UNIFAC

Documentation
DDBSP Dortmund Data Bank Software Package
DDBST Dortmund Data Bank Software & Separation Technology GmbH
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DDBSP- Dortmund Data Bank Software 6ackage $#".
Table of Contents
7ntroduction((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((.
Tutorial(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((.
Building a Sy3tem(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((+
hecking 6arameter 89ailability(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((%
alculation(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((/
73othermal alculation o9er a oncentration :ange((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((/
alculation at on3tant ompo3ition3 o9er a Temperature :ange((((((((((((((((((((((((((((((((((((((((((&
:e3ult Grid(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((&
8cti9ity oefficient Diagram((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((("#
The Menu3(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((("#
8ppendi1((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((""
;<708(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((""
Table of Figures
0igure ") ;<708 Graphical ;3er 7nterface((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((+
0igure $) omponent Selection((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((+
0igure .) omponent =i3t(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((>
0igure +) Group 833ignment Detail3((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((>
0igure >) 6arameter 89ailability(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((%
0igure %) alculation Setting3(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((/
0igure ?) alculation at on3tant Temperature((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((/
0igure /) ompo3ition Setting3((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((/
0igure &) Special ompo3ition3((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((&
0igure "#) alculation Setting for on3tant ompo3ition3((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((&
0igure "") :e3ult Grid(((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((&
0igure "$) :e3ult Grid with ==2 alculation((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((&
0igure ".) Temperature-dependent 8cti9ity oefficient3((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((((("#
;<708 6age $ of "$
DDBSP- Dortmund Data Bank Software 6ackage $#".
Introduction
Thi3 3oftware allow3 calculating acti9ity coefficient3@ heat3 of mi1ing@ and e1ce33 heat capacity by
the acti9ity coefficient model3 ;<708
"
and modified ;<708 ,Dortmund-
$
for mi1ture3 with up to
fifty component3(
7f the ==2 e1ten3ion licen3e i3 a9ailable it i3 al3o po33ible to calculate the liAuid-liAuid eAuilibrium
for binary and ternary 3y3tem3(
The 3oftware i3 an integral part of the Dortmund Data Bank 3oftware package and u3e3 the
component@ the group3 a33ignment@ and other tool3 from thi3 package( The package therefore
include3
"( the main calculation program ,de3cribed here-
$( a component 3election tool ,de3cribed in BomponentManagement(pdfC-
.( a component editing tool ,de3cribed in BomponentManagement(pdfC-
+( a ;<708 interaction parameter editor ,de3cribed in BG Model 6arameter3(pdfC-
>( a DDB configuration editing tool ,de3cribed in BDDBonfiguration(pdfC-
The 3oftware come3 with a li3t of more than .$### component3 from the main DDB component li3t and
appro1( "%### of them ha9e a ;<708 group a33ignment and about "+>## ha9e a group a33ignment for
modified ;<708 ,Dortmund-( 0or mo3t component3 the DDB pro9ide3 8S regi3try number3 ,$">##-@
empirical formula molecular weight3 ,almo3t all-( 8ll other component3 are applicable in both method3 ,e( g(
3alt3@ metal3 and metal comple1e3@ etc(-(
The late3t ;<708 parameter3 ha9e been publi3hed in $##.
.
@ the late3t parameter for mod( ;<708
,Dortmund- ha9e been publi3hed $##$
+
@ $##%
>
and $#"" ,ionic liAuid3-
%
(
Mo3t current parameter3 can be obtained from the ;<708 on3ortium(
Tutorial
Thi3 tutorial 3how3 all function3 in3ide the main calculation 3oftware( 8dditional 6D03 are a9ailable
for editing@ adding@ and 3earching component3@ a3 well a3 for modifyingDunder3tanding the DDB
configuration@ and the interaction parameter editor(
" 0reden3lund 8(@ Eone3 :(=(@ 6rau3nitF E(M(@ BGroup-ontribution 23timation of 8cti9ity oefficient3 in <onideal
