Jens Ahlers, Jrgen Rarey, Jrgen Gmehling

Chair of Industrial Chemistry

University of Oldenburg, Germany
DDBST GmbH

Present status and potential of

group contribution methods
for process development
AIChE Regional
Process Technology Conference
Galveston, TX October 2009
Prof. Gmehling Rossini Lecture Award 2008
 Overview on the Requirement and the Available VLE Data for
Binary Systems (2008, 1973)

Assuming that 1000 compounds are of technical interest

VLE data for appr. 500 000 binary systems are required

Number of VLE Data Sets stored in the Dortmund Data Bank:

55 450 isothermal / isobaric VLE data sets

DDB
DDB
(but 240 data sets for ethanol-water, 150 data sets for
acetic acid-water, 175 data sets for methanol-water, ..

VLE data for 10 520 binary systems: 2.10 %

Situation 1973: 17600 isothermal / isobaric data sets

VLE data for 3 803 binary systems: 0.76 %

 06.02.03

Group Contribution Method

gl_e.cdr

Distillation Symposium Brighton 1969

-OH -CH3 ASOG (solution of groups concept)
-CH2 -CH2 -CH2 ln i = ln iC + ln iR
-CH2 -OH ln iR = k( i ) (ln k ln (ki ) )
i

(based on the Wilson and Flory-

Huggins equation)
Ethanol: -CH3 -CH2 -OH

1975 the UNIFAC method was

n-Hexane: -CH3 -CH2 -CH2 -CH2 -CH2 -CH3
published by Aa. Fredenslund et al.
(based on the UNIQUAC equation,
Prof. Dr. Ulfert Onken also published 1975)
Great advantage:
(University
Number of possible of groups << number of different components
structural
Dortmund)
Required group interaction parameters are fitted to experimental VLE data
Experimental and Predicted Vapor-Liquid Equilibria
Using UNIFAC
 12.01.00

From UNIFAC to mod. UNIFAC F = VLE (+ LLE + )

8
1.2
acetone + heptane no data for heptane in

8
700.
50C compounds of very 1.0
600. n-alkanes
500.
different size
0.8
P / mmHg

40C
400.
0.6
300. no quantitative
200. 0.4
information
0C
100. about (T) 0.2
0.0 25. 50.
0.
0.0 0.5 1.0 number of carbon-atoms
x1, y1 2000.
10.
acetone + heptane
heptane in
8

ln hE

hE
8. acetone
i = i
1 R 1000.
extrapolation to 6. T
infinite dilution can 90C
be dangerous 4. 35C
8

acetone 10C
in heptane 0.
2. 0.0 0.5 1.0
x1
/ C
 12.01.00

From UNIFAC to mod. UNIFAC

(U. Weidlich, J. Gmehling 1987)
acetone + heptane 10.
700. heptane in

8
mixture information
600. 50C for the dilute region 8. acetone
500. is used for fitting
P / mmHg

40C
400. 6.

300.
4.

8
200. quantitative information acetone in
100.
0C about (T) from heptane
2.
excess enthalpies 20. 40. 60. 80. 100.
0. / C
0.0 0.5 1.0
x 1, y 1 1.2 2000.

1.0

hE
0.8 acetone +
improved results for 1000. heptane
asymmetric mixtures 0.6 heptane in ln hE 90C
8

using a modified 0.4 i = i 35C

combinatorial part n-alkanes 1 R 10C
T
0.2 0.
0. 25. 50. 0.0 0.5 1.0
number of carbon-atoms x1
 10.02.03

Data Base (Objective Function) Used

for Fitting Modified UNIFAC (Dortmund) Parameters

Objective Function:

