane rich phase Sulfolane rich phase
x1h x2h x3h x1s x2s
0.008 0.118 0.874 0.928 0.054
0.011 0.295 0.694 0.85 0.13
0.021 0.485 0.494 0.803 0.177
0.071 0.599 0.33 0.752 0.228
0.155 0.624 0.221 0.707 0.272
0.341 0.562 0.097 0.571 0.397

Data reorganization to plot tie-lines

x1 x2
0.008 0.118
0.928 0.054

0.011 0.295
0.85 0.13

0.021 0.485
0.803 0.177

0.071 0.599
0.752 0.228

0.155 0.624
0.707 0.272
0.341 0.562
0.571 0.397

0.9

0.8

0.7

0.6

Benzene
0.5

0.4

0.3

0.2

0.1

0
0 0.1 0.2 0
Letcher et al., 1996
QUAC model

It is common to report UNIQUAC binary interaction parameters as a12/R, a21/R, etc in Kelvin.
In this case, use R=1 in the spreadsheet; otherwise use units compatible with the aij values.

lngama(2) lngama(3) gama(1) gama(2) gama(3)


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

ata using Excel Solver

ineering Thermodynamics, 6th edition, Mc-Graw-Hill, 2001 (reference to the data points available there).

rium data minimizing the summation of the squared difference between experimental and calculated pressures.

84.562
19.953

mmon to report UNIQUAC binary interaction parameters as a12/R, a21/R, etc in Kelvin.
case, use R=1 in the spreadsheet; otherwise use units compatible with the aij values.

These 2 columns were calculated These final columns were calculated with spreadsheet form
with array function uniquac.
Pexp(kPa) lngamma1 lngamma2 gamma1 gamma2
19.953 #NAME? #NAME? 2.379606509 1
39.223 #NAME? #NAME? #NAME? #NAME?
42.984 #NAME? #NAME? #NAME? #NAME?
48.852 #NAME? #NAME? #NAME? #NAME?
52.784 #NAME? #NAME? #NAME? #NAME?
56.652 #NAME? #NAME? #NAME? #NAME?
60.614 #NAME? #NAME? #NAME? #NAME?
63.998 #NAME? #NAME? #NAME? #NAME?
67.924 #NAME? #NAME? #NAME? #NAME?
70.229 #NAME? #NAME? #NAME? #NAME?
72.832 #NAME? #NAME? #NAME? #NAME?
84.562 #NAME? #NAME? #NAME? #NAME?

33, respectively,

separation vessel. Assume:

84.562
19.953
60

mmon to report UNIQUAC binary interaction parameters as a12/R, a21/R, etc in Kelvin.
case, use R=1 in the spreadsheet; otherwise use units compatible with the aij values.

Spreadsheet These 2 columns were calculated Spreadsheet


formula with array function uniquac. formula
Mole fraction (2) lngamma(1) lngamma(2) G/(RT)
0.33
0.4846465176 #NAME? #NAME? 14.7820211214
0.1967248094 19.3281013304
Liquid+vapor 34.1101224517 Use Solver to minimize the total Gibbs
The liquid flowrates of methanol and w
variables in the solution procedure imp
el in the energy balance (try to prove that) and are not necessary.

mmon to report UNIQUAC binary interaction parameters as a12/R, a21/R, etc in Kelvin.
case, use R=1 in the spreadsheet; otherwise use units compatible with the aij values.

4 columns were calculated with array function uniquacxs. Spreadsheet


formula
He/(RT) Se/R Cpe/R He(J/mol)
#NAME? #NAME? #NAME? -162.67
#NAME? #NAME? #NAME? -275.14
#NAME? #NAME? #NAME? -273.06
mmon to report UNIQUAC binary interaction parameters as a12/R, a21/R, etc in Kelvin.
case, use R=1 in the spreadsheet; otherwise use units compatible with the aij values.

4 columns were calculated with array function uniquacxs. Spreadsheet


formula
he/(RT) se/R cpe/R he(J/mol)
#NAME? #NAME? #NAME? -162.6709938407
#NAME? #NAME? #NAME? -275.1355112999
#NAME? #NAME? #NAME? -279.1967637536
r and q were computed from the molar volume and bulk factor

These values are used as feed flows in a flash-like calculation


Calculated Calculated: mole numbers in
Average mole fractions multiplied by 100 n-heptane rich phase
x3s n1 n2 n3 n1h
0.018 46.8 8.6 44.6 0.0566325003
0.02 43.05 21.25 35.7 0.4738792627
0.02 41.2 33.1 25.7 1.8304848095
0.02 41.15 41.35 17.5 4.8250119439
0.021 43.1 44.8 12.1 8.3941880075
0.032 45.6 47.95 6.45 17.8253786795
1

0.9

0.8
Experimental n-heptane
0.7 ri ch phase
Experimental sulfol ane
ri ch phase
0.6 Calculated n-heptane rich
phase+UNIQUAC
Calculated sulfolane rich
0.5 phase
Experimental tie-lines
Exp tieline 2
0.4 Exp tieline 3
Exp tieline 4
0.3 Exp tieline 5
Exp tieline 6
Calculated tie-lines
0.2 Calc 2
Calc3
Calc4
0.1 Calc5

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Sulfolane
xgama(1) xgama(2) xgama(3)
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?

alculated with spreadsheet formulas.

Pcalc(kPa) deltaP deltaP^2 y1calc y2calc


19.953 0 0 0 1
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
Objective function: Sum(deltaP^2) 1.0761125321

Hint: use Solver to minimize the objective function cell


changing the two cells that correspond to the binary
interaction parameters of the UNIQUAC model.

lver to minimize the total Gibbs free energy/(RT).


uid flowrates of methanol and water are the independent
es in the solution procedure implemented here.
ted: mole numbers in Calculated: mole numbers in
ne rich phase sulfolane rich phase
n2h n3h n1s n2s n3s
5.8735577044 43.9233228871 46.7433674997 2.7264422956 0.6766771129
14.639538106 34.8314200803 42.5761207373 6.610461894 0.8685799197
23.32383812 24.6370240964 39.3695151905 9.77616188 1.0629759036
30.425720154 16.3836875784 36.3249880561 10.924279846 1.1163124216
33.0560783683 10.9562707769 34.7058119925 11.7439216317 1.1437292231
35.2684740723 5.3965787067 27.7746213205 12.6815259277 1.0534212933
-7.771561172E-16
0.1043990948
0.1218441457
0.1428062734
0.1506464987
0.1527209407
0.1471587404
0.1357249984
0.1189501625
0.1066737659
0.0904897355
1.589839371E-16
Calculated: mole fractions in Calculated: mole fractions in
n-heptane rich phase sulfolane rich phase
x1h x2h x3h x1s x2s x3s
0.00114 0.11782 0.88105 0.93214 0.05437 0.01349
0.00949 0.29311 0.69740 0.85058 0.13206 0.01735
0.03676 0.46843 0.49481 0.78412 0.19471 0.02117
0.09345 0.58925 0.31730 0.75105 0.22587 0.02308
0.16017 0.63076 0.20906 0.72921 0.24675 0.02403
0.30476 0.60298 0.09226 0.66911 0.30551 0.02538

Data reorganization to plot tie-lines

x1 x2
0.00114 0.11782
0.93214 0.05437

0.00949 0.29311
0.85058 0.13206

0.03676 0.46843
0.78412 0.19471

0.09345 0.58925
0.75105 0.22587

0.16017 0.63076
0.72921 0.24675
0.30476 0.60298
0.66911 0.30551
Calculated: ln(gamma) in Calculated: ln(gamma) in Calculated: n(i)*ln(x(i)*gamma(i)) in
n-heptane rich phase sulfolane rich phase n-heptane rich phase
1 2 3 1 2 3 1
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
culated: n(i)*ln(x(i)*gamma(i)) in Calculated: n(i)*ln(x(i)*gamma(i)) in Calculated: deltaG
eptane rich phase sulfolane rich phase Sum (n*ln(x*gamma) for all
2 3 1 2 3 components in all phases
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
Use Solver to minimize this cell in each row by changing the blue cells of the same row.
Calculation of activity coefficients and excess properties using the UNIFAC model

Reference:
Reid, R.C., J.M. Prausnitz, and B.E. Poling
The Properties of Gases and Liquids
4th ed., McGraw-Hill, New York, 1987.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

acetone(1)+n-pentane(2)
Example taken from Reid, R.C., J.M. Prausnitz and B. Poling, The Properties of Gases and Liquids, 4th edition, McGraw

CH3 CH2 CH3CO


r 0.9011 0.6744 1.6724
q 0.848 0.54 1.488
CH3 0 0 476.4
CH2 0 0 476.4
CH3CO 26.76 26.76 0
acetone 1 0 1 Group description of acetone: 1 CH3 a
n-pentane 2 3 0 Group description of n-pentane: 2 CH

R 1 The unit of R should be compatible with the unit of the UNIFAC binary interac
T (K) 307

These 2 columns were calculated These two columns were calculated


with array function unifac. with spreadsheet formulas.
x1 x2 lngama(1) lngama(2) gama(1)
0.047 0.953 #NAME? #NAME? 4.9920343115

diethylamine(1)+n-heptane(2)
Example taken from Smith, J.M., H.C. Van Ness, and M.M. Abbott, Introduction to Chemical Engineering Thermodynam

CH3 CH2 CH2NH


r 0.9011 0.6744 1.207
q 0.848 0.54 0.936
CH3 0 0 255.7
CH2 0 0 255.7
CH2NH 65.33 65.33 0
diethylamine 2 1 1 Group description of diethylamine: 2 C
n-heptane 2 5 0 Group description of n-heptane: 2 CH

R 1 The unit of R should be compatible with the unit of the UNIFAC binary interac
T (K) 308.15

These 2 columns were calculated These two columns were calculated


with array function unifac. with spreadsheet formulas.
x1 x2 lngama(1) lngama(2) gama(1)
0.4 0.6 #NAME? #NAME? 1.1330392999
FAC model

iquids, 4th edition, McGraw-Hill, pages 322-332.

scription of acetone: 1 CH3 and 1 CH3CO.


scription of n-pentane: 2 CH3 and 3 CH2.

of the UNIFAC binary interaction parameters. These are normally given in Kelvin. In this case, use R=1, as done here.

wo columns were calculated These 4 columns were calculated with array function unifacxs.
eadsheet formulas.
gama(2) gert hert ser cper
1.0052602112 #NAME? #NAME? #NAME? #NAME?

There is a small discrepancy with respect to the values reported in the Reid et al., possibly caused by round-offs.

Engineering Thermodynamics, 6th edition, McGraw-Hill, pages 767-769.

scription of diethylamine: 2 CH3, 1 CH2, and 1 CH2NH


scription of n-heptane: 2 CH3 and 5 CH2.

of the UNIFAC binary interaction parameters. These are normally given in Kelvin. In this case, use R=1, as done here.
wo columns were calculated These 4 columns were calculated with array function unifacxs.
eadsheet formulas.
gama(2) gert hert ser cper
1.0470238738 #NAME? #NAME? #NAME? #NAME?

There is perfect agreement with the activity coefficient values reported by Smith et al.
1, as done here.

caused by round-offs.

1, as done here.
Calculation of activity coefficients and excess properties using the Modified UNIFAC model

References:

Weidlich, U. and J. Gmehling


A Modified UNIFAC Model. 1. Prediction of VLE, hE, and gamma at infinite dilution
Ind. Eng. Chem. Res. 1987, 26, 1372-1381.

Jakob, A., H. Grensemann, J. Lohmann, J. Gmehling


Further Development of Modified UNIFAC (Dortmund): Revision and Extension 5
Ind. Eng. Chem. Res. 2006, 45, 7924-7933

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

n-pentane(1)+ benzene(2)

CH3 CH2 ACH


r 0.6325 0.6325 0.3763
q 1.0608 0.7081 0.4321
CH3 0 0 114.2
a CH2 0 0 114.2
ACH 16.07 16.07 0
CH3 0 0 0.0933
b CH2 0 0 0.0933
ACH -0.2998 -0.2998 0
CH3 0 0 0
c CH2 0 0 0
ACH 0 0 0
n-pentane 2 3 0 Group description of n-pentane: 2 CH3 and 3 CH2.
benzene 0 0 6 Group description of benzene: 6 ACH.