=iAuid Mi1ture3C@ 87h2 E(@ $",%-@ "#/%-"#&&@ "&?>
$ 5eidlich ;(@ Gmehling E(@ B8 Modified ;<708 Model( "( 6rediction of G=2@ h2@ and H
IC
@ 7nd( 2ng( hem( :e3(@
$%,?-@ ".?$-"./"@ "&/?
. 5ittig :(@ =ohmann E(@ Gmehling E(@ BGapor-=iAuid 2Auilibria by ;<708 Group ontribution( %( :e9i3ion and
21ten3ionC@ 7nd( 2ng( hem( :e3(@ +$,"-@ "/.-"//@ $##.
+ Gmehling E(@ 5ittig :(@ =ohmann E(@ Eoh :(@ B8 Modified ;<708 ,Dortmund- Model( +( :e9i3ion and 21ten3ionC@
7nd( 2ng( hem( :e3(@ +",%-@ "%?/-"%//@ $##$
> Eakob 8(@ Gren3emann H(@ =ohmann E(@ Gmehling E(@ B0urther De9elopment of Modified ;<708 ,Dortmund-)
:e9i3ion and 21ten3ion >C@ 7nd( 2ng( hem( :e3(@ +>,$.-@ ?&$+-?&..@ $##%
% <ebig S(@ Gmehling E(@ B6rediction of pha3e eAuilibria and e1ce33 propertie3 for 3y3tem3 with ionic liAuid3 u3ing
modified ;<708) Typical re3ult3 and pre3ent 3tatu3 of the modified ;<708 matri1 for ionic liAuid3C@ 0luid 6ha3e
2Auilib(@ .#$,"-$-@ $$#-$$>@ $#""
;<708 6age . of "$
DDBSP- Dortmund Data Bank Software 6ackage $#".
Building a System
8 3y3tem contain3 of 3e9eral pure component3( omponent can be added by the B8dd omponentC
button( The call3 the 3tandard DDB component 3election package which i3 de3cribed in detail3 in a
3eparate 6D0 ,Bomponent Management@ hapter &-(
The dialog allow3 3earching for name3@ formula3@ 8S regi3try number3@ and many more criteria(
;<708 6age + of "$
Figure 1: UNIFAC Graphical User Interface
Figure 2: Component Selection
Sy3tem
,=i3t of
omponent3-
8dd
omponent3
omponent
=i3t
Search
DDBSP- Dortmund Data Bank Software 6ackage $#".
The component li3t 3hown i3 the complete li3t of component3 a9ailable in the Dortmund Data Bank(
7t include3 al3o many component3 for which no group a33ignment3 are a9ailable(
8fter a component ha3 been 3elected ,by a double-click or by -
the component i3 added to the component li3t(
Thi3 li3t di3play3 the DDB internal number@ an 2ngli3h name@ the empirical formula@ the molecular
weight@ and both the group a33ignment3 for ;<708 and modified ;<708 ,Dortmund-( 7f a group
a33ignment i3 not gi9en a Bn(a(C i3 written(
Single component3 can be remo9ed by double-clicking the line@ the
complete li3t can be cleared by clicking the B:emo9e 8llC button(
The 3y3tem table ha3 a conte1t menu which allow3
"( :emo9e all component3
$( :emo9e the 3elected component
.( opying@ printing@ and 3a9ing the component li3t
+( 8uto-3iFe the column3 of the table
>( Di3play detail3 of the group a33ignment
The normal di3play in the component li3t only di3play3 the 3ub group3 of the component3 and thi3
dialog add3 information about the main group3(
;<708 6age > of "$
Figure 3: Component List
Mi33ing
Group
833ignment
Group
833ignment3
Figure 4: Group Assignment etails
DDBSP- Dortmund Data Bank Software 6ackage $#".
Checking Parameter Aailability
;<708 need3 the component 3pecific group a33ignment and interaction parameter3 between all
main group3 pre3ent in the current mi1ture(
The dialog ha3 two page3)
"( The fir3t page only di3play3 if all parameter3 are a9ailable
$( The 3econd page gi9e3 detail3 about the group a33ignment for all component3 and all main
group interaction3( The e1ample 3how3 that for the gi9en 3y3tem ;<708 can be u3ed but
modified ;<708 ,Dortmund- will fail becau3e of a mi33ing interaction parameter(
;<708 6age % of "$
Figure !: "arameter A#aila$ilit%
DDBSP- Dortmund Data Bank Software 6ackage $#".
UNIFAC
Component 11: Ethanol
Subgroups: 1 (CH3 ) 2 (CH2 ) 14 (OH )
Component 12: Diethyl ether
Subgroups: 1 (CH3 ) 2 (CH2 ) 25 (OCH2 )
Component 1: !niline
Subgroups: " (!CH ) 3# (!C$H2 )
Component 15: %ormi& a&i'
Subgroups: 43 (HCOOH )
(ist o) *ain +roups
*aingroups: 1 (CH2 ) 3 (!CH ) 5 (OH ) 13 (CH2O ) 1 (!C$H2 ) 2,
(COOH )
-ntera&tion parameters
1 . 3: 1 parameter/s
1 . 5: 1 parameter/s
1 . 13: 1 parameter/s
1 . 1: 1 parameter/s
1 . 2,: 1 parameter/s
3 . 5: 1 parameter/s
3 . 13: 1 parameter/s
3 . 1: 1 parameter/s
3 . 2,: 1 parameter/s
5 . 13: 1 parameter/s
5 . 1: 1 parameter/s
5 . 2,: 1 parameter/s
13 . 1: 1 parameter/s
13 . 2,: 1 parameter/s
1 . 2,: 1 parameter/s
System has all parameters available.
mod. UNIFAC (Dortmund)
Component 11: Ethanol
Subgroups: 1 (CH3 ) 2 (CH2 ) 14 (OH (0) )
Component 12: Diethyl ether
Subgroups: 2 (CH2 ) 1 (CH3 ) 25 (OCH2 )
Component 1: !niline
Subgroups: " (!CH ) 3# (!C$H2 )
Component 15: %ormi& a&i'
Subgroups: 43 (HCOOH )
(ist o) *ain +roups