F = w VLEVLE+ w AZDAZD+ whE hE + wcE c p + w + wLLE LLE+ wSLESLE

E
P

mixture data type delivers the required information

VLE, azeotropic data = f (x)
Gibbs-Helmholtz equation = f (T)
Eh E
E
lnlni i hhiEEi
h ( cEP ) ==
(cP ) ((11// T
T)) R R supporting data at high temperature

the only reliable information in the dilute

range and about asymmetric systems
SLE hm,Tm,i supporting data at low temperature
(eutectic ln xLi iL = 1 T
RT Tm,i (T < 273 K)
systems)
LLE often the only information for strong real
mixtures
Experimental and Predicted Mod. UNIFAC (Do) Results
for Different Alkane - Ketone - Systems
 DDB 2009 The Growth

PCP CPE VE hE POLY

400000,0 AAE KI AZD ESLE SLE
CRI EGLE GLE ACM ACT
LLE ELE HPV VLE
ACT and AZD: 10 data points
300000,0 taken as 1 data set
Data Sets

200000,0

100000,0

,0
1995

1997

1999

2001

2003

2005

2007

2009
Year
140 data sets per working day (yearly increase last 2 years 6.5 %)
 Status of the Dortmund Data Bank* (April 2009)
61000 References, 1800 Journals, 28600 Compounds incl. Salts, Adsorbents and Polymers

29700 (VLE) 29200 (HPV) 30400 data sets for 55200 data points for pure solvents
non-electrolytes
VLE** Polymers new
(E)SLE 16950 data sets
7700 (ELE) 1410 data sets KI
27700 data sets KOW
(total: 66600 data sets) for solvent mixtures
for electrolytes
9150 data points
19400 data sets
hE LLE
DDB 20200 data sets
3100 data sets
cPE azeotr. data

38300 data sets 51300 data points

vE 18800 data sets
Pure Component Properties
for non-electrolytes
CRI AAE
c P Pi S (E)GLE

1960 data sets 3600 data sets 1500 data sets for electrolytes
183000 data sets
* detailed information is available via internet (www.ddbst.de)
** including unpublished VLE data from chemical companies, e.g. from the former German Democratic Republic
Different Ways to Keep the DDB Growing

Constant further back-evaluation of older sources

Integration of unpublished data
from chemical industry
MSc. and PhD. thesis from well known research groups
These data will not be provided by online-services
Evaluation of new non-english scientific publications

only 10 15 % of the data stored in

the DDB are published in book form

Digging for Data

 11.02.03

Experimental and Predicted Azeotropic Data for the Quaternary System

at P = 101.325 kPa Benzene (1) - Cyclohexane (2) - Acetone (3) - Ethanol (4)

predicted (mod. UNIFAC (Do)) experimental*

system
type of / C y1,az y2,az type of / C y1,az y2,az
azeotrope azeotrope
1-2 homPmax 77.5 0.543 homPmax 77.6 0.543
1-3 none none
1-4 homPmax 68.0 0.537 homPmax 67.9 0.552
2-3 homPmax 54.3 0.221 homPmax 53.2 0.248
2-4 homPmax 65.3 0.545 homPmax 64.8 0.553
3-4 none none
1-2-3 none none
1-2-4 homPmax 65.1 0.126 0.441 homPmax 64.9 0.113 0.462
1-3-4 none none
2-3-4 none none
1-2-3-4 none n.a.

* mean values of the experimental data stored in the Dortmund Data Bank

n.a.: not available

 11.02.03

Selection of Selective Solvents for Extractive Distillation

homogeneous pressure
Components to be separated
maximum azeotrope
(1) Cyclohexane Tb = 353.86 K
Tb = 351.47 K at P = 101.32 kPa
(2) Benzene Tb = 353.25 K

modified UNIFAC (Dortmund)

selective solvent (3) (1,2), inf. (T [K])
Adipodinitrile 8.70 (353.56K)

K i i Pi S 2,5-Hexanedione 4.95 (353.56K)

ij = = = 1( or 1) N-Methyl-2-pyrrolidone 4.93 (353.56K)
K j j Pj S
Furfural 4.11 (353.56K)
Aniline 4.02 (353.56K)

selection criterion: Acetophenone 3.83 (353.56K)

Triethylene glycol 3.03 (353.56K)
Nitrobenzene 2.88 (353.56K)
Cyclohexylamine 2.80 (353.56K)