R 1 The unit of R should be compatible with the unit of the Modified UNIFAC bina
T (K) 298.15

These 4 columns were calculated with Spreadsheet


array function modunifacxs. formula
x1 x2 gert hert ser cper he(J/mol)
0 1 #NAME? #NAME? #NAME? #NAME? 0
0.02 0.98 #NAME? #NAME? #NAME? #NAME? #NAME?
0.04 0.96 #NAME? #NAME? #NAME? #NAME? #NAME?
0.06 0.94 #NAME? #NAME? #NAME? #NAME? #NAME?
0.08 0.92 #NAME? #NAME? #NAME? #NAME? #NAME?
0.1 0.9 #NAME? #NAME? #NAME? #NAME? #NAME?
0.12 0.88 #NAME? #NAME? #NAME? #NAME? #NAME?
0.14 0.86 #NAME? #NAME? #NAME? #NAME? #NAME?
0.16 0.84 #NAME? #NAME? #NAME? #NAME? #NAME?
0.18 0.82 #NAME? #NAME? #NAME? #NAME? #NAME?
0.2 0.8 #NAME? #NAME? #NAME? #NAME? #NAME?
0.22 0.78 #NAME? #NAME? #NAME? #NAME? #NAME?
0.24 0.76 #NAME? #NAME? #NAME? #NAME? #NAME?
0.26 0.74 #NAME? #NAME? #NAME? #NAME? #NAME?
0.28 0.72 #NAME? #NAME? #NAME? #NAME? #NAME?
0.3 0.7 #NAME? #NAME? #NAME? #NAME? #NAME?
0.32 0.68 #NAME? #NAME? #NAME? #NAME? #NAME?
0.34 0.66 #NAME? #NAME? #NAME? #NAME? #NAME?
0.36 0.64 #NAME? #NAME? #NAME? #NAME? #NAME?
0.38 0.62 #NAME? #NAME? #NAME? #NAME? #NAME?
0.4 0.6 #NAME? #NAME? #NAME? #NAME? #NAME?
0.42 0.58 #NAME? #NAME? #NAME? #NAME? #NAME?
0.44 0.56 #NAME? #NAME? #NAME? #NAME? #NAME?
0.46 0.54 #NAME? #NAME? #NAME? #NAME? #NAME?
0.48 0.52 #NAME? #NAME? #NAME? #NAME? #NAME?
0.5 0.5 #NAME? #NAME? #NAME? #NAME? #NAME?
0.52 0.48 #NAME? #NAME? #NAME? #NAME? #NAME?
0.54 0.46 #NAME? #NAME? #NAME? #NAME? #NAME?
0.56 0.44 #NAME? #NAME? #NAME? #NAME? #NAME?
0.58 0.42 #NAME? #NAME? #NAME? #NAME? #NAME?
0.6 0.4 #NAME? #NAME? #NAME? #NAME? #NAME?
0.62 0.38 #NAME? #NAME? #NAME? #NAME? #NAME?
0.64 0.36 #NAME? #NAME? #NAME? #NAME? #NAME?
0.66 0.34 #NAME? #NAME? #NAME? #NAME? #NAME?
0.68 0.32 #NAME? #NAME? #NAME? #NAME? #NAME?
0.7 0.3 #NAME? #NAME? #NAME? #NAME? #NAME?
0.72 0.28 #NAME? #NAME? #NAME? #NAME? #NAME?
0.74 0.26 #NAME? #NAME? #NAME? #NAME? #NAME?
0.76 0.24 #NAME? #NAME? #NAME? #NAME? #NAME?
0.78 0.22 #NAME? #NAME? #NAME? #NAME? #NAME?
0.8 0.2 #NAME? #NAME? #NAME? #NAME? #NAME?
0.82 0.18 #NAME? #NAME? #NAME? #NAME? #NAME?
0.84 0.16 #NAME? #NAME? #NAME? #NAME? #NAME?
0.86 0.14 #NAME? #NAME? #NAME? #NAME? #NAME?
0.88 0.12 #NAME? #NAME? #NAME? #NAME? #NAME?
0.9 0.1 #NAME? #NAME? #NAME? #NAME? #NAME?
0.92 0.08 #NAME? #NAME? #NAME? #NAME? #NAME?
0.94 0.06 #NAME? #NAME? #NAME? #NAME? #NAME?
0.96 0.04 #NAME? #NAME? #NAME? #NAME? #NAME?
0.98 0.02 #NAME? #NAME? #NAME? #NAME? #NAME?
1 0 #NAME? #NAME? #NAME? #NAME? #NAME?
Exce ss e nth alpy (J/ m o l)

1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fracton of n-pentane

12

n-pentane
Natural logarithm of actvity coefcient

10
benzene

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fracton of n-pentane
the Modified UNIFAC model (Dortmund version)

ion of n-pentane: 2 CH3 and 3 CH2.


ion of benzene: 6 ACH.

with the unit of the Modified UNIFAC binary interaction parameters. These are normally given in Kelvin. In this case, use R=1, as done here.

These 2 columns were calculated


with array function modunifac.
lngamma1 lngamma2
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
7 0.8 0.9 1
use R=1, as done here.
Physical properties from the van der Waals equation of state

Reference:
Reid, R.C., J.M. Prausnitz, and B.E. Poling
The Properties of Gases and Liquids
4th ed., McGraw-Hill, New York, 1987.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Normal boiling temperature of n-hexane (i.e., at a pressure of 1 atm = 1.0132 bar)

R 83.14
T(K) 300 Compute using Solver

n-hexane
Tc(K) 507.5
Pc(bar) 30.1
kij 0

Computed with Computed with


function function
vdwlnphil vdwlnphiv
x Pespec lnphiL lnphiV
1 1.0132 0.7663151887 -0.0340823103

Example of sound speed calculation

Use SI units throught the calculation


Nitrogen
Tc(K) 126.2
Pc(Pa) 3.39E+06
kij 0
Temperature (K) 300
Molar mass (g/mol) 28.013
Molar mass (kg/mol) 0.028013
Ideal gas cp coefficients

R (SI) 8.314

Spreadsheet Spreadsheet
formula formula
x Pespec (bar) Pespec(Pa) cpig (J/(mol.K))
1 1.0132 101320 2.95E+01
1 1.5132 151320 2.95E+01
1 2.0132 201320 2.95E+01
1 2.5132 251320 2.95E+01
1 3.0132 301320 2.95E+01
1 3.5132 351320 2.95E+01
1 4.0132 401320 2.95E+01
1 4.5132 451320 2.95E+01
1 5.0132 501320 2.95E+01
1 5.5132 551320 2.95E+01
1 6.0132 601320 2.95E+01
1 6.5132 651320 2.95E+01
1 7.0132 701320 2.95E+01
1 7.5132 751320 2.95E+01
1 8.0132 801320 2.95E+01
1 8.5132 851320 2.95E+01
1 9.0132 901320 2.95E+01
1 9.5132 951320 2.95E+01
1 10.0132 1001320 2.95E+01
1 10.5132 1051320 2.95E+01
1 11.0132 1101320 2.95E+01
1 11.5132 1151320 2.95E+01
1 12.0132 1201320 2.95E+01
1 12.5132 1251320 2.95E+01
1 13.0132 1301320 2.95E+01
1 13.5132 1351320 2.95E+01
1 14.0132 1401320 2.95E+01
1 14.5132 1451320 2.95E+01
1 15.0132 1501320 2.95E+01
1 15.5132 1551320 2.95E+01
1 16.0132 1601320 2.95E+01
1 16.5132 1651320 2.95E+01
1 17.0132 1701320 2.95E+01
1 17.5132 1751320 2.95E+01
1 18.0132 1801320 2.95E+01
1 18.5132 1851320 2.95E+01
1 19.0132 1901320 2.95E+01
1 19.5132 1951320 2.95E+01
1 20.0132 2001320 2.95E+01
1 20.5132 2051320 2.95E+01
1 21.0132 2101320 2.95E+01
1 21.5132 2151320 2.95E+01
1 22.0132 2201320 2.95E+01
1 22.5132 2251320 2.95E+01
1 23.0132 2301320 2.95E+01
1 23.5132 2351320 2.95E+01
1 24.0132 2401320 2.95E+01
1 24.5132 2451320 2.95E+01
1 25.0132 2501320 2.95E+01
1 25.5132 2551320 2.95E+01
atm = 1.0132 bar)

Computed with
spreadsheet
function.
deltalnphi
0.800397499 Use Solver to zero this cell by changing T.

31.15 -1.36E-02 2.68E-05 -1.17E-09

These 4 columns were calculated with array function svsoundspeedv.These columns were calculated using spreadsh
rho (mol/m3) dpdrho (Pa/(mol/m3)) cprr (K) dpdt (Pa/K) cpresidual (J/(mol.K))
#NAME? #NAME? #NAME? #NAME? 0.0371750624
#NAME? #NAME? #NAME? #NAME? 0.0555741664
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
mns were calculated using spreadsheet formulas
cp (J/(mol.K)) cv (J/(mol.K)) gama=cp/cv sound speed (m/s)
29.4966390624 #NAME? 1.394939315 352.1909781689
29.5150381664 #NAME? 1.395809435 352.1873763833
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
Physical properties from the Redlich-Kwong equation of state

Reference:
Reid, R.C., J.M. Prausnitz, and B.E. Poling
The Properties of Gases and Liquids
4th ed., McGraw-Hill, New York, 1987.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Normal boiling temperature of n-hexane (i.e., at a pressure of 1 atm = 1.0132 bar)

R 83.14
T(K) 300 Compute using Solver

n-hexane
Tc(K) 507.5
Pc(bar) 30.1
kij 0

Computed wit Computed with Computed with


function function spreadsheet
rklnphil rklnphiv function.
x Pespec lnphiL lnphiV deltalnphi
1 1.0132 -0.678940756 -0.0497334708 -0.6292072852

Example of sound speed calculation


Example of sound speed calculation
Use SI units throught the calculation
Nitrogen
Tc(K) 126.2
Pc(Pa) 3.39E+06
kij 0
Temperature (K) 300
Molar mass (g/mol) 28.013
Molar mass (kg/mol) 0.028013
Ideal gas cp coefficients 31.15

R (SI) 8.314

Spreadsheet Spreadsheet These 4 columns were calculated w


formula formula
x Pespec (bar) Pespec(Pa) cpig (J/(mol.K)) rho (mol/m3)
1 1.0132 101320 2.95E+01 #NAME?
1 1.5132 151320 2.95E+01 #NAME?
1 2.0132 201320 2.95E+01 #NAME?
1 2.5132 251320 2.95E+01 #NAME?
1 3.0132 301320 2.95E+01 #NAME?
1 3.5132 351320 2.95E+01 #NAME?
1 4.0132 401320 2.95E+01 #NAME?
1 4.5132 451320 2.95E+01 #NAME?
1 5.0132 501320 2.95E+01 #NAME?
1 5.5132 551320 2.95E+01 #NAME?
1 6.0132 601320 2.95E+01 #NAME?
1 6.5132 651320 2.95E+01 #NAME?
1 7.0132 701320 2.95E+01 #NAME?
1 7.5132 751320 2.95E+01 #NAME?
1 8.0132 801320 2.95E+01 #NAME?
1 8.5132 851320 2.95E+01 #NAME?
1 9.0132 901320 2.95E+01 #NAME?
1 9.5132 951320 2.95E+01 #NAME?
1 10.0132 1001320 2.95E+01 #NAME?
1 10.5132 1051320 2.95E+01 #NAME?
1 11.0132 1101320 2.95E+01 #NAME?
1 11.5132 1151320 2.95E+01 #NAME?
1 12.0132 1201320 2.95E+01 #NAME?
1 12.5132 1251320 2.95E+01 #NAME?
1 13.0132 1301320 2.95E+01 #NAME?
1 13.5132 1351320 2.95E+01 #NAME?
1 14.0132 1401320 2.95E+01 #NAME?
1 14.5132 1451320 2.95E+01 #NAME?
1 15.0132 1501320 2.95E+01 #NAME?
1 15.5132 1551320 2.95E+01 #NAME?
1 16.0132 1601320 2.95E+01 #NAME?
1 16.5132 1651320 2.95E+01 #NAME?
1 17.0132 1701320 2.95E+01 #NAME?
1 17.5132 1751320 2.95E+01 #NAME?
1 18.0132 1801320 2.95E+01 #NAME?
1 18.5132 1851320 2.95E+01 #NAME?
1 19.0132 1901320 2.95E+01 #NAME?
1 19.5132 1951320 2.95E+01 #NAME?
1 20.0132 2001320 2.95E+01 #NAME?
1 20.5132 2051320 2.95E+01 #NAME?
1 21.0132 2101320 2.95E+01 #NAME?
1 21.5132 2151320 2.95E+01 #NAME?
1 22.0132 2201320 2.95E+01 #NAME?
1 22.5132 2251320 2.95E+01 #NAME?
1 23.0132 2301320 2.95E+01 #NAME?
1 23.5132 2351320 2.95E+01 #NAME?
1 24.0132 2401320 2.95E+01 #NAME?
1 24.5132 2451320 2.95E+01 #NAME?
1 25.0132 2501320 2.95E+01 #NAME?
1 25.5132 2551320 2.95E+01 #NAME?
Use Solver to zero this cell by changing T.

-1.36E-02 2.68E-05 -1.17E-09

e 4 columns were calculated with array function svsoundspeedv. These columns were calculated using spreadsheet formul

dpdrho (Pa/(mol/m3)) cprr (K) dpdt (Pa/K) cpresidual (J/(mol.K)) cp (J/(mol.K))


#NAME? #NAME? #NAME? 0.04572326 29.50518726
#NAME? #NAME? #NAME? 0.0682896949 29.5277536949
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
ed using spreadsheet formulas

cv (J/(mol.K)) gama=cp/cv sound speed (m/s)


#NAME? 1.3947405535 352.2656937379
#NAME? 1.3955097528 352.2988983822
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
Physical properties from the Soave-Redlich-Kwong equation of state

Reference:
Reid, R.C., J.M. Prausnitz, and B.E. Poling
The Properties of Gases and Liquids
4th ed., McGraw-Hill, New York, 1987.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Normal boiling temperature of n-hexane (i.e., at a pressure of 1 atm = 1.0132 bar)

R 83.14
T(K) 300 Compute using Solver

n-hexane
Tc(K) 507.5
Pc(bar) 30.1
omega 0.299
kij 0

x Pespec
1 1.0132

Example of sound speed calculation

Use SI units throught the calculation


Nitrogen
Tc(K) 126.2
Pc(Pa) 3.39E+06
omega 0.039
kij 0
Temperature (K)
Molar mass (g/mol)
Molar mass (kg/mol)
Ideal gas cp coefficients

R (SI)
x Pespec (bar)
1 1.0132
1 1.5132
1 2.0132
1 2.5132
1 3.0132
1 3.5132
1 4.0132
1 4.5132
1 5.0132
1 5.5132
1 6.0132
1 6.5132
1 7.0132
1 7.5132
1 8.0132
1 8.5132
1 9.0132
1 9.5132
1 10.0132
1 10.5132
1 11.0132
1 11.5132
1 12.0132
1 12.5132
1 13.0132
1 13.5132
1 14.0132
1 14.5132
1 15.0132
1 15.5132
1 16.0132
1 16.5132
1 17.0132
1 17.5132
1 18.0132
1 18.5132
1 19.0132
1 19.5132
1 20.0132
1 20.5132
1 21.0132
1 21.5132
1 22.0132
1 22.5132
1 23.0132
1 23.5132
1 24.0132
1 24.5132
1 25.0132
1 25.5132

Effect of external fields (gravitational and centrifugal) on phase equilibrium.