*aingroups: 1 (CH2) 3 (!CH) 5 (OH) 13 (CH2O) 1 (!C$H2) 44 (HCOOH)
-ntera&tion parameters
1 . 3: 2 parameter/s
1 . 5: 3 parameter/s
1 . 13: 2 parameter/s
1 . 1: 3 parameter/s
1 . 44: 1 parameter/s
3 . 5: 3 parameter/s
3 . 13: 2 parameter/s
3 . 1: 3 parameter/s
3 . 44: 3 parameter/s
5 . 13: 3 parameter/s
;<708 6age ? of "$
DDBSP- Dortmund Data Bank Software 6ackage $#".
5 . 1: 3 parameter/s
5 . 44: , parameter/s
13 . 1: 2 parameter/s
13 . 44: 1 parameter/s
1 . 44: , parameter/s
0arameters are missing1
Calculation
Isothermal Calculation over a Concentration Range
0or a con3tant temperature it i3 po33ible to
enter compo3ition3 manually or let the
program calculate 3ome auto-di3tributed
compo3ition point3(
The BSet ompo3ition3C button open3 a
dialog where compo3ition3 can be created
,Breate Data 6oint3C-( 7n thi3 dialog it i3
po33ible to enter compo3ition3 directly in the
data grid and it allow3 creating data point3 o9er
a compo3ition range(
Special ca3e like con3tant compo3ition3 or
compo3ition ratio3 for 3ingle or few
component3 are al3o 3upported( The
compo3ition grid can be copied to the 5indow3
clipboard a3 well a3 data can be pa3ted from the
clipboard( Thi3 allow3 creating and managing
compo3ition3 out3ide thi3 program ,maybe in
Micro3oft 21cel or 'pen'ffice alc-(
ompo3ition3 can al3o be 3a9ed to and re3tored
,B'penC- from file3(
The number of po33ible data point3 i3 limited to
"###"(
Special compo3ition3 can be con3tant
compo3ition3 for 3ingle component3 or 3pecial
;<708 6age / of "$
Data Grid
Figure &: Composition Settings
Figure ': Calculation at Constant (emperature
Figure ): Calculation Settings
DDBSP- Dortmund Data Bank Software 6ackage $#".
compo3ition ratio3 ,3pecified by integer 9alue3 like + and > four a
+
D
>
ratio- for a li3t of component3(
Calculation at Constant Compositions over a Temperature Range
Thi3 calculation type allow3 the 3pecification of a 3ingle compo3ition line and a temperature range( The
compo3ition can be entered a3 mole fraction3 and a3 weight fraction3(
Result Grid
Figure 11: *esult Gri+
The re3ult grid 3how3 all gi9en compo3ition3 and the wanted temperature3 fir3t followed by the
calculated acti9ity coefficient3@ the heat of mi1ing and the e1ce33 heat capacity(
Figure 12: *esult Gri+ ,ith LL- Calculation
;<708 6age & of "$
Figure .: Special Compositions
Figure 1/: Calculation Setting for Constant Compositions
DDBSP- Dortmund Data Bank Software 6ackage $#".
7f the ==2 calculation i3 acti9e the initial concentration3 are treated a3 feed( The re3ult grid will then
be e1tended by two pha3e column3 for each component and two acti9ity coefficientDh2Dcp2 column3
for the 3econd pha3e( The additional column3 will be pre3ent e9en if no ==2 wa3 found(
The table can be 3a9ed a3 Micro3oft 21cel ,B1l3C- file , - or copied to the 5indow3
clipboard , -(
Activity Coefficient Diagram
7n ca3e of the calculation at a fi1ed 3ingle compo3ition at different temperature3 a diagram with the
temperature-dependent acti9ity coefficient3 i3 di3played(
The Menus
;<708 6age "# of "$
Figure 13: (emperature0+epen+ent Acti#it% Coefficients
DDBSP- Dortmund Data Bank Software 6ackage $#".
omponent li3t3 are file3
containing raw data 3et
number3( The3e file ha9e the
e1ten3ion B3tlC(
The 3y3tem grid can al3o be
3a9ed a3 a comma 3eparated file
which can be loaded in 3pread
3heet program3(
The 3y3tem grid ,component
li3t- can be copied and printed(
Bomponent3C 3tart3 the
omponent 2ditor ,de3cribed in
BomponentManagement(pdfC-
BShow Hint3C acti9ate3
additional hint for many item3
on the form(
B7nteraction 6arameter Matri1C
3tart3 the parameter editor
,de3cribed in BG Model
6arameter3(pdfC-
BDDB onfigurationC 3tart3 the
configuration program
,de3cribed in
BDDBonfiguration(pdfC-
Appendix
UNIFAC
The 2$-%!C group contribution model
?
ha3 been de9eloped to e3timate the real 9apor-liAuid
eAuilibrium beha9ior( 7n a group contribution model the mi1ture i3 not 3een a3 a mi1ture of
component3 but a3 a mi1ture of group3( The large ad9antage i3 that the number of 3tructural group3 i3
much 3maller ,doFen3- than the number of component3 ,million3-( Thi3 mean3 that it i3 po33ible to
calculate mo3t 3y3tem3 of commercial intere3t with 9ery few group information(
2$-%!C i3 ba3ed on the 2$-32!C eAuation( Therefore acti9ity coefficient3 are calculated from two
term3@
*
i
C
i
ln ln ln + = (
The combinatorial part i3 calculated in the 3ame manner a3 in 2$-32!C@
|
|
.
|