S = i
>> (<< )1 3-Methylphenol 2.10 (353.56K)
ij ,entrainer

j
Tetrahydrofurfuryl alcohol 2.07 (353.56K)
Cyclohexanone 2.06 (353.56K)
Anisole 1.72 (353.56K)
Modified UNIFAC (Do) parameter matrix for ionic liquids

[BTI]-
F
C
O F C
N+ F
N
S O

C
N-
C
F
F S
[Imidazolium]+ C O
O

[Pyrrolidinium]+
F

F
N+ F O
C C O
C S
C F
C
[OTF]- O-

C N
+
[BF4]- F

B-
C C F F

F = ( P ) + ( ) + ( h )
C C
2 2 E 2
[Pyridinium]+
F
Experimental and predicted activity coefficients at infinite dilution
for different alkanes and alkenes in 1-alkyl-3-methylimidazolium
trifluoromethanesulfonate [RMIM]+[OTF]-
Experimental and predicted VLE data for cyclohexane
benzene with and without ionic liquid
Limit of the Methods UNIFAC and Modified UNIFAC

HRh(CO)[P(C6H4S3O3 Na )] 3
propylene + CO + H2 (n / i)-butyraldehyde

51 bar
125 C
55 bar
reactor design: column
design:
gas solubilities
gas solubilities
LLE VLE
VLE

phases: propylene
gas / vapor CO + H2
organic crude
aqueous (n/i)-butyraldehyde

The components propylene, CO and H2 are in the supercritical state.

=> UNIFAC and Modified UNIFAC (Dortmund) cannot be used !
 05.02.03

Equations of State: van der Waals (1873)

P = Prep + P att
RT a
P rep
= P att
= 2
v b v nobel
price
a - intermolecular attraction
winner
b - closest packing
P volume
=
2P
=0
for
v 2
v Tkr Tkr physics
1910

RT 2 a ab
v b +
3
v + v =0
P P P
 09.01.00

Otto Redlich, John M. Prausnitz, Jrgen Gmehling

RT a a (T )
P= 1/ 2 P=
RT

v b T v(v + b) v b v (v + b)

a(T) = a(Tc) (T)

Otto Redlich, J. M. Prausnitz, ... Giorgio Soave

 05.02.03

Introduction of Improved Mixing Rules (GE-Mixing Rules)

Jean Vidal

Acetone (1)
- Water (2)
at 60oC

classical
mixing rule

gE mixing rule

E P = , gE model : Wilson,NRTL,..
g
= xi ln i = ln xi ln i* a(T) x a (T)
= i ii +
gE
RT b bi -0.6931
 05.02.03

PSRK (Predictive SRK Equation of State)

Huron, Vidal (1979) PSRK (Predictive SRK)*

P= Pref = 1 atm

a(T) x i a ii (T) gE g E + RT xi ln b b
= + a(T ) x a (T )
= i ii + i i
b bi - 0.6931 b i bi 0.64663

gE-model: original UNIFAC

Group interaction parameters:
UNIFAC matrix + parameters for 30
gases, such as CO2, CH4, H2, H2S, ..
gE-model: Wilson, NRTL, ...
fitted to VLE of normal and low
boiling substances, gas solubilities
*Holderbaum, Gmehling (1991)
 10.02.03

Experimental and Predicted Results Using PSRK

with already Available UNIFAC Parameters (VLE Data)

Ethanol (1) + Water (2) Acetone (1) + Water (2)

325C 250C
300C

200C
log P / bar

log P / bar
250C

150C
200 C

100C
150C

x1,y1 x1,y1
09 00 006 GC-EOS
 10.02.03

Experimental and Predicted VLE Data for Different

CO2 + n-Alkane Systems Using PSRK

CO2 (1) + Propane (2) CO2 (1) + Butane (2)

328 K 294 K 344 K
378 K
311 K
411 K

278 K
311 K

CO2 (1) + Hexane (2) CO2 (1) + Decane (2)