When a substance (or mixture) is present in a large system with depths of hundreds of meters the effect of position
This is formulated by modifying the formula for the fugacity (ln fug (CO2)) in the table below) to account for the effe

R (bar.cm3/(mol.K)) 83.14
T(K) 333

R (for gravitational and centrifugal fields) 8314


Gravity acceleration (m/s^2) 9.81
Radial speed (radians/s) 0

CO2
Molar mass 44
Tc(K) 304.1
Pc(bar) 73.8
omega 0.239
kij 0

The CO2 pressure is specified at level 0 m. Find its pressure 200 m below.

Level (m) Radial position (m) x(CO2)


0 0 1
-200 0 1

Isenthalpic expansion

The expansion of a fluid stream (pure substance or mixture) from a high pressure to a low pressure condition in a p

Consider the expansion of a Nitrogen stream, initially at 250 K and 100 bar, to a final condition at 10 bar, and determ
Use SI units throught the calculation
Nitrogen
Tc(K) 126.2
Pc(Pa) 3.39E+06
omega 0.039
kij 0

(T^0) coefficient (T^1) coefficient


Ideal gas cp coefficients (cp in J/(mol.K)) 31.15 -1.36E-02
R (J/(mol.K)) 8.314

Reference T (K) for enthalpy calculations 300

Mole fraction Pressure (Pascal)


Before the valve 1 10000000
After the valve 1 1000000

Isentropic expansion

The expansion of a fluid stream (pure substance or mixture) from a high pressure to a low pressure condition in a p

Consider the expansion of a Nitrogen stream, initially at 250 K and 100 bar, to a final condition at 70 bar, and determ

Use SI units throught the calculation


Nitrogen
Tc(K) 126.2
Pc(Pa) 3.39E+06
omega 0.039
kij 0

(T^0) coefficient (T^1) coefficient


Ideal gas cp coefficients (cp in J/(mol.K)) 31.15 -1.36E-02
R (J/(mol.K)) 8.314

Reference T (K) for entropy calculations 300


Reference P (Pascal) for entropy calculations 100000
Mole fraction Pressure (Pascal)
Before the equipment 1 10000000
After the equipment 1 7000000

Observe that the final temperatures of the isenthalpic and isentropic expansions are similar (about 226 K),
even though the specified final pressures are very different. Try to undestand this by looking at a PH diagram.
n of state

h as this one are problem specifications.

meric cells are results of calculations.

atm = 1.0132 bar)

using Solver

Computed with Computed with Computed with


function function spreadsheet
srklnphil srklnphiv function.
lnphiL lnphiV deltalnphi
-1.5582455743 -0.0574828321 -1.5007627422 Use Solver to zero this cell by changing T.

300
28.013
0.028013
cp coefficients 31.15 -1.36E-02 2.68E-05

8.314
Spreadsheet Spreadsheet These 4 columns were calculated with array function srksoundspeedv.
formula formula
Pespec(Pa) cpig (J/(mol.K)) rho (mol/m3) dpdrho (Pa/(mol/m3)) cprr (K)
101320 2.95E+01 #NAME? #NAME? #NAME?
151320 2.95E+01 #NAME? #NAME? #NAME?
201320 2.95E+01 #NAME? #NAME? #NAME?
251320 2.95E+01 #NAME? #NAME? #NAME?
301320 2.95E+01 #NAME? #NAME? #NAME?
351320 2.95E+01 #NAME? #NAME? #NAME?
401320 2.95E+01 #NAME? #NAME? #NAME?
451320 2.95E+01 #NAME? #NAME? #NAME?
501320 2.95E+01 #NAME? #NAME? #NAME?
551320 2.95E+01 #NAME? #NAME? #NAME?
601320 2.95E+01 #NAME? #NAME? #NAME?
651320 2.95E+01 #NAME? #NAME? #NAME?
701320 2.95E+01 #NAME? #NAME? #NAME?
751320 2.95E+01 #NAME? #NAME? #NAME?
801320 2.95E+01 #NAME? #NAME? #NAME?
851320 2.95E+01 #NAME? #NAME? #NAME?
901320 2.95E+01 #NAME? #NAME? #NAME?
951320 2.95E+01 #NAME? #NAME? #NAME?
1001320 2.95E+01 #NAME? #NAME? #NAME?
1051320 2.95E+01 #NAME? #NAME? #NAME?
1101320 2.95E+01 #NAME? #NAME? #NAME?
1151320 2.95E+01 #NAME? #NAME? #NAME?
1201320 2.95E+01 #NAME? #NAME? #NAME?
1251320 2.95E+01 #NAME? #NAME? #NAME?
1301320 2.95E+01 #NAME? #NAME? #NAME?
1351320 2.95E+01 #NAME? #NAME? #NAME?
1401320 2.95E+01 #NAME? #NAME? #NAME?
1451320 2.95E+01 #NAME? #NAME? #NAME?
1501320 2.95E+01 #NAME? #NAME? #NAME?
1551320 2.95E+01 #NAME? #NAME? #NAME?
1601320 2.95E+01 #NAME? #NAME? #NAME?
1651320 2.95E+01 #NAME? #NAME? #NAME?
1701320 2.95E+01 #NAME? #NAME? #NAME?
1751320 2.95E+01 #NAME? #NAME? #NAME?
1801320 2.95E+01 #NAME? #NAME? #NAME?
1851320 2.95E+01 #NAME? #NAME? #NAME?
1901320 2.95E+01 #NAME? #NAME? #NAME?
1951320 2.95E+01 #NAME? #NAME? #NAME?
2001320 2.95E+01 #NAME? #NAME? #NAME?
2051320 2.95E+01 #NAME? #NAME? #NAME?
2101320 2.95E+01 #NAME? #NAME? #NAME?
2151320 2.95E+01 #NAME? #NAME? #NAME?
2201320 2.95E+01 #NAME? #NAME? #NAME?
2251320 2.95E+01 #NAME? #NAME? #NAME?
2301320 2.95E+01 #NAME? #NAME? #NAME?
2351320 2.95E+01 #NAME? #NAME? #NAME?
2401320 2.95E+01 #NAME? #NAME? #NAME?
2451320 2.95E+01 #NAME? #NAME? #NAME?
2501320 2.95E+01 #NAME? #NAME? #NAME?
2551320 2.95E+01 #NAME? #NAME? #NAME?

equilibrium.

hundreds of meters the effect of position on properties is relevant.


n the table below) to account for the effect of the gravitational field.

Function Spreadsheet Spreadsheet


srklnphiv formula formula
Pespec (bar) lnphiv (CO2) ln fug (CO2) Function This function is the difference betw
8 #NAME? 2.05217
8.2667762786 -0.0281835748 2.05288 4.98E-07 Use Solver to zero this cell
Compute using
Solver

essure to a low pressure condition in a perfectly insulated valve (throtlting) is an isenthalpic process.

to a final condition at 10 bar, and determine its final temperature.


(T^2) coefficient (T^3) coefficient
2.68E-05 -1.17E-09

Spreadsheet These 4 columns were calculated with array function srkresv.


formula
Temperature (K) Ideal gas h (J/mol) gr/(RT) hr/(RT) sr/R
250 -1471.30 #NAME? #NAME? #NAME?
250.00 -1471.30 #NAME? #NAME? #NAME?
Compute using
Solver

essure to a low pressure condition in a perfectly insulated reversible turbine is an isentropic process.

to a final condition at 70 bar, and determine its final temperature.

(T^2) coefficient (T^3) coefficient


2.68E-05 -1.17E-09

Spreadsheet These 4 columns were calculated with array function srkresv.


formula
Temperature (K) Ideal gas s (J/(mol.K)) gr/(RT) hr/(RT) sr/R
250 -43.65 #NAME? #NAME? #NAME?
250.00 -40.69 #NAME? #NAME? #NAME?
Compute using
Solver

sions are similar (about 226 K),


nd this by looking at a PH diagram.
y changing T.

-1.17E-09
nction srksoundspeedv. These columns were calculated using spreadsheet formulas

dpdt (Pa/K) cpresidual (J/(mol.K)) cp (J/(mol.K)) cv (J/(mol.K))


#NAME? #NAME? 29.5125879833 #NAME?
#NAME? #NAME? 29.53879011 #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?

nction is the difference between ln fug values at two different positions.

ver to zero this cell


nction srkresv. Spreadsheet Spreadsheet
formula formula
cpr/R Residual h (J/mol) Molar h (J/mol)
#NAME? -821.24 -2292.54
#NAME? -93.05 -1564.35

Delta h (J/mol) 728.1883839424 Use Solver to zero this cell

The flowrates before and after the valve are equal (steady-state assumption).
Therefore, if the enthalpies are equal, the molar enthalpies must be equal.

Hint: use Solver to zero the Delta h cell by


changing the temperature after the valve.

nction srkresv. Spreadsheet Spreadsheet


formula formula
cpr/R Residual s (J/(mol.K)) Molar s (J/(mol.K))
#NAME? -2.91E+00 -46.56
#NAME? -2.12E+00 -42.81

Delta s (J/(mol.K)) 3.7558435905 Use Solver to zero this cell

The flowrates before and after the valve are equal (steady-state assumption).

Hint: use Solver to zero the Delta s cell by


changing the temperature after the valve.

Therefore, if the entropies are equal, the molar entropies must be equal.
gama=cp/cv sound speed (m/s)
1.3948883707 #NAME?
1.3957297384 #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
#NAME? #NAME?
assumption).
assumption).

must be equal.
Physical properties from the Peng-Robinson equation of state

Reference:
Reid, R.C., J.M. Prausnitz, and B.E. Poling
The Properties of Gases and Liquids
4th ed., McGraw-Hill, New York, 1987.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Normal boiling temperature of n-hexane (i.e., at a pressure of 1 atm = 1.0132 bar)

R 83.14
T(K) 300 Compute using Solver

n-hexane
Tc(K) 507.5
Pc(bar) 30.1
omega 0.299
kij 0

Computed with
function
prlnphil
x Pespec lnphiL
1 1.0132 -1.5312439398

Example of sound speed calculation

Use SI units throught the calculation


Nitrogen
Tc(K) 126.2
Pc(Pa) 3.39E+06
omega 0.039
kij 0
Temperature (K) 300
Molar mass (g/mol) 28.013
Molar mass (kg/mol) 0.028013
Ideal gas cp coefficients

R (SI) 8.314

Spreadsheet
formula
x Pespec (bar) Pespec(Pa)
1 1.0132 101320
1 1.5132 151320
1 2.0132 201320
1 2.5132 251320
1 3.0132 301320
1 3.5132 351320
1 4.0132 401320
1 4.5132 451320
1 5.0132 501320
1 5.5132 551320
1 6.0132 601320
1 6.5132 651320
1 7.0132 701320
1 7.5132 751320
1 8.0132 801320
1 8.5132 851320
1 9.0132 901320
1 9.5132 951320
1 10.0132 1001320
1 10.5132 1051320
1 11.0132 1101320
1 11.5132 1151320
1 12.0132 1201320
1 12.5132 1251320
1 13.0132 1301320
1 13.5132 1351320
1 14.0132 1401320
1 14.5132 1451320
1 15.0132 1501320
1 15.5132 1551320
1 16.0132 1601320
1 16.5132 1651320
1 17.0132 1701320
1 17.5132 1751320
1 18.0132 1801320
1 18.5132 1851320
1 19.0132 1901320
1 19.5132 1951320
1 20.0132 2001320
1 20.5132 2051320
1 21.0132 2101320
1 21.5132 2151320
1 22.0132 2201320
1 22.5132 2251320
1 23.0132 2301320
1 23.5132 2351320
1 24.0132 2401320
1 24.5132 2451320
1 25.0132 2501320
1 25.5132 2551320

Bubble temperature of n-hexane + pseudocomponent (hydrocarbon of 11.6 carbon atoms) (i.e., at a

R 83.14
T(K) 366.5005982776 Compute using Solver
P (bar) 1.0132
C atoms 11.6

n-hexane pseudocomponent
Tc(K) 507.5 660.00 calculated using Whitson interpolation tabl
Pc(bar) 30.1 21.40 calculated using Whitson interpolation tabl
omega 0.299 0.44 calculated using Whitson interpolation tabl
kij 0.00 0.00
0.00 0.00

Mole fraction 1 Mole fraction 2 ln phi1


Liquid 0.5 0.5 #NAME?
Vapor 0.9813669634 0.0186330366 #NAME?

Advanced example

Phase equilibrium of a semicontinuous mixture

Assumption: the probability density distribution function of the continuous family is a decaying exponential function

Characterization of the continuous fraction


Cm 7 Cm: minimum number of Carbon atoms in a su
CM 45 CM: maximum number of Carbon atoms in a s
MW 170 MW: average molar mass
eta 6.5
phi 45.5
CN 12.4285714286 CN: average number of atoms of carbon in the

delta 6.514726342

Find delta -0.000000078 Use Solver to zero this by cell changing delta.

D 0.1670442652

C 0.4954810563

Shape of the probability distribution function

Plot of the probability density function.