\
|
+ + =
i
i
i
i
i i i
C
i
F
1
F
1
2 1 1 ln " > ln " ln
with

=
3
3 3
i
i
4 r
r
1
and

=
3
3 3
i
i
4 2
2
F
(
0or the calculation of the combinatorial part only the relati9e 9an der 5aal3 9olume
i
r
and 3urface
i
2

together with the mole fraction3
i
4
are needed(
? Gmehling E(@Jolbe B(@ BThermodynamikC@ Gerlag hemie@ 5einheim ,"&/?-
;<708 6age "" of "$
DDBSP- Dortmund Data Bank Software 6ackage $#".
The 9an der 5aal3 9olume and 3urface can be calculated from group 9olume3 and 3urface3@

=
5
5
i
5 i
* r
- ,
v

=
5
i
5 i
6 2
- ,
v
with
- ,i
5
v a3 the number of 3tructural group3 of type 5 in the molecule i (
The re3idual part ha3 to be calculated from the group acti9ity coefficient3
5
I
@
( )

I I =
- , - ,
ln ln ln
i
5 5
i
5
*
i
v
(
The concentration dependency of the group acti9ity coefficient3 in the mi1ture
5
I
,and in the pure
component
- ,i
5
I - mu3t be calculated in analogy to the 2$-32!C eAuation@
(
(
(

+ O
+ O
|
.
|

\
|
+ O = I

m
n
n n
m m
m
m m 5 5
6 ln " ln
(
The 3urface contribution
m
O
and the mole fraction
m
7
of the group i3 defined by

= O
n
n n
m m
m
7 6
7 6

=
3 n
3 3 n
3
3
m
3
m
4
4
7
@
v
v
and the parameter
nm
+
i3 defined a3
(
a
nm
nm
e

= +
with
nm
a
a3 group interaction parameter3 between the group3
n
and
m
(
Modified ;<708 ,Dortmund- u3e3 temperature-dependent interaction parameter3)
(
( c
(
( $
(
a
nm
nm nm nm
e
$

+

+

= +
;<708 6age "$ of "$