511 K
393 K
353 K 444 K
378 K

313 K
311 K

09 00 008 GC-EOS
 Experimental and Predicted (PSRK) Henry Coefficients
of CH4, CO2, COS and H2S in Methanol

Methanreinigung.cdr

CH4

CO2 PSRK (UNIFAC)

H2S

COS
 Experimental and Calculated Gas Solubilities
(LIFAC PSRK)
ln i = ln iLR + ln iMR + ln iSR

long-range middle-range short-range

(Debye-Hckel) (Pitzer) (UNIFAC)
H2O CO2 NaNO3 H2O CO2 NaCl
10000 10000
40 C
8000 8000
100 C

P / kPa
P / kPa

6000 6000

4000 4000
m = 0 mol/kg m = 0 mol/kg
m = 1.00 mol/kg m = 0.52 mol/kg
2000 m = 2.50 mol/kg 2000 m = 2.50 mol/kg
m = 5.00 mol/kg m = 4.00 mol/kg
m = 10.1 mol/kg m = 4.00 mol/kg; Maurer et al.
PSRK / LIFACPSRK PSRK / LIFACPSRK (new)
0 0
0.00 0.01 0.02 0.03 0.00 0.01 0.02 0.03
x 1 (salt-free) x 1 (salt-free)
 Conclusion

great progress has been achieved for predictive thermodynamic models

a comprehensive data bank was a prerequisite for this development

Predictive model Data used for fitting the parameters

UNIFAC VLE (LLE)

Modified UNIFAC VLE (LLE), azeotropic data, hE, , SLE of eutectic systems

LIQUAC (LIFAC) VLE of electrolyte systems, osmotic coefficients, mean activity

coefficients, salt solubilities
Group contribution VLE of normal boiling and low boiling substances, gas solubilities
EOS PSRK

Recent development: improved group contribution equation of state

VTPR (volume-translated Peng-Robinson)
Research Industrial
Industrial Chemistry
Chemistry
University
University of
of Oldenburg
Oldenburg
Prof.
Prof. Dr.
Dr. J.
J. Gmehling
Gmehling -- Research
Research Projects,
Projects, Model
Model Development
Development
UNIFAC
UNIFAC Consortium
Consortium TRU
TRU
Durban,
Durban, SA
SA
Mixture
Mixture Property
Property Estimation
Estimation Pure
Pure Component
Component Property
Property Estimation
Estimation

CAT - Center for Applied Thermodynamics

Products DDBST LTP (Associated Institute)

Data Banks, Software, Consulting Experimental Services, Consulting

Education Graduate
Graduate Courses
Courses Thermodynamics,
Thermodynamics, Training
Training Courses
Courses DDB/DDBSP
DDB/DDBSP
Text
Text books:
books: Industrial
Industrial Chemistry,
Chemistry, Unit
Unit Operations,
Operations, Thermodynamics,
Thermodynamics,

Sales, Marketing, Custom Tailored Products

DECHEMA
DECHEMA FIZ
FIZ CHEMIE
CHEMIE EPCON
EPCON Int.
Int. Mitsubishi
Mitsubishi Chemical
Chemical
Frankfurt,
Frankfurt, Germany
Germany Berlin,
Berlin, Germany
Germany Houston,
Houston, Texas
Texas Kurashiki,
Kurashiki, Japan
Japan
 Companies founded

LTP DDBST
GmbH GmbH
www.ltp- www.ddbst.de
oldenburg.de
Members of the UNIFAC Consortium (2009)

Eastman Chemical Company

UNIFAC Sponsor-Meeting 2008
 Parameter Matrix for Modified UNIFAC (Dortmund)

1
1 CH2
2
2 C=C

New Structural
3
3 ACH
4
5
ACCH2
OH
4
5
Published Consortium
Groups:
6
6 CH3 OH
7
7 H 2O
8