I F(I)
6.5 0.1672921019
7 0.1538871075
7.5 0.1415562455
8 0.1302134465
8.5 0.1197795377
9 0.1101816905
9.5 0.1013529118
10 0.0932315767
10.5 0.0857609982
11 0.0788890318
11.5 0.0725677111
12 0.0667529132
Probability density
12.5 0.0614040508
0.18
13 0.0564837889
13.5 0.0519577839 0.16
14 0.0477944445
14.5 0.0439647104 0.14
15 0.0404418502
15.5 0.0372012741 0.12
16 0.0342203631
16.5 0.0314783103 0.1
17 0.0289559762
17.5 0.0266357549 0.08
18 0.0245014512
18.5 0.0225381677
0.06
19 0.0207322007
0.04
19.5 0.0190709446
20 0.0175428037 0.02

1.04083408558608E-17
0 5
-0.02
0.08

0.06

0.04

0.02
20.5 0.0161371116
21 0.0148440566 1.04083408558608E-17
21.5 0.0136546131 0 5
22 0.0125604789 -0.02
22.5 0.0115540168
23 0.0106282019
23.5 0.0097765718
24 0.0089931822
24.5 0.0082725651
25 0.0076096904
25.5 0.0069999315
26 0.0064390321
26.5 0.0059230771
27 0.0054484652
27.5 0.0050118837
28 0.0046102851
28.5 0.0042408663
29 0.0039010488
29.5 0.0035884606
30 0.0033009198
30.5 0.0030364195
31 0.0027931134
31.5 0.0025693033
32 0.0023634269
32.5 0.0021740472
33 0.0019998424
33.5 0.0018395965
34 0.0016921909
34.5 0.0015565969
35 0.0014318679
35.5 0.0013171334
36 0.0012115925
36.5 0.0011145084
37 0.0010252037
37.5 0.0009430549
38 0.0008674886
38.5 0.0007979773
39 0.000734036
39.5 0.0006752182
40 0.0006211135
40.5 0.0005713441
41 0.0005255627
41.5 0.0004834498
42 0.0004447113
42.5 0.0004090769
43 0.0003762979
43.5 0.0003461454
44 0.000318409
44.5 0.0002928951
45 0.0002694256
45.5 0.0002478368

Phase equilibrium example

A more sophisticated integration method can be used (e.g., Rochocz, G.L., M. Castier, and S.I. Sandler,
Critical point calculations for semi-continuous mixtures, Fluid Phase Equilibria 139 (1997) 137-153) but
here we use Simpson's rule to locate the collocation points.

# of intervals 6
phi-eta 39
deltan 6.5

Pseudo-components 1 2 3
I 6.5 13 19.5

Tc(K) 530.00 687.00 784.00


Pc(bar) 32.25 19.60 14.50
omega 0.265 0.484 0.676
kij 0 0 0
0 0 0
0 0 0
0 0 0
0 0 0
0 0 0
0 0 0

R (bar.cm3/(mol.K)) 83.14
T (K) 601.3686847789
P (bar) 1.0132

Assumption: liquid phase follows the distribution above, as in a dew point calculation

Mole fraction 1 Mole fraction 2 Mole fraction 3


Vapor 0.4298118006 0.4225915874 0.1426820138

Renormalized vapor 0.403157819 0.3963853539 0.1338338534


Liquid 0.0123 0.0759 0.1341
ecifications.

= 1.0132 bar)

Computed with Computed with


function spreadsheet
prlnphiv function.
lnphiV deltalnphi
-0.059179726 -1.4720642138 Use Solver to zero this cell by changing T.
31.15 -1.36E-02 2.68E-05 -1.17E-09

Spreadsheet These 4 columns were calculated with array function svsoundspeedv.


formula
cpig (J/(mol.K)) rho (mol/m3) dpdrho (Pa/(mol/m3)) cprr (K) dpdt (Pa/K)
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?
2.95E+01 #NAME? #NAME? #NAME? #NAME?

n of 11.6 carbon atoms) (i.e., at a pressure of 1 atm = 1.0132 bar)

ated using Whitson interpolation tables


ated using Whitson interpolation tables
ated using Whitson interpolation tables

ln phi2 (ln x + lnphi +lnP) 1 (ln x + lnphi +lnP) 2


#NAME? -0.0396481105 -4.0568371344
#NAME? -0.0396448874 -4.0568157162
delta -3.223098092621E-06 -2.1418191004763E-05
delta^2 1.038836131466E-11 4.58738905916504E-10

Total delta^2 4.6912726723116E-10

y is a decaying exponential function with finite lower and upper limits of the independent variable

nimum number of Carbon atoms in a substance of the continuous fraction


aximum number of Carbon atoms in a substance of the continuous fraction
verage molar mass
erage number of atoms of carbon in the molecules of the continuous family
Probability density

0.18

0.16

0.14

0.12

0.1

0.08

0.06

0.04

0.02

1.04083408558608E-17
0 5 10 15 20 25 30 35 40 45 50
-0.02
0.08

0.06

0.04

0.02

1.04083408558608E-17
0 5 10 15 20 25 30 35 40 45 50
-0.02

Number of Carbon atoms


and S.I. Sandler,
97) 137-153) but

4 5 6 7
26 32.5 39 45.5 (approximated as 45 because this
45
850.00 901.50 940.00 971.00 Critical properties and acentric fac
11.90 9.39 7.95 6.96
0.844 0.915 0.985 1.048
0 0 0 0
0 0 0 0
0 0 0 0
0 0 0 0
0 0 0 0
0 0 0 0
0 0 0 0

Mole fraction 4 Mole fraction 5 Mole fraction 6 Mole fraction 7 Summation


0.0481745441 0.0162654468 0.0054917958 0.0010958332 1.0661130215

0.0451870891 0.0152567752 0.0051512323 0.0010278771


0.1944 0.2385 0.2311 0.1138
These columns were calculated using spreadsheet formulas

cpresidual (J/(mol.K)) cp (J/(mol.K)) cv (J/(mol.K)) gama=cp/cv sound speed (m/s)


0.0537373106 29.5132013106 #NAME? 1.3950857653 352.2891540726
0.0802373844 29.5397013844 #NAME? 1.3960243576 352.3341153584
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
5 50
5 50
ximated as 45 because this is the maximum value in the Whitson interpolation tables)

properties and acentric factor from Whitson interpolation tables

ln phi 1 ln phi 2 ln phi 3 ln phi 4 ln phi 5


There is a residue from the numerical integration: the rigorous value of the sum with an infinite number ot terms if 1.

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


#NAME? #NAME? #NAME? #NAME? #NAME?
ln phi 6 ln phi 7 ln fugacity 1 ln fugacity 2 ln fugacity 3
infinite number ot terms if 1.

#NAME? #NAME? -0.8972041105 #NAME? #NAME?


#NAME? #NAME? -0.8972049325 #NAME? #NAME?

delta ln fugacity 8.22051683058E-07 #NAME? #NAME?

delta^2 6.75768969619E-13 #NAME? #NAME?

Sum (delta^2) 3.452274E-10


ln fugacity 4 ln fugacity 5 ln fugacity 6 ln fugacity 7

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


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

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

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


Physical properties from the Peng-Robinson equation of state with quadratic mixing rule fo

Reference:
Reid, R.C., J.M. Prausnitz, and B.E. Poling
The Properties of Gases and Liquids
4th ed., McGraw-Hill, New York, 1987.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Comments about this model

(1) This version of the Peng-Robinson EOS is identical to the original model with exception of the b parameter, which is given b

c
bi b j
c
b xi x j 1 ij
i 1 j 1 2

Flash separation of a binary mixture of CO2 and a pseudocomponent that represents clove oil.

Reference
Souza, A.T., M.L. Corazza, L. Cardozo-Filho, R. Guirardello, and M.A.A. Meireles
Phase Equilibrium Measurements for the System Clove (Eugenia caryophyllus) Oil + CO2
J. Chem. Eng. Data 2004, 49, 352-356

R 83.14
T(K) 318.2
P (bar) 100

CO2 Clove oil


Tc(K) 304.21 763.2
Pc(bar) 73.83 30.97
omega 0.2236 0.6286
kij 0 0.02945
0.02945 0
lij 0 -0.04411
-0.04411 0

theta CO2 theta Clove oil


Liquid 0.1867947007 0.9776214605
Vapor 0.8132052993 0.0223785395
Moles CO2 Moles Clove oil Total
Global 0.93 0.07 1
Liquid 0.1737190717 0.0684335022 0.242152574
Vapor 0.7562809283 0.0015664978 0.757847426

ln (fugacity coefficients) ln (mole fraction)+ln phi


mole fraction CO2 mole fraction Clove oil CO2 Clove oil CO2
Liquid 0.717395107 0.282604893 #NAME? #NAME? -0.521421463
Vapor 0.9979329642 0.0020670358 #NAME? #NAME? -0.521421483

Gliquid -1.116685392
Gvapor -0.417829482

Gtotal -1.5345149
quadratic mixing rule for the b-parameter

he b parameter, which is given by:

represents clove oil.

yllus) Oil + CO2


(mole fraction)+ln phi
Clove oil
-14.99418423
-14.99418619

Minimize this cell by changing the blue cells


Physical properties from an extended Peng-Robinson equation of state for confined fluids

Reference:
Unpublished work by Travalloni, L., F.W. Tavares, M. Castier, and S.I. Sandler

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Nitrogen adsorption in activated Carbon JX101

R (J/(mol.K)) 8.314
T(K) 298

Nitrogen
Tc(K) 126.2
Pc(Pa) 3.39E+06
omega 0.039
kij 0

Adsorbent JX101 Data from: Qin Wu, Li Zhou, Jiaquan Wu, and Yaping Zhou, J. Chem. Eng. Data 2005, 50
Specific pore volume (mL/g) 0.52
Specific pore volume (m3/kg) 0.00052

Experimental data
P bulk (bar) Adsorbed amount (mmol/g) x
0.18 0.04 1
Confined fluid 0.39 0.0942 1
0.57 0.1566 1
0.84 0.2278 1
1.095 0.2964 1
1.47 0.388 1
1.845 0.4729 1
2.19 0.5437 1
2.52 0.6141 1
2.88 0.6897 1
3.27 0.7661 1
3.69 0.8565 1
4.35 0.9705 1
4.965 1.079 1
5.565 1.176 1
6.135 1.2655 1
6.69 1.3457 1
7.35 1.4329 1
8.04 1.5298 1
8.955 1.6365 1
9.81 1.735 1

2.0

1.8

1.6

Adsorbed amount (mol/kg)


1.4

1.2

1.0

0.8

0.6

0.4

0.2

0.0
0 0.1
of state for confined fluids

em specifications.

of calculations.

g Zhou, J. Chem. Eng. Data 2005, 50, 635-642

Unconfined fluid
P (Pa) Pore radius (m) delta/sigma Ep/k lnphiV
1.80E+04 100 0 0 -8.107416502881E-05
3.90E+04 100 0 0 -0.0001755171
5.70E+04 100 0 0 -0.0002563451
8.40E+04 100 0 0 -0.0003773742
1.10E+05 100 0 0 -0.0004914448
1.47E+05 100 0 0 -0.0006587818
1.85E+05 100 0 0 -0.000825626
2.19E+05 100 0 0 -0.0009786876
2.52E+05 100 0 0 -0.0011247043
2.88E+05 100 0 0 -0.0012835603
3.27E+05 100 0 0 -0.0014551423
3.69E+05 100 0 0 -0.0016393276
4.35E+05 100 0 0 -0.0019275147
4.97E+05 100 0 0 -0.0021946813
5.57E+05 100 0 0 -0.0024540574
6.14E+05 100 0 0 -0.0026992993
6.69E+05 100 0 0 -0.002936997
7.35E+05 100 0 0 -0.0032182644
8.04E+05 100 0 0 -0.0035106911
8.96E+05 100 0 0 -0.003895913
9.81E+05 100 0 0 -0.0042532365

2.0

1.8

1.6
Adsorbed amount (mol/kg)

1.4

1.2

1.0

0.8

0.6

0.4

0.2

0.0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Pressure (MPa)
Use Solver to zero this cell by changing P of the confined fluid

Confined fluid
ln fug = ln phi + ln P x P (Pa) Pore radius (m)
9.79805 1 2.42E+05 6.93E-10
10.57114 1 5.20E+05 6.93E-10
10.95055 1 7.56E+05 6.93E-10
11.33819 1 1.10E+06 6.93E-10
11.60319 1 1.42E+06 6.93E-10
11.89753 1 1.89E+06 6.93E-10
12.12458 1 2.34E+06 6.93E-10
12.29585 1 2.75E+06 6.93E-10
12.43606 1 3.13E+06 6.93E-10
12.56943 1 3.54E+06 6.93E-10
12.69626 1 3.98E+06 6.93E-10
12.81691 1 4.43E+06 6.93E-10
12.98117 1 5.13E+06 6.93E-10
13.11314 1 5.77E+06 6.93E-10
13.22697 1 6.37E+06 6.93E-10
13.32424 1 6.93E+06 6.93E-10
13.41060 1 7.45E+06 6.93E-10
13.50441 1 8.07E+06 6.93E-10
13.59384 1 8.70E+06 6.93E-10
13.70124 1 9.50E+06 6.93E-10
13.79207 1 1.02E+07 6.93E-10