Parameter Pairs
8 ACOH

46 cy-CONC
9
10
11
CH2 CO
CHO
CCOO
9
10
11
12
653* 1332
47 CONR
12 HCOO

Main Groups
13

53 87
13 CH2 O
14
14 CH2 NH2

48 CONR2
15
15 CH2 NH
16
16 (C)3N
17

49 HCONR
17 ACNH2
18
18 Pyridin
19
19 CH2 CN

50 ACCN
20
20 COOH
21
21 CCl
22
published parameters I to IX
51 NCO
22 CCl2
23
23 CCl3
24
24 CCl4

52 ACS
25
25 ACCl
26
26 CNO2
27 parameters only members of the consortium
53 Epoxy
27 ACNO2
28
28 CS2 29
29 CH3 SH
54 Anhydrides 30
31
Furfural
DOH
30
31
published parameters but revised within the consortium
55 Carbonates
32
32 I
33
33 Br
34

56 Sulfones
34 C C
35
36
DMSO
Acryl
35
36 no parameters available
57 ACCHO 37
38
ClC=C
ACF
37
38

58 ACCOOH
39

* in the meantime 255 parameter

39 DMF
40
40 CF2
41
59 ACCOO 41
42
COO
CY-CH2
42
43

60 OCCOH
pairs revised within the
43 CY-CH2O
44
44 HCOOH
45

61 CH2S
45 CHCl3
46
46 CY-CONC
CONR 47
47
62 Lactames consortium
48
48 CONR2
49
49 HCONR

63 Lactones
50
50 ACCN
51
51 NCO 52

64 Peroxides 52
53
ACS
Epoxy
53
54

74 Acetals
54 Anhydrides 55
55 Carbonates 56
56 Sulfones 57
75 ACNR2 57
58
ACCHO
ACCOOH
58
59

76 ACNHR
59 ACCOO 60
60 OCCOH
61

77 Furan
61 CH2 S 62
62 Lactames 63

78 cy-CNH
63 Lactones 64
64 Peroxides
74

79 cy-CNR
74 Acetals
75
75 ACNR2
76
76 ACNHR
80 SiH 77 Furan
77
78

81 SiO
78 cy-CNH
79
79 cy-CNR
80

82 Oxime
80 SiH
81 81
SiO
82
83 ACCO
82 Oxime
83 ACCO 83
 Deviations Between Experimental and Calculated
VLE ( Data Base: 1358 Consistent Data Sets )

UNIQUAC
UNIFAC 7.96

Mod. UNIFAC(Do)
Mod. UNIFAC(Ly)
ASOG 5.90

COSMO-RS(Ol)
Raoults
Ideal law 4.28

2.51

1.89 1.81
1.6 6
1.45 1.46 1.42 1.4 0
1.23
0.94 1.0 5 0.92 0.89
0.74
0.59 0.61
0 .46
0.29

yabs [%] P [kPa] T [K]

 UNIFAC Parameter Matrix

Consortium Meeting 2009 / Constantinescu

 PSRK Matrix

Consortium Meeting 2009 / Constantinescu

 Summary

Group interaction parameters:

method parameter pairs
New in revised published consortium
2009
UNIFAC 6 -- 635 985
50 main groups 67 main groups
Modified UNIFAC 39 255 653 1332
53 main groups 87 main groups
Modified UNIFAC 25 -- 8 106
(COSMO-RS(Ol))

PSRK 6 1 955 1086

82 main groups 89 main groups
 Mod. UNIFAC Matrix - Gaps filled with COSMO-RS (Ol)

Measurement difficult (highly reactive, explosive or toxic components):

Prediction with the quantum-mechanical method COSMO

Isocyanate group
NCO
(main group 51)
Peroxide group
(main group 64)
 Overview Delivery 2009

Experimental Delivery 2009

2009 Total
Vapor-Liquid Equilibrium Data 20 231
Heats of Mixing Data 23 257
Solid-Liquid Equilibrium Data 13
Azeotropic Data 3
Gas-Liquid Data 12 27
Activity Coefficients at infinite dilution 24 28

Consortium Meeting 2009 / Constantinescu

 Experimental Facilities
vapor-liquid equilibria (VLE) excess enthalpies (hE)
storage vessel T P pressure
controller
thermostatted
vacuum pressure sensor
T
T second piston injector vacuum Peltier-cooler
P

thermostated
piston injector
PP

teflon N2
sealing pump
pressure

gear wheel thermostat

transmission cell stirrer stirrer T = const.
HPLC-pumps
thermostat insulation
stepping
motor stepping motor driven mixing-tube control heater
injection valves calibration resistor

computer-driven static apparatus isothermal flow calorimetry

azeotropic data (AZD) activity coefficients at solid-liquid equilibria (SLE)
motor
infinite dilution (ACT)
constant pressure controller A: equilibrium cell
C M B: Pt-resistance thermometer
temperature sensor B P P
L C: temperature display
vacuum pump D: cryostat
H
E: contakt liquid
magnetic vapor F: cryostat liquid
C
sampling valve F G: vacuum
G
reflux buffer volume H: magnetic stirrer
A J
B K: nitrogen flask
vacuum jacket condenser D
I E L: bubble counter
sample vessel E L
F A M: seal
K G
rotating band K Specifications:
TH2
temperature sensor
TH1
T-range - 90C < T < 50C
heating jacket A - carrier gas supply F,J - tempering coil
D H Dev. in x: max 0.0001
B - needle valve H - injection block
C - heating coil I - chromatographic column Dev. in T: max 15 mK
magnetic stirrer D,G,K - saturators L - soap bubble flowmeter
E - thermal conductivity detector TH1,TH2 - thermostats

wire band column GLC visual method

Consortium Meeting 2009 / Constantinescu
 Overview Delivery 2009

- systematic measurements for main groups:

11 CCOO (acetate group)
12 HCOO (formide group)
78 cy-C-NH (cyclic amine group)

- two new main groups in Modified UNIFAC (Dortmund):

86 C2Cl4 (Tetrachloroethylene)
87 C4H9N+ (Pyrrol)

(+ 5 new subgroups)

3 new subgroups in UNIFAC

Consortium Meeting 2009 / Constantinescu

 Objectives 2009/2010

Revision and Extension of current Parameter Matrices for UNIFAC, Mod. UNIFAC

Filling Gaps
New Main Group for acroleine
Subgroup upgrading

Definition of new Main Groups for PSRK

adapt PSRK matrix to UNIFAC

Filling Gaps in the Modified UNIFAC Matrix with COSMO-RS (Ol)

systems where no experimental data are available

Experimental work:

Determination of Phase Equilibrium Data for the Revision of Interaction Parameters

Systematic Measurements (VLE, AZD, hE, ACT, SLE, GLE) for filling Gaps
Consortium Meeting 2009 / Constantinescu
UNIFAC Consortium Team ( Sept. 2009)
Dr. Dana Experimental work:
Constantinescu
VLE, GLE, hE, SLE,
(UNIFAC, mod. , azeotropic data
UNIFAC, management
consortium,
customization files, ..) Rainer Blts

Denis Krotov
(PSRK) Helmut Stojek

Kathrin Schreiber

most of them working part time on the project

 Acknowledgement
Prof. Gmehling would like to thank

Prof. Dr. Ulfert Onken, Dr. Hermann Stage, Prof. Dr. Aage Fredenslund,
Prof. Dr. Jiding Li, Prof. Dr. Jian Chen, Prof. Dr. Weidong Yan,
Prof. Dr. John M. Prausnitz, Dr. Antje Jakob

all PhD students, in particular:

Jrgen Rarey, Jochen Menke, Wolfgang Arlt, Ulrich Weidlich, Brbel Kolbe,
Hans-Martin Polka, Thomas Holderbaum, Martin Schiller, Kai Fischer, Jens
Ahlers

the long standing technical co-workers Rainer Blts, Bernd Werner

a large number of foreign guests

and the different institutions:

Deutsche Forschungsgemeinschaft (DFG), the Ministry of Research (BMFT), AiF,
DDBST team, members of the UNIFAC consortium