Calculated
Experimental

0.6 0.7 0.8 0.9 1

MPa)
y changing P of the confined fluid

delta/sigma Ep/k lnphiV ln fug = ln phi + ln P


0.40292 923.261 -2.5988703239 9.79805
0.40292 923.261 -2.5911446412 10.57114
0.40292 923.261 -2.5846593417 10.95055
0.40292 923.261 -2.5751554604 11.33819
0.40292 923.261 -2.566412957 11.60319
0.40292 923.261 -2.5539407055 11.89753
0.40292 923.261 -2.5418934826 12.12458
0.40292 923.261 -2.5311575539 12.29585
0.40292 923.261 -2.5211787529 12.43606
0.40292 923.261 -2.5105956564 12.56943
0.40292 923.261 -2.4994642144 12.69626
0.40292 923.261 -2.4878384368 12.81691
0.40292 923.261 -2.4702672674 12.98117
0.40292 923.261 -2.4545950662 13.11314
0.40292 923.261 -2.4398972587 13.22697
0.40292 923.261 -2.4264312479 13.32424
0.40292 923.261 -2.4137493165 13.41060
0.40292 923.261 -2.3991784605 13.50441
0.40292 923.261 -2.3844927549 13.59384
0.40292 923.261 -2.3658071141 13.70124
0.40292 923.261 -2.3490876947 13.79207
Equilibrium condition Confined fluid
delta (ln fug) Molar volume (m3/mol) Molar density (mol/m3)
0.00000E+00 0.0103046422 97.0436410855
0.00000E+00 0.0048297439 207.0503159158
0.00000E+00 0.0033472481 298.7528747703
0.00000E+00 0.0023141647 432.1213581804
0.00000E+00 0.001805768 553.7809862035
0.00000E+00 0.0013779276 725.7275530752
0.00000E+00 0.0011234638 890.1043113701
0.00000E+00 0.0009659508 1035.2494111797
0.00000E+00 0.0008553722 1169.0817110158
0.00000E+00 0.0007633954 1309.9371383709
0.00000E+00 0.0006863681 1456.9442106217
0.00000E+00 0.0006213945 1609.283642539
0.00000E+00 0.0005442658 1837.3375711304
0.00000E+00 0.0004905201 2038.652280799
0.00000E+00 0.0004492829 2225.7689518187
0.00000E+00 0.0004173877 2395.8541488598
0.00000E+00 0.0003914024 2554.9154464735
0.00000E+00 0.0003654447 2736.3924895087
0.00000E+00 0.0003427019 2917.9876330619
0.00000E+00 0.0003177384 3147.243302651
6.24819E-08 0.0002984397 3350.7610138691
Calc Adsorbed amount (mol/kg) Exper. Adsorbed amount (mol/kg) Deviation^2 (mol/kg)^2
0.05046 0.04 1.09468E-04
0.10767 0.0942 1.81338E-04
0.15535 0.1566 1.55877E-06
0.22470 0.2278 9.59075E-06
0.28797 0.2964 7.11305E-05
0.37738 0.388 1.12820E-04
0.46285 0.4729 1.00917E-04
0.53833 0.5437 2.88402E-05
0.60792 0.6141 3.81616E-05
0.68117 0.6897 7.28068E-05
0.75761 0.7661 7.20633E-05
0.83683 0.8565 3.87007E-04
0.95542 0.9705 2.27541E-04
1.06010 1.079 3.57241E-04
1.15740 1.176 3.45965E-04
1.24584 1.2655 3.86352E-04
1.32856 1.3457 2.93916E-04
1.42292 1.4329 9.95187E-05
1.51735 1.5298 1.54914E-04
1.63657 1.6365 4.42456E-09
1.74240 1.735 5.46968E-05

Total (deviation)^2 3.10585E-03


Unconfined fluid
P (MPa)
0.018
0.039
0.057
0.084
0.1095
0.147
0.1845
0.219
0.252
0.288
0.327
0.369
0.435
0.4965
0.5565
0.6135
0.669
0.735
0.804
0.8955
0.981
Physical properties from the Patel-Teja-Valderrama equation of state

Reference:
J. O. Valderrama, Ind. Eng. Chem. Res. 42 (2003) 16031618.

Color convention: Cells such as this one are problem specificatio

Other numeric cells are results of calculations.

Normal boiling temperature of n-hexane (i.e., at a pressure of 1 atm = 1.0132 bar)

R 83.14
T(K) 300 Compute using Solver

n-hexane DIPPR data


Tc(K) 507.6
Pc(bar) 3.03E+01
omega 0.301261
Zc 0.266
kij 0

x Pespec
1 1.0132

Example of sound speed calculation

Use SI units throught the calculation


Nitrogen DIPPR data
Tc(K) 126.2
Pc(Pa) 3.40E+06
omega 0.0377215
Zc 0.289
kij 0
Temperature (K)
Molar mass (g/mol)
Molar mass (kg/mol)
Ideal gas cp coefficients

R (SI)
x Pespec (bar)
1 1.0132
1 1.5132
1 2.0132
1 2.5132
1 3.0132
1 3.5132
1 4.0132
1 4.5132
1 5.0132
1 5.5132
1 6.0132
1 6.5132
1 7.0132
1 7.5132
1 8.0132
1 8.5132
1 9.0132
1 9.5132
1 10.0132
1 10.5132
1 11.0132
1 11.5132
1 12.0132
1 12.5132
1 13.0132
1 13.5132
1 14.0132
1 14.5132
1 15.0132
1 15.5132
1 16.0132
1 16.5132
1 17.0132
1 17.5132
1 18.0132
1 18.5132
1 19.0132
1 19.5132
1 20.0132
1 20.5132
1 21.0132
1 21.5132
1 22.0132
1 22.5132
1 23.0132
1 23.5132
1 24.0132
1 24.5132
1 25.0132
1 25.5132

Effect of external fields (gravitational and centrifugal) on phase equilibrium.

When a substance (or mixture) is present in a large system with depths of hundreds of meters the effect of position
This is formulated by modifying the formula for the fugacity (ln fug (CO2)) in the table below) to account for the effec

R (bar.cm3/(mol.K)) 83.14
T(K) 333

R (for gravitational and centrifugal fields) 8314


Gravity acceleration (m/s^2) 9.81
Radial speed (radians/s) 0

CO2 DIPPR data


Molar mass 44
Tc(K) 304.21
Pc(bar) 73.83
omega 0.223621
Zc 0.274
kij 0

The CO2 pressure is specified at level 0 m. Find its pressure 200 m below.

Level (m) Radial position (m) x(CO2)


0 0 1
-200 0 1

Isenthalpic expansion

The expansion of a fluid stream (pure substance or mixture) from a high pressure to a low pressure condition in a pe

Consider the expansion of a Nitrogen stream, initially at 250 K and 100 bar, to a final condition at 10 bar, and determ

Use SI units throught the calculation


Nitrogen
Nitrogen DIPPR data
Tc(K) 126.2
Pc(Pa) 3.40E+06
omega 0.0377215
Zc 0.289
kij 0

(T^0) coefficient (T^1) coefficient


Ideal gas cp coefficients (cp in J/(mol.K)) 31.15 -1.36E-02
R (J/(mol.K)) 8.314

Reference T (K) for enthalpy calculations 300

Mole fraction Pressure (Pascal)


Before the valve 1 10000000
After the valve 1 1000000

Isentropic expansion

The expansion of a fluid stream (pure substance or mixture) from a high pressure to a low pressure condition in a pe

Consider the expansion of a Nitrogen stream, initially at 250 K and 100 bar, to a final condition at 70 bar, and determ

Use SI units throught the calculation


Nitrogen DIPPR data
Tc(K) 126.2
Pc(Pa) 3.40E+06
omega 0.0377215
Zc 0.289
kij 0

(T^0) coefficient (T^1) coefficient


Ideal gas cp coefficients (cp in J/(mol.K)) 31.15 -1.36E-02
R (J/(mol.K)) 8.314

Reference T (K) for entropy calculations 300


Reference P (Pascal) for entropy calculations 100000

Mole fraction Pressure (Pascal)


Before the equipment 1 10000000
After the equipment 1 7000000
Observe that the final temperatures of the isenthalpic and isentropic expansions are similar (about 226 K),
even though the specified final pressures are very different. Try to undestand this by looking at a PH diagram.
ne are problem specifications.

are results of calculations.

Computed with Computed with Computed with


function function spreadsheet
ptvnphil ptvlnphiv function.
lnphiL lnphiV deltalnphi
#NAME? #NAME? #NAME? Use Solver to zero this cell by changing T.

300
28.013
0.028013
31.15 -1.36E-02 2.68E-05

8.314
Spreadsheet Spreadsheet These 4 columns were calculated with array function svsoundspeedv.
formula formula
Pespec(Pa) cpig (J/(mol.K)) rho (mol/m3) dpdrho (Pa/(mol/m3)) cprr (K)
101320 2.95E+01 #NAME? #NAME? #NAME?
151320 2.95E+01 #NAME? #NAME? #NAME?
201320 2.95E+01 #NAME? #NAME? #NAME?
251320 2.95E+01 #NAME? #NAME? #NAME?
301320 2.95E+01 #NAME? #NAME? #NAME?
351320 2.95E+01 #NAME? #NAME? #NAME?
401320 2.95E+01 #NAME? #NAME? #NAME?
451320 2.95E+01 #NAME? #NAME? #NAME?
501320 2.95E+01 #NAME? #NAME? #NAME?
551320 2.95E+01 #NAME? #NAME? #NAME?
601320 2.95E+01 #NAME? #NAME? #NAME?
651320 2.95E+01 #NAME? #NAME? #NAME?
701320 2.95E+01 #NAME? #NAME? #NAME?
751320 2.95E+01 #NAME? #NAME? #NAME?
801320 2.95E+01 #NAME? #NAME? #NAME?
851320 2.95E+01 #NAME? #NAME? #NAME?
901320 2.95E+01 #NAME? #NAME? #NAME?
951320 2.95E+01 #NAME? #NAME? #NAME?
1001320 2.95E+01 #NAME? #NAME? #NAME?
1051320 2.95E+01 #NAME? #NAME? #NAME?
1101320 2.95E+01 #NAME? #NAME? #NAME?
1151320 2.95E+01 #NAME? #NAME? #NAME?
1201320 2.95E+01 #NAME? #NAME? #NAME?
1251320 2.95E+01 #NAME? #NAME? #NAME?
1301320 2.95E+01 #NAME? #NAME? #NAME?
1351320 2.95E+01 #NAME? #NAME? #NAME?
1401320 2.95E+01 #NAME? #NAME? #NAME?
1451320 2.95E+01 #NAME? #NAME? #NAME?
1501320 2.95E+01 #NAME? #NAME? #NAME?
1551320 2.95E+01 #NAME? #NAME? #NAME?
1601320 2.95E+01 #NAME? #NAME? #NAME?
1651320 2.95E+01 #NAME? #NAME? #NAME?
1701320 2.95E+01 #NAME? #NAME? #NAME?
1751320 2.95E+01 #NAME? #NAME? #NAME?
1801320 2.95E+01 #NAME? #NAME? #NAME?
1851320 2.95E+01 #NAME? #NAME? #NAME?
1901320 2.95E+01 #NAME? #NAME? #NAME?
1951320 2.95E+01 #NAME? #NAME? #NAME?
2001320 2.95E+01 #NAME? #NAME? #NAME?
2051320 2.95E+01 #NAME? #NAME? #NAME?
2101320 2.95E+01 #NAME? #NAME? #NAME?
2151320 2.95E+01 #NAME? #NAME? #NAME?
2201320 2.95E+01 #NAME? #NAME? #NAME?
2251320 2.95E+01 #NAME? #NAME? #NAME?
2301320 2.95E+01 #NAME? #NAME? #NAME?
2351320 2.95E+01 #NAME? #NAME? #NAME?
2401320 2.95E+01 #NAME? #NAME? #NAME?
2451320 2.95E+01 #NAME? #NAME? #NAME?
2501320 2.95E+01 #NAME? #NAME? #NAME?
2551320 2.95E+01 #NAME? #NAME? #NAME?

ters the effect of position on properties is relevant.


w) to account for the effect of the gravitational field.

Function Spreadsheet Spreadsheet


ptvlnphiv formula formula
Pespec (bar) lnphiv (CO2) ln fug (CO2) Function This function is the difference be
8 #NAME? #NAME?
8 #NAME? #NAME? #NAME? Use Solver to zero this cell
Compute using
Solver

pressure condition in a perfectly insulated valve (throtlting) is an isenthalpic process.

ition at 10 bar, and determine its final temperature.


(T^2) coefficient (T^3) coefficient
2.68E-05 -1.17E-09

Spreadsheet These 4 columns were calculated with array function ptvresv.


formula
Temperature (K) Ideal gas h (J/mol) gr/(RT) hr/(RT) sr/R
250 -1471.30 #NAME? #NAME? #NAME?
250.00 -1471.30 #NAME? #NAME? #NAME?
Compute using
Solver

pressure condition in a perfectly insulated reversible turbine is an isentropic process.

ition at 70 bar, and determine its final temperature.

(T^2) coefficient (T^3) coefficient


2.68E-05 -1.17E-09

Spreadsheet These 4 columns were calculated with array function ptvresv.


formula
Temperature (K) Ideal gas s (J/(mol.K)) gr/(RT) hr/(RT) sr/R
250 -4.37E+01 #NAME? #NAME? #NAME?
250.00 -4.07E+01 #NAME? #NAME? #NAME?
Compute using
Solver

r (about 226 K),


ng at a PH diagram.
changing T.

-1.17E-09
svsoundspeedv. These columns were calculated using spreadsheet formulas

dpdt (Pa/K) cpresidual (J/(mol.K)) cp (J/(mol.K)) cv (J/(mol.K)) gama=cp/cv


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

nction is the difference between ln fug values at two different positions.

lver to zero this cell


Spreadsheet Spreadsheet
formula formula
cpr/R Residual h (J/mol) Molar h (J/mol)
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?

Delta h (J/mol) #NAME? Use Solver to zero this cell

The flowrates before and after the valve are equal (steady-state assumption).
Therefore, if the enthalpies are equal, the molar enthalpies must be equal.

Hint: use Solver to zero the Delta h cell by


changing the temperature after the valve.

Spreadsheet Spreadsheet
formula formula
cpr/R Residual s (J/(mol.K))Molar s (J/(mol.K))
#NAME? #NAME? #NAME?
#NAME? #NAME? #NAME?
Delta s (J/(mol.K)) #NAME? Use Solver to zero this cell

The flowrates before and after the valve are equal (steady-state assumption).

Hint: use Solver to zero the Delta s cell by


changing the temperature after the valve.