I thank Todd Willman for the inventation to this conference and you for your
attention and patience !
 Data published by E. Sapei, P. Uusi-Kyyny. K. I. Keskinen,
J. Aittamaa, Fluid Phase Equilib. 279, 81-86 (2009)
_____
modified UNIFAC
90
80

70
80

60

P [kPa]
P [kPa]

70 50

40

60
30

0 0,2 0,4 0,6 0,8 1 0 0,2 0,4 0,6 0,8 1

x1,y1 x1,y1

2,2,4-trimethylpentane (1) cyclohexane (1) - 3-methylthiophene (2)

3-methylthiophene (2) at 368.15 K at 348.15 K
Data published by E. Sapei, P. Uusi-Kyyny. K. I. Keskinen,
J. Aittamaa, Fluid Phase Equilib. 279, 81-86 (2009)
_____
modified UNIFAC
85 90

80
80

70

75
60

P [kPa]
P [kPa]

70 50

40
65

30
60

20

55
0 0,2 0,4 0,6 0,8 1
0 0,2 0,4 0,6 0,8 1
x1,y1
x1,y1

2,4,4-trimethyl-1-pentene (1) 1-hexene (1) - 3-methylthiophene (2)

3-methylthiophene (2) at 368.15 K at 333.15 K
 Results predicted with mod. UNIFAC(Do) for hE Data by using new
Parameters - Measurements performed in our laboratory

0
E
H exp.
E 400
H exp.
-30
mod. UNIFAC
mod. UNIFAC 323.15K
-60 300
HE/Jmol-1

HE/Jmol-1
-90
200

-120
363 K
363.15 K

100 HE exp.
-150 HE exp.
413 K
mod. UNIFAC(Do)
mod. UNIFAC(Do)
-180 0
0,0 0,2 0,4 0,6 0,8 1,0 0,0 0,2 0,4 0,6 0,8 1,0

x1 x1

Diethyl ether(1) + Thiophene(2) Pyrrolidine(1) + Toluene (2)

Interaction parameters between Interaction parameters between
main groups 13/52 CH2O / ACS main groups 78/4 cy-C-NH /
ACCH2
Consortium Meeting 2009 / Constantinescu
 Results predicted with the new added main group 86 (C2Cl4)
in Mod. UNIFAC (Dortmund)

Exp. Data P=1 bar

600 405 Exp. Data P=1 bar
Mod. UNIFAC(Do)
Mod. UNIFAC(Do)

400
HE/Jmol-1

400

T/K
395

200

Exp.Data T=298.15 K
390
mod. UNIFAC(Do)
0
0,0 0,2 0,4 0,6 0,8 1,0 0,0 0,2 0,4 0,6 0,8 1,0

x1 x1,y1

Cl
Tetrachloroethylene(1) + 2-Ethoxyethanol(2)
Cl H2
Interaction parameters between main groups C O CH3
Cl
86/60 C2Cl4 / OCCOH HO C
H2
C
H2
Cl

Consortium Meeting 2009 / Constantinescu

 Results predicted with the new added main group 86 (C2Cl4)
in Mod. UNIFAC (Dortmund

40
Exp.Data T=313.15 K H2 Cl
35 Exp. Data T= 323.15 K C
Mod. UNIFAC(Do) H2 C CH2 Cl
30
H2 C CH2 Cl
25 C
H2 Cl
P/kPa

20
Cyclohexane (1) + Tetrachloroethylene (2)
15 Interaction parameters between
main groups 42/86 cy-CH2 / C2Cl4
10

0
0,0 0,2 0,4 0,6 0,8 1,0

x1,y1

Consortium Meeting 2009 / Constantinescu

 Results predicted with the new added main group 86 (C2Cl4)
in Mod. UNIFAC (Dortmund

435 400
Exp. Data P=1 bar Exp. Data P=1 bar
430 Exp. Data P= 1bar Exp. DataP= 1 bar
mod. UNIFAC(Do) mod. UNIFAC(Do)
425
mod. UNIFAC(Do) mod. UNIFAC(Do)
390
420

415
T/K

T/K
410 380

405

400

370
395

390
0,0 0,2 0,4 0,6 0,8 1,0 0,0 0,2 0,4 0,6 0,8 1,0

x1, y1 x1, y1

Tetrachloroethylene (1) + Furfural (2) Heptane (1) + Tetrachloroethylene

Interaction parameters between (2)
main groups 86/30 C2Cl4 / Furfural Interaction parameters between
main groups 1/86 CH2 / C2Cl4

Consortium Meeting 2009 / Constantinescu

 Weaknesses of group contribution methods

Isomer effects can not be described correctly

(but the influence of the standard fugacity Pis, Pisubl (hm,Tm) is

more important), e.g. in the case of VLE, SLE, ..
no improvement is achieved with other approaches, e.g.
COSMO-RS

Problems exist, when a large number of functional groups is

present (proximity effects)

Poor -results and LLE for water with alkanes (alkenes) or

naphthenes
 Number of hE-Data Sets Stored in the DDB
as a Function of Temperature

12000
Total:
10000 ~19600 data sets
(Juli 2008)
Number of data sets

8000
mainly measurements
(~900 data sets)
6000 from our
research group
4000

2000

0
260 300 340 380 420

Temperature [K]
Experimental and predicted activity coefficients at infinite
dilution of different alkanes in alkylmethylimidazolium-
bistrifluorosulfonylimide [RMIM]+[BTI]-

experimental data
mod. UNIFAC (Do)
 18.03.99

The LIFAC (LIQUAC)-Model

LIFAC Parameter Matrix

lni = lniLR + lniMR + lniSR 1

2
CH2
OH
1

2
UNIFAC parameters
3
4
CHOH
HO2
3 3

4
(Hansen et al. 1991)
5
6
CHCO
CCOO
2 5

6
fitted parameters
7
8
CHO
Ccl2
2 7

8
no parameter available
9
10
Li+
Na+
9

10
set to zero
11 K+ 11

12 NH4+ 12
Long Range Middle Range Short Range 13 Ca2+ 13

14 Mg2+ 14
15 Ba2+ 15

Debye-Hckel empirical version UNIFAC 16 Sr2+ 16

17 Cu2+ 17

equation of the Pitzer (UNIQUAC) 18 Zn2+ 18

19 Co2+ 19
for solvent approach 20 Ni2+ 20

21 Hg2+
mixtures 22 F_
_
21

22

23 Cl_ 23

24 Br 24
_
25 I _ 25

26 NO3 26
no further required original 27 CHCOO
3
_
27
_
28
parameters parameters UNIFAC 29
SCN_
SO42
28

29

required b0 , b1 parameters

bo and b1 fitted simultaneously to VLE of electrolyte systems,

mean activity coefficients and osmotic coefficients
53
 Solubility and Mean Activity Coefficients of Different Salts in Water
[mol/kg]

[mol/kg]

[mol/kg]
[mol/kg]

[mol/kg]
4

[mol/kg]
SolubilityLslichkeit

SolubilityLslichkeit

SolubilityLslichkeit
ideal ideal
ideal
LIQUAC
LIQUAC LIQUAC
exp. exp.
exp.

Temperature [C]
Temperatur [C] Temperature [C]
Temperatur [C] Temperature [C]
Temperatur [C]
1.0 1.0
1.0

0.9 0.9
KCl NaCl NH4Cl
0.9
0.8 0.8

LIQUAC 0.8
0.7 0.7
25C
25C LIQUAC
0.6 0.7 0.6 25C
LIQUAC
0.0 2.0 4.0 6.0 0.0 2.0 4.0 6.0 8.0 0.0 2.0 4.0 6.0 8.0
m mol/kg m mol/kg m mol/kg
Experimental and Predicted Solubility (LIQUAC) of KCl
in the System Water(1)-Methanol(2)

organic
aqueous
solution

salt

salt ( org) = salt ( s) = salt ( aq)