Therefore, if the entropies are equal, the molar entropies must be equal.
sound speed (m/s)
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
#NAME?
e assumption).
ust be equal.
e assumption).

s must be equal.
delta^2 0 0

Sum (delta^2) 0
0 0 0 0 0
Physical properties from the Stryjek-Vera equation of state

Reference:
Stryjek, R. and Vera, J.H.,
PRSV: An Improved Peng-Robinson Equation of State for Pure Compounds and Mixtures
Can. J. Chem. Engng. (1986) 64, 323-333.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Normal boiling temperature of n-hexane (i.e., at a pressure of 1 atm = 1.0132 bar)

R ((bar.cm3/(mol.K)) 83.14
T(K) 300 Compute using Solver

n-hexane
Tc(K) 507.5
Pc(bar) 30.1236
omega 0.30075
K1 0.05104
kij 0

Computed with Computed with


function function
svlnphil svlnphiv
x P (bar) lnphiL lnphiV
1 1.0132 -1.5603227559 -0.0593922395

Example of sound speed calculation

Use SI units throught the calculation


Nitrogen
Tc(K) 126.2
Pc(Pa) 3.39E+06
omega 0.039
kij 0
Temperature (K) 300
Molar mass (g/mol) 28.013
Molar mass (kg/mol) 0.028013
Ideal gas cp coefficients

R (SI) 8.314
Spreadsheet Spreadsheet
formula formula
x Pespec (bar) Pespec(Pa) cpig (J/(mol.K))
1 1.0132 101320 2.95E+01
1 1.5132 151320 2.95E+01
1 2.0132 201320 2.95E+01
1 2.5132 251320 2.95E+01
1 3.0132 301320 2.95E+01
1 3.5132 351320 2.95E+01
1 4.0132 401320 2.95E+01
1 4.5132 451320 2.95E+01
1 5.0132 501320 2.95E+01
1 5.5132 551320 2.95E+01
1 6.0132 601320 2.95E+01
1 6.5132 651320 2.95E+01
1 7.0132 701320 2.95E+01
1 7.5132 751320 2.95E+01
1 8.0132 801320 2.95E+01
1 8.5132 851320 2.95E+01
1 9.0132 901320 2.95E+01
1 9.5132 951320 2.95E+01
1 10.0132 1001320 2.95E+01
1 10.5132 1051320 2.95E+01
1 11.0132 1101320 2.95E+01
1 11.5132 1151320 2.95E+01
1 12.0132 1201320 2.95E+01
1 12.5132 1251320 2.95E+01
1 13.0132 1301320 2.95E+01
1 13.5132 1351320 2.95E+01
1 14.0132 1401320 2.95E+01
1 14.5132 1451320 2.95E+01
1 15.0132 1501320 2.95E+01
1 15.5132 1551320 2.95E+01
1 16.0132 1601320 2.95E+01
1 16.5132 1651320 2.95E+01
1 17.0132 1701320 2.95E+01
1 17.5132 1751320 2.95E+01
1 18.0132 1801320 2.95E+01
1 18.5132 1851320 2.95E+01
1 19.0132 1901320 2.95E+01
1 19.5132 1951320 2.95E+01
1 20.0132 2001320 2.95E+01
1 20.5132 2051320 2.95E+01
1 21.0132 2101320 2.95E+01
1 21.5132 2151320 2.95E+01
1 22.0132 2201320 2.95E+01
1 22.5132 2251320 2.95E+01
1 23.0132 2301320 2.95E+01
1 23.5132 2351320 2.95E+01
1 24.0132 2401320 2.95E+01
1 24.5132 2451320 2.95E+01
1 25.0132 2501320 2.95E+01
1 25.5132 2551320 2.95E+01
Computed with
spreadsheet
function.
deltalnphi
-1.5009305164 Use Solver to zero this cell by changing T.

31.15 -1.36E-02 2.68E-05 -1.17E-09


These 4 columns were calculated with array function svsoundspeedv. These columns were calculated using

rho (mol/m3) dpdrho (Pa/(mol/m3)) cprr (K) dpdt (Pa/K) cpresidual (J/(mol.K))
#NAME? #NAME? #NAME? #NAME? 0.0538038441
#NAME? #NAME? #NAME? #NAME? 0.0803364153
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME?
mns were calculated using spreadsheet formulas

cp (J/(mol.K)) cv (J/(mol.K)) gama=cp/cv sound speed (m/s)


29.5132678441 #NAME? 1.395084412 352.2906421553
29.5398004153 #NAME? 1.3960223205 352.3363347104
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
Physical properties from the Predictive SRK Equation of State

Reference:
Horstmann, S., A. Jabloniec, J. Krafczyk, K. Fischer, J. Gmehling
PSRK group contribution equation of state: comprehensive revision and extension IV: including critical con
Fluid Phase Equilibria 227 (2005) 157-164.

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Vapor-liquid equilibrium of the mixture HCl+Cl2

HCl Cl2
Tc (K) 324.6 417
Pc (bar) 83.0865 77.007
c1 0.66635 0.55192
c2 0.35497 0.01934
c3 -1.3766 0.59414
HCl Cl2
r 1.056 1.53
q 1.256 1.44
HCl 0 2.0069
a Cl2 132 0
HCl 0 0
b Cl2 0 0
HCl 0 0
c Cl2 0 0
HCl 1 0
Cl2 0 1

R ((bar.cm3)/(mol.K)) 83.14
T (K) 273.15

Calculated as
(1-x1) with
spreadsheet These 2 columns were calculated with
formula array function psrklnphil.
x1 x2 ln phi 1 l ln phi 2 l
0.02 0.98 #NAME? #NAME?
0.05 0.95 #NAME? #NAME?
0.1 0.9 #NAME? #NAME?
0.15 0.85 #NAME? #NAME?
0.2 0.8 #NAME? #NAME?
0.25 0.75 #NAME? #NAME?
0.3 0.7 #NAME? #NAME?
0.35 0.65 #NAME? #NAME?
0.4 0.6 #NAME? #NAME?
0.45 0.55 #NAME? #NAME?
0.5 0.5 #NAME? #NAME?
0.55 0.45 #NAME? #NAME?
0.6 0.4 #NAME? #NAME?
0.65 0.35 #NAME? #NAME?
0.7 0.3 #NAME? #NAME?
0.75 0.25 #NAME? #NAME?
0.8 0.2 #NAME? #NAME?
0.85 0.15 #NAME? #NAME?
0.9 0.1 #NAME? #NAME?
0.95 0.05 #NAME? #NAME?
0.99 0.01 #NAME? #NAME?

HCl+Cl2 at 273.15K

Pressure (MPa)
3

2.5

1.5

0.5

0
0 0.2 0.4 0.6

Mole fracton of HCl

Vapor-liquid equilibrium of the mixture HCN+H2O

HCN H2O
Tc (K) 456.8 647.3
Pc (bar) 53.9049 220.48321
c1 1.62716 1.0783
c2 -5.00731 -0.58321
c3 10.34189 0.54619
HCN H2O
r 1.2 0.92
q 1.19 1.4
HCN 0 79.524
a H2O 261.73 0
HCN 0 0
b H2O 0 0
HCN 0 0
c H2O 0 0
HCN 1 0
H2O 0 1
R ((bar.cm3)/(mol.K)) 83.14
T (K) 291.15

Calculated as
(1-x1) with
spreadsheet These 2 columns were calculated with
formula array function psrklnphil.
x1 x2 ln phi 1 l ln phi 2 l
0.01 0.99 #NAME? #NAME?
0.05 0.95 #NAME? #NAME?
0.1 0.9 #NAME? #NAME?
0.15 0.85 #NAME? #NAME?
0.2 0.8 #NAME? #NAME?
0.25 0.75 #NAME? #NAME?
0.3 0.7 #NAME? #NAME?
0.35 0.65 #NAME? #NAME?
0.4 0.6 #NAME? #NAME?
0.45 0.55 #NAME? #NAME?
0.5 0.5 #NAME? #NAME?
0.55 0.45 #NAME? #NAME?
0.6 0.4 #NAME? #NAME?
0.65 0.35 #NAME? #NAME?
0.7 0.3 #NAME? #NAME?
0.75 0.25 #NAME? #NAME?
0.8 0.2 #NAME? #NAME?
0.85 0.15 #NAME? #NAME?
0.9 0.1 #NAME? #NAME?
0.95 0.05 #NAME? #NAME?
0.99 0.01 #NAME? #NAME?

HCN+H2O at 291.15K
Pressure (kPa)

90
80
70
60
50
40
30
20
10
0
0 0.2 0.4 0.6 0.8

Mole fracton of HCN


Vapor-liquid equilibrium and residual properties of the mixture n-pentane+benzene

n-pentane benzene
Tc (K) 469.7 562.1
Pc (bar) 33.69056 48.93997
c1 0.92983 0.8356
c2 -0.57909 -0.375
c3 1.1375 0.9715
CH3 CH2 ACH
r 0.9011 0.6744 0.5313
q 0.848 0.54 0.4
CH3 0 0 61.13
a CH2 0 0 61.13
ACH -11.12 -11.12 0
CH3 0 0 0
b CH2 0 0 0
ACH 0 0 0
CH3 0 0 0
c CH2 0 0 0
ACH 0 0 0
n-pentane 2 3 0
benzene 0 0 6

R ((bar.cm3)/(mol.K)) 83.14 P (bar)


T (K) 353.15

Calculated as
(1-x1) with
spreadsheet These 2 columns were calculated with
formula array function psrklnphil.
x1 x2 ln phi 1 l ln phi 2 l
0.71 0.29 #NAME? #NAME?

Chemical Equilibrium

This is an advanced example with four simultaneous chemical reactions, originally discussed in th
The four reactions are:

H2 C2H4 C3H6
Tc (K) 33.2 282.35 365
Pc (bar) 12.9696 50.41628 46.2042
c1 0.1252 0.61252 0.7091
c2 0 0 -0.10396
c3 0 0 0.14989
CH3 CH2 CH2=CH
r 0.9011 0.6744 1.3454
q 0.848 0.54 1.176
CH3 0 0 86.02
CH2 0 0 86.02
a CH2=CH -35.36 -35.36 0
CH2=CH2 -35.36 -35.36 0
CH4 68.141 68.141 18.78
H2 315.96 315.96 399.44
CH3 0 0 0
CH2 0 0 0
b CH2=CH 0 0 0
CH2=CH2 0 0 0
CH4 -0.7386 -0.7386 0
H2 -0.4563 -0.4563 -0.5806
CH3 0 0 0
CH2 0 0 0
c CH2=CH 0 0 0
CH2=CH2 0 0 0
CH4 0 0 0
H2 -0.00156 -0.00156 0
H2 0 0 0
C2H4 0 0 0
Description C3H6 1 0 1
by groups CH4 0 0 0
C2H6 2 0 0
C3H8 2 1 0

Parameters of the chemical reaction equilibrium constants were taken from the work Carrero-Mantilla and L

T (K) 700

Equilibrium constants

A B*10^3 C*10^6 D
Reaction 1' 0.131000 -0.624000 0.123300 0.000000
Reaction 2' -3.673000 2.828500 -0.318167 -4150.000000
Reaction 3' -2.5660 2.947000 -0.400333 0.000000
Reaction 4' -1.913000 2.655000 -0.378000 0.000000

Stoichiometric coefficients

H2 C2H4 C3H6 CH4


Reaction 1' 0 -1 1 0
Reaction 2' -1 0 -1 0
Reaction 3' 0 -1 0 -2
Reaction 4' 0 -1 0 -1

R (bar.cm3/(mol.K)) 83.14
P (bar) 50

Numerical solution

The initial amounts are specified. The unknowns are the extents of reaction.

For a given estimate of the extents of reaction, the amounts of all components can be computed, and then, their mo

If the extents of reaction are not correct, the chemical equilibrium equations will not be satisfied and there will be a r

Excel Solver was used to minimize this residue by simultaneously changing the values of the four extents of reaction

This is a difficult example because the calculations are sensitive to the initial values used for the extents of reaction.
These initial values should be carefully chosen in such a way that the component amounts and mole fractions are al

The extents of reaction provided in this file are good initial estimates for the problem conditions and will lea
You may try other initial values to observe it is not easy to provide initial values in this problem.

Initial amounts
H2 C2H4 C3H6 CH4
1 2 2 0
Equilibrium mole fractions
H2 C2H4 C3H6 CH4
2.55753821600315E-06 0.0511507643 0.6930954141 0.1790276751

Fugacities
H2 C2H4 C3H6 CH4
#NAME? #NAME? #NAME? #NAME?

Chemical Equilibrium equations


Reaction 1' Reaction 2' Reaction 3' Reaction 4'
-0.3913426311 0.5827264941 -0.2891092317 -0.2677299136
V: including critical constants and alpha-function parameters for 1000 components

Calculated as
(1-y2) with
These columns were calculated with spreadsheet The values in these two columns
spreadsheet formulas. formula were computed using Excel Solver.
Ln(x1)+ ln phi1 l Ln(x2)+ ln phi2 l y1 y2 P(bar)
#NAME? #NAME? 0.1815864913 0.8184135087 4.6157230032
#NAME? #NAME? 0.352012917 0.647987083 5.7627795809
#NAME? #NAME? 0.5128624169 0.4871375831 7.4984096134
#NAME? #NAME? 0.6059511509 0.3940488491 9.0450857865
#NAME? #NAME? 0.6674625011 0.3325374989 10.4350489534
#NAME? #NAME? 0.7118313132 0.2881686868 11.6964260313
#NAME? #NAME? 0.7459566681 0.2540433319 12.8536671753
#NAME? #NAME? 0.77356105 0.22643895 13.9280242799
#NAME? #NAME? 0.7968392431 0.2031607569 14.937999251
#NAME? #NAME? 0.8171781992 0.1828218008 15.8997465094
#NAME? #NAME? 0.8355062153 0.1644937847 16.8274268558
#NAME? #NAME? 0.8524766539 0.1475233461 17.733513849
#NAME? #NAME? 0.8685711384 0.1314288616 18.6290553279
#NAME? #NAME? 0.8841607717 0.1158392283 19.5238931929
#NAME? #NAME? 0.8995442238 0.1004557762 20.4268445495
#NAME? #NAME? 0.914972488 0.085027512 21.3458469818
#NAME? #NAME? 0.9306656738 0.0693343262 22.2880702505
#NAME? #NAME? 0.94682492 0.05317508 23.2599960864
#NAME? #NAME? 0.9636412757 0.0363587243 24.2674671062
#NAME? #NAME? 0.9813027078 0.0186972922 25.3157051337
#NAME? #NAME? 0.996168283 0.003831717 26.1867534589

HCl+Cl2 at 273.15K

Bubble line
Dew line

0.6 0.8 1

e fracton of HCl
Calculated as
(1-y2) with
These columns were calculated with spreadsheet Computed using These 2 columns were calculated with
spreadsheet formulas. formula. Excel Solver. array function psrklnphiv.
Ln(x1)+ ln phi1 l Ln(x2)+ ln phi2 l y1 y2 ln phi 1 v
#NAME? #NAME? 0.7280824512 0.2719175488 #NAME?
#NAME? #NAME? 0.9198676064 0.0801323936 #NAME?
#NAME? #NAME? 0.9504081555 0.0495918445 #NAME?
#NAME? #NAME? 0.9604572116 0.0395427884 #NAME?
#NAME? #NAME? 0.9651329703 0.0348670297 #NAME?
#NAME? #NAME? 0.9676416693 0.0323583307 #NAME?
#NAME? #NAME? 0.9690914183 0.0309085817 #NAME?
#NAME? #NAME? 0.9699789274 0.0300210726 #NAME?
#NAME? #NAME? 0.970571543 0.029428457 #NAME?
#NAME? #NAME? 0.9710372107 0.0289627893 #NAME?
#NAME? #NAME? 0.9714977162 0.0285022838 #NAME?
#NAME? #NAME? 0.972053883 0.027946117 #NAME?
#NAME? #NAME? 0.9727991976 0.0272008024 #NAME?
#NAME? #NAME? 0.9738283176 0.0261716824 #NAME?
#NAME? #NAME? 0.9752433417 0.0247566583 #NAME?
#NAME? #NAME? 0.9771593133 0.0228406867 #NAME?
#NAME? #NAME? 0.9797098696 0.0202901304 #NAME?
#NAME? #NAME? 0.9830537619 0.0169462381 #NAME?
#NAME? #NAME? 0.9873829974 0.0126170026 #NAME?
#NAME? #NAME? 0.9929335527 0.0070664473 #NAME?
#NAME? #NAME? 0.9984488458 0.0015511542 #NAME?

HCN+H2O at 291.15K

Bubble line
Dew line

0.6 0.8 1

cton of HCN
e+benzene

3.0396186642 Computed using


Excel Solver.

These 4 columns were calculated with array function psrkresl. These columns were calculated with
spreadsheet formulas.
gr/(RT) liquid hr/(RT) liquid sr/R liquid cpr/R liquid Ln(x1)+ ln phi1 l
#NAME? #NAME? #NAME? #NAME? -0.2188591531

Objective function: residue

inally discussed in the following reference:


CH4 C2H6 C3H8
190.6 305.4 369.95
46.00155 48.83865 42.45518
0.49258 0.68638 0.75108
0 -0.42475 -0.31941
0 0.72531 0.59617
CH2=CH2 CH4 H2
1.3564 1.1292 0.416
1.3098 1.124 0.571
86.02 -39.101 613.3
86.02 -39.101 613.3
0 38.602 585
0 38.602 585
18.78 0 253.92
399.44 128.55 0
0 0.8459 -2.5418
0 0.8459 -2.5418
0 0 -0.8727
0 0 -0.8727
0 0 0
-0.5806 0 0
0 0 0.006638
0 0 0.006638
0 0 0
0 0 0
0 0 0
0 0 0
0 0 1
1 0 0
0 0 0
0 1 0
0 0 0
0 0 0

k Carrero-Mantilla and Llano Restrepo (2006)

E*10^(-3) F ln K
1.426171 0.220200 2.7393956667
14.127914 7.665200 5.6013949973
8.028224 -0.543700 -4.0181438811
9.588485 -4.958900 -2.1200009667

C2H6 C3H8
1 -1
0 1
2 0
0 1

puted, and then, their mole fractions, fugacity coefficients, and fugacities.

sfied and there will be a residue.

he four extents of reaction.

or the extents of reaction.


and mole fractions are all positive.

m conditions and will lead to convergence when Solver is applied.


his problem.

Extents of reaction
C2H6 C3H8 csi 1 csi 2 csi 3
0 0 1.71 0.99999 -0.79
Fugacity coefficients
C2H6 C3H8 H2 C2H4 C3H6
0.0332479968 0.0434755921 #NAME? #NAME? #NAME?

C2H6 C3H8
#NAME? #NAME?

Residue
0.6479826763
These 2 columns were calculated with These columns were calculated with
array function psrklnphiv. spreadsheet formulas.
ln phi 1 v ln phi 2 v Ln(y1)+ ln phi1 v Ln(y2)+ ln phi2 v
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME?

Excellent agreement with the results of Horstmann et al. (2005).


columns were calculated with These columns were calculated with Computed using
nction psrklnphiv. spreadsheet formulas. Excel Solver.
ln phi 2 v Ln(y1)+ ln phi1 v Ln(y2)+ ln phi2 v P (bar)
#NAME? #NAME? #NAME? 0.0756726818
#NAME? #NAME? #NAME? 0.2487601073
#NAME? #NAME? #NAME? 0.3887115143
#NAME? #NAME? #NAME? 0.4744563146
#NAME? #NAME? #NAME? 0.5266844852
#NAME? #NAME? #NAME? 0.558227264
#NAME? #NAME? #NAME? 0.577159648
#NAME? #NAME? #NAME? 0.5886380668
#NAME? #NAME? #NAME? 0.5960041728
#NAME? #NAME? #NAME? 0.6014579535
#NAME? #NAME? #NAME? 0.6064746112
#NAME? #NAME? #NAME? 0.6120667381
#NAME? #NAME? #NAME? 0.61895169
#NAME? #NAME? #NAME? 0.6276600033
#NAME? #NAME? #NAME? 0.6386066007
#NAME? #NAME? #NAME? 0.6521381234
#NAME? #NAME? #NAME? 0.6685646187
#NAME? #NAME? #NAME? 0.6881806144
#NAME? #NAME? #NAME? 0.7112785036
#NAME? #NAME? #NAME? 0.7381556896
#NAME? #NAME? #NAME? 0.7625823848

Excellent agreement with the results of Horstmann et al. (2005).


Calculated as
(1-y1) with
olumns were calculated with Computed using spreadsheet These 2 columns were calculated with
heet formulas. Excel Solver. formula. array function psrklnphiv.
Ln(x2)+ ln phi2 l y1 y2 ln phi 1 v
-2.1070798931 0.8677828253 0.1322171747 #NAME?

1.552590592993E-12
Solver was used to
minimize this residue
by changing P and y1.
Equilibrium amounts
csi 4 H2 C2H4 C3H6
0.88 0.00001 0.2 2.71001
0
coefficients
CH4 C2H6 C3H8
#NAME? #NAME? #NAME?
Solver was used
to minimize this Unit conversion
residue by using
changing y2 spreadsheet
and P (bar). formula
residue P (Mpa)
#NAME? 0.4615723003
#NAME? 0.5762779581
#NAME? 0.7498409613
#NAME? 0.9045085787
#NAME? 1.0435048953
#NAME? 1.1696426031
#NAME? 1.2853667175
#NAME? 1.392802428
#NAME? 1.4937999251
#NAME? 1.5899746509
#NAME? 1.6827426856
#NAME? 1.7733513849
#NAME? 1.8629055328
#NAME? 1.9523893193
#NAME? 2.042684455
#NAME? 2.1345846982
#NAME? 2.2288070251
#NAME? 2.3259996086
#NAME? 2.4267467106
#NAME? 2.5315705134
#NAME? 2.6186753459

of Horstmann et al. (2005).


Solver was used
to minimize this Unit conversion
residue by using
changing y2 spreadsheet
and P (bar). formula
residue P (kPa)
#NAME? 7.5672681815
#NAME? 24.8760107251
#NAME? 38.8711514334
#NAME? 47.4456314556
#NAME? 52.6684485182
#NAME? 55.8227263976
#NAME? 57.7159648
#NAME? 58.8638066823
#NAME? 59.6004172783
#NAME? 60.1457953534
#NAME? 60.6474611189
#NAME? 61.2066738076
#NAME? 61.895168996
#NAME? 62.7660003305
#NAME? 63.860660067
#NAME? 65.2138123357
#NAME? 66.8564618727
#NAME? 68.8180614416
#NAME? 71.1278503629
#NAME? 73.8155689637
#NAME? 76.2582384803

of Horstmann et al. (2005).


umns were calculated with These 4 columns were calculated with array function psrkresv.
on psrklnphiv.
ln phi 2 v gr/(RT) vapor hr/(RT) vapor sr/R vapor cpr/R vapor
#NAME? #NAME? #NAME? #NAME? #NAME?
CH4 C2H6 C3H8 Total
0.7 0.13 0.16999 3.91001
These columns were calculated with
spreadsheet formulas.
Ln(y1)+ ln phi1 v Ln(y2)+ ln phi2 v
-0.2188602839 -2.1070793697
Physical properties from the electrolattice equation of state for ions of equal diameters

Reference:
Work in progress

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Vapor pressure of: water

vcell 5

sum q 1.742253
Fractional q 0.492302209 0.408785062
Vinf 5.290993373 4.393397011

Vinf (cm3/mol) 5.290993373 4.393397011

R (J/(mol.K)) 8.314

r 2.14949

Water
D-group alpha group
Vinf (m3/mol) 0.000005291 4.393397011E-06
Qa 0.857715 0.712207
B (Kelvin) D-group 700.671 700.671
alpha group 700.671 700.671
beta group 700.671 0
Na+ (group) 0 0
Cl- (group) 0 0
u00 (Kelvin) D -535.864 -535.864
alpha -535.864 -535.864
beta -535.864 -2625.69
Na+ (group) -277.068 -277.068
Cl- (group) -277.068 -277.068
Frequency water 1 1
Na+ ion 0 0
Cl-ion 0 0
Charge 0 0
Sigma (meters) 1 1
Dielectric coeff 1 -19.29050 0
Dielectric coeff 2 29814.5 0
Dielectric coeff 3 -0.019678 0
Dielectric coeff 4 0.00013189 0
Dielectric coeff 5 -0.0000003 0
T(K) P (Pa) H2O
373.3315654979 1.01E+05 1.00E+00
373.2004612477 1.01E+05 9.90E-01
372.4470440862 1.01E+05 9.80E-01
371.2170164273 1.01E+05 9.70E-01
369.5611148467 1.01E+05 9.60E-01

These are specifications


ate for ions of equal diameters

s one are problem specifications.

lls are results of calculations.

0.09891273
1.063059616

1.063059616 5 5

12.7 12.7

beta group Na+ (group) Cl- (group)


1.063059616E-06 0.0000635 0.0000635
0.172331 10.36 10.36
700.671 0 0
0 0 0
700.671 0 0
0 0 0
0 0 0
-535.864 -277.068 -277.068
-2625.69 -277.068 -277.068
-535.864 -277.068 -277.068
-277.068 -468.877 -468.877
-277.068 -468.877 -468.877
1 0 0
0 1 0
0 0 1
0 1 -1
1 2.536E-10 2.536E-10
0 0 0
0 0 0
0 0 0
0 0 0
0 0 0

x liquid
Na+ Cl- H2O
1.00E-04 1.00E-04 #NAME?
5.10E-03 5.10E-03 #NAME?
1.01E-02 1.01E-02 #NAME?
1.51E-02 1.51E-02 #NAME?
2.01E-02 2.01E-02 #NAME?
???????

???????

red: for now just arbitrary values

Yellow: always zero

Green: always non-zero, any value

ln fi y vapor
Na+ Cl- H2O Na+ Cl- H2O
#NAME? #NAME? 1.00E+00 1.00E-20 1.00E-20 #NAME?
#NAME? #NAME? 1.00E+00 1.00E-20 1.00E-20 #NAME?
#NAME? #NAME? 1.00E+00 1.00E-20 1.00E-20 #NAME?
#NAME? #NAME? 1.00E+00 1.00E-20 1.00E-20 #NAME?
#NAME? #NAME? 1.00E+00 1.00E-20 1.00E-20 #NAME?
ln fi
Na+ Cl- delta ln fugacity delta^2
#NAME? #NAME? 9.74E-06 9.49E-11
#NAME? #NAME? 8.53E-03 7.28E-05
#NAME? #NAME? 3.03E-02 9.21E-04
#NAME? #NAME? 6.29E-02 3.96E-03
#NAME? #NAME? 1.06E-01 1.13E-02

sum 1.62E-02
Physical properties from the electrolattice equation of state for ions of unequal diameters

Reference:
Work in progress

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Vapor pressure of: water

vcell 5

sum q 1.742253
Fractional q 0.492302209 0.408785062 0.09891273
Vinf 5.290993373 4.393397011 1.063059616

Vinf (cm3/mol) 5.290993373 4.393397011 1.063059616 5

R (J/(mol.K)) 8.314

r 2.14949 12.7

Water
D-group alpha group beta group Na+ (group)
Vinf (m3/mol) 0.000005291 4.393397011E-06 1.06306E-06 0.0000635
Qa 0.857715 0.712207 0.172331 10.36
B (Kelvin) D-group 700.671 700.671 700.671 0
alpha group 700.671 700.671 0 0
beta group 700.671 0 700.671 0
Na+ (group) 0 0 0 0
Cl- (group) 0 0 0 0
u00 (Kelvin) D -535.864 -535.864 -535.864 -277.068
alpha -535.864 -535.864 -2625.69 -277.068
beta -535.864 -2625.69 -535.864 -277.068
Na+ (group) -277.068 -277.068 -277.068 -468.877
Cl- (group) -277.068 -277.068 -277.068 -468.877
Frequency water 1 1 1 0
Na+ ion 0 0 0 1
Cl-ion 0 0 0 0
Charge 0 0 0 1
Sigma (meters) 1 1 1 2.536E-10
Dielectric coeff 1 -19.29050 0 0 0
Dielectric coeff 2 29814.5 0 0 0
Dielectric coeff 3 -0.019678 0 0 0
Dielectric coeff 4 0.00013189 0 0 0
Dielectric coeff 5 -0.0000003 0 0 0

x
T(K) P (Pa) H2O Na+ Cl-
373.3315654979 1.01E+05 1.00E+00 1.00E-04 1.00E-04
373.2004612477 1.01E+05 9.90E-01 5.10E-03 5.10E-03
372.4470440862 1.01E+05 9.80E-01 1.01E-02 1.01E-02
371.2170164273 1.01E+05 9.70E-01 1.51E-02 1.51E-02
369.5611148467 1.01E+05 9.60E-01 2.01E-02 2.01E-02
s of unequal diameters

pecifications.

5 ???????

12.7

Cl- (group)
0.0000635 ???????
10.36
0
0
0 red: for now just arbitrary values
0
0
-277.068
-277.068
-277.068
-468.877
-468.877
0
0
1
-1
2.536E-10
0 Yellow: always zero
0
0 Green: always non-zero, any value
0
0

liquid ln fi y vapor ln fi
H2O Na+ Cl- H2O Na+ Cl- H2O Na+
#NAME? #NAME? #NAME? 1.00E+00 1.00E-20 1.00E-20 #NAME? #NAME?
#NAME? #NAME? #NAME? 1.00E+00 1.00E-20 1.00E-20 #NAME? #NAME?
#NAME? #NAME? #NAME? 1.00E+00 1.00E-20 1.00E-20 #NAME? #NAME?
#NAME? #NAME? #NAME? 1.00E+00 1.00E-20 1.00E-20 #NAME? #NAME?
#NAME? #NAME? #NAME? 1.00E+00 1.00E-20 1.00E-20 #NAME? #NAME?
Cl- delta ln fugacitydelta^2
#NAME? 9.74E-06 9.49E-11
#NAME? 8.53E-03 7.28E-05
#NAME? 3.03E-02 9.21E-04
#NAME? 6.29E-02 3.96E-03
#NAME? 1.06E-01 1.13E-02

sum 1.62E-02
Physical properties and phase equilibrium of petroleum fractions and lumps

Color convention: Cells such as this one are problem specifications.

Other numeric cells are results of calculations.

Bubble point of a mixture of carbon dioxide, n-hexane, and an oil fraction characterized by its norm

oil fraction Tb (K) SG


500 0.8045745 Specifed values of normal boiling point and specific gravity

R (bar.cm3/(mol.K)) 83.14

CO2 n-hexane oil fraction


Tc(K) 304.21 507.5 683.121481 Critical properties and acentric factor of the oil fraction computed
Pc(bar) 73.83 30.1 20.1123919
omega 0.2236 0.299 0.52470282 Souahi, F. and H. Kaabeche, Oil & Gas Science and Technology
kij 0 0 0
0 0 0
0 0 0

T (K) 400
P(bar) 5
Mole fractions ln phi
CO2 n-hexane oil fraction CO2 n-hexane oil fraction CO2
Liquid 0.05 0.7 0.25 #NAME? #NAME? #NAME? #NAME?
Vapor 0.55 0.4 0.05 #NAME? #NAME? #NAME? #NAME?

delta -0.73897988
delta ^ 2 0.54609127

Isothermal flash calculation for a mixture of carbon dioxide, n-hexane, and an oil fraction character

Mole numbers
CO2 n-hexane oil fraction Total
Total 0.8 0.79 0.9 2.49
Liquid 0.2 0.64 0.85 1.69
Vapor 0.6 0.15 0.05 0.8

T (K) 350
P(bar) 5
Mole fractions ln phi
CO2 n-hexane oil fraction CO2 n-hexane oil fraction CO2
Liquid 0.1183432 0.3786982 0.50295858 #NAME? #NAME? #NAME? #NAME?
Vapor 0.75 0.1875 0.0625 #NAME? #NAME? #NAME? #NAME?
cterized by its normal boiling point and specific gravity

he oil fraction computed with the correlations published by:

Science and Technology Rev. IFP, Vol. 63 (2008), No. 2, pp. 229-237.

ln fugacity
n-hexane oil fraction
#NAME? #NAME?
#NAME? #NAME?

-0.4823991 2.6308062945 Difference between ln fugacity in the liquid and vapor phases
0.23270893 6.9211417591 The values above raised to power 2 so that all are not negative.

sum delta^2 7.6999419565 Use solver to minimize this cell by changing the blue cells

To avoid numerical problems, in Solver, do the following:


a) add constraints to force that all unknowns (blue cells) are
than a small number: 1e-08, for example;
b) in the Solver options, choose "Automatic scaling".

il fraction characterized by its normal boiling point and specific gravity


ln fugacity
n-hexane oil fraction delta G/(RT)
#NAME? #NAME? -5.0650407074
#NAME? #NAME? 0.6827580846

Total (liquid+vapor) -4.3822826228 Use solver to minimize this cell by changing the blue cells

To avoid numerical problems, in Solver, do the following:


a) add constraints to force that all unknowns (blue cells) are
than a small number: 1e-08, for example;
b) in the Solver options, choose "Automatic scaling".
nging the blue cells

r, do the following:
nowns (blue cells) are

matic scaling".
IN PREPARATION
Azeotrope in the 2-propanol (1) + water (2) mixture
R (cal/(mol.K)) T(K)
1.987 353.15
2-propanol water
V (cm3/mol) 76.92 18.07
Binary interactions (cal/mol) 0.00 437.98
1238.00 0.00

Antoine A 16.6780 16.2887


Antoine B 3640.20 3816.44
Antoine C 53.54 46.13

Psat (kPa) 92.5922335187 47.3756867345

x1 x2
0 1
0.005 0.995
0.01 0.99
0.015 0.985
0.02 0.98
0.025 0.975
0.03 0.97
0.035 0.965
0.04 0.96
0.045 0.955
0.05 0.95
0.055 0.945
0.06 0.94
0.065 0.935
0.07 0.93
0.075 0.925
0.08 0.92
0.085 0.915
0.09 0.91
0.095 0.905
0.1 0.9
0.105 0.895
0.11 0.89
0.115 0.885
0.12 0.88
0.125 0.875
0.13 0.87
0.135 0.865
0.14 0.86
0.145 0.855
0.15 0.85
0.155 0.845
0.16 0.84
0.165 0.835
0.17 0.83
0.175 0.825
0.18 0.82
0.185 0.815
0.19 0.81
0.195 0.805
0.2 0.8
0.205 0.795
0.21 0.79
0.215 0.785
0.22 0.78
0.225 0.775
0.23 0.77
0.235 0.765
0.24 0.76
0.245 0.755
0.25 0.75
0.255 0.745
0.26 0.74
0.265 0.735
0.27 0.73
0.275 0.725
0.28 0.72
0.285 0.715
0.29 0.71
0.295 0.705
0.3 0.7
0.305 0.695
0.31 0.69
0.315 0.685
0.32 0.68
0.325 0.675
0.33 0.67
0.335 0.665
0.34 0.66
0.345 0.655
0.35 0.65
0.355 0.645
0.36 0.64
0.365 0.635
0.37 0.63
0.375 0.625
0.38 0.62
0.385 0.615
0.39 0.61
0.395 0.605
0.4 0.6
0.405 0.595
0.41 0.59
0.415 0.585
0.42 0.58
0.425 0.575
0.43 0.57
0.435 0.565
0.44 0.56
0.445 0.555
0.45 0.55
0.455 0.545
0.46 0.54
0.465 0.535
0.47 0.53
0.475 0.525
0.48 0.52
0.485 0.515
0.49 0.51
0.495 0.505
0.5 0.5
0.505 0.495
0.51 0.49
0.515 0.485
0.52 0.48
0.525 0.475
0.53 0.47
0.535 0.465
0.54 0.46
0.545 0.455
0.55 0.45
0.555 0.445
0.56 0.44
0.565 0.435
0.57 0.43
0.575 0.425
0.58 0.42
0.585 0.415
0.59 0.41
0.595 0.405
0.6 0.4
0.605 0.395
0.61 0.39
0.615 0.385
0.62 0.38
0.625 0.375
0.63 0.37
0.635 0.365
0.64 0.36
0.645 0.355
0.65 0.35
0.655 0.345
0.66 0.34
0.665 0.335
0.67 0.33
0.675 0.325
0.68 0.32
0.685 0.315
0.69 0.31
0.695 0.305
0.7 0.3
0.705 0.295
0.71 0.29
0.715 0.285
0.72 0.28
0.725 0.275
0.73 0.27
0.735 0.265
0.74 0.26
0.745 0.255
0.75 0.25
0.755 0.245
0.76 0.24
0.765 0.235
0.77 0.23
0.775 0.225
0.78 0.22
0.785 0.215
0.79 0.21
0.795 0.205
0.8 0.2
0.805 0.195
0.81 0.19
0.815 0.185
0.82 0.18
0.825 0.175
0.83 0.17
0.835 0.165
0.84 0.16
0.845 0.155
0.85 0.15
0.855 0.145
0.86 0.14
0.865 0.135
0.87 0.13
0.875 0.125
0.88 0.12
0.885 0.115
0.89 0.11
0.895 0.105
0.9 0.1
0.905 0.095
0.91 0.09
0.915 0.085
0.92 0.08
0.925 0.075
0.93 0.07
0.935 0.065
0.94 0.06
0.945 0.055
0.95 0.05
0.955 0.045
0.96 0.04
0.965 0.035
0.97 0.03
0.975 0.025
0.98 0.02
0.985 0.015
0.99 0.01
0.995 0.005
1 0

Solubility of palmitic acid in ethanol

Original reference
Calvo, Beatriz, I. Collado, and E.A. Cepeda
Solubilities of Palmitic Acid in Pure Solvents and Its Mixtures
J. Chem. Eng. Data, 2009, 54 (1), 64-68.

Mr. Mohammed Faraj Al Falahi and Mr. Mohammed Al Shekaili assisted in the preparation of this example.

A rigorous formula for solid solubilities in fluids is:

However, it is common to use the following simplified formula:

where the subscript "f" indicates fusion properties. This is the formula used here.

Activity coefficient calculations using the NRTL model.

Palmitic acid
delta hf (J/mol) 53711
Tf (K) 335.8

R (J/(mol.K))
8.314
Palmitic acid (1) ethanol (2)
0 0.3
alfa 0.3 0
0 -2111.4
Binary interactions (J/mol) 6427.06 0

Experimental Experimental Experimental Calculated Calculated


T (K) x1 x2 T (K) ln (gamma1)
292.85 0.0119 0.9881 290.3924945347 #NAME?
297.25 0.02 0.98 296.1865817118 #NAME?
301.65 0.0328 0.9672 301.5260898776 #NAME?
304.05 0.0429 0.9571 304.2834487025 #NAME?
306.55 0.0566 0.9434 306.9833923114 #NAME?
310.25 0.086 0.914 310.7095627611 #NAME?
312.05 0.1096 0.8904 312.6605302771 #NAME?
315.45 0.1649 0.8351 315.6588288161 #NAME?
317.95 0.2221 0.7779 317.7623952595 #NAME?
321.05 0.3115 0.6885 320.3700220217 #NAME?
322.95 0.3768 0.6232 322.0895205549 #NAME?
317.05 0.2053 0.7947 317.2012377257 #NAME?
319.25 0.2513 0.7487 318.668393711 #NAME?
321.55 0.3241 0.6759 320.7089554112 #NAME?
323.65 0.395 0.605 322.5560418561 #NAME?

0.45

0.4
Liquid mole fracton of palmitc acid

0.35

0.3

0.25

0.2 Experimental
0.15 Calculated

0.1

0.05

0
285 290 295 300 305 310 315 320 325 330
Temperature (K)

VLE of acetone (1) + 2,3-butadione (2)

Original reference
Vapor-Liquid Equilibrium for Binary Systems of Diacetyl with Methanol and Acetone
Soni, M., D. Ramjugernath, and J.D. Raal
J. Chem. Eng. Data 2006, 51, 2083-2087

R (J/(mol.K))
8.314

alfa 0 0.3
0.3 0
Binary interactions (cal/mol) 0 -2724.817
3921.795 0

T(K) x1 x2 P1sat (kPa) P2sat (kPa)


323.15 0.754 0.246 81.65 22.77
lngamma1 lngamma2 gamma1 gamma2 P (kPa) y1
#NAME? #NAME? 10.4169443925 1 47.37569 0
#NAME? #NAME? 9.713909731 1.0001736979 51.64416 0.08708
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
#NAME? #NAME? #NAME? #NAME? #NAME? #NAME?
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ation of this example.


Calculated Simplified solubility (Simplified solubility
ln (gamma1) equation equation)^2
#NAME? 8.606314823467E-06 7.4069E-11
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#NAME? 3.145945895344E-06 9.8970E-12
#NAME? 3.12688882651E-05 9.7774E-10
#NAME? 0.000020011 4.0044E-10
#NAME? -0.000010106 1.0213E-10

Sum of squares 5.2593E-09


Use Solver to minimize this cell by changing the blue cells
In this way, the temperatures of all data points are found in a
single operation.

Experimental
Calculated

0
ln(gama1) ln(gama2) gama1 gama2 P (kPa) y1
#NAME? #NAME? 0.9924545367 0.9840969576 66.61191 0.917247
y2
1
0.91292
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#NAME? 54
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52
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#NAME? 50
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#NAME? 48
#NAME?
P (kPa)

#NAME?
#NAME? 46
#NAME?
#NAME? 44
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42
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#NAME? 40
#NAME? 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
#NAME? x1,y1
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y2
0.082753
0.7 0.8 0.9 1