User Guide for

Models and Physical Properties

Infochem Computer Services Ltd
Version 4.1
26 January 2012
Infochem Computer Services Ltd
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Infochem Computer Services Ltd
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London S#& L'( U)
Tel*+44 ,-.- /!0/ -1--
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correct and that the software and data to which it relates are free from errors( no guarantee is
given or implied as to their correctness or accuracy. 8either Infochem Computer Services Ltd nor
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or error in this document( the software or the data.
Contents
Overview......................................................................................................................
Introduction.................................................................................................................0
7hat types of model are availa%le:........................................................................0
!hermodynamic properties from an "#uation of State.....................$
Introduction.................................................................................................................1
#nthalpy........................................................................................................................1
#ntropy..........................................................................................................................3
Fugacity coefficients................................................................................................&-
Gi%%s #nergy and Internal #nergy........................................................................&&
;eat Capacity( constant pressure.........................................................................&&
;eat Capacity( constant volume...........................................................................&&
Isothermal compressi%ility....................................................................................&
Iso%aric e2pansivity or thermal e2pansion........................................................&
<ctivity Coefficient..................................................................................................&
Speed of Sound.........................................................................................................&
"#uations of state provided in Multiflash..............................................%&
7hen to use e9uation of state models...............................................................&4
Ideal gas e9uation of state.....................................................................................&0
'eng4=o%inson e9uation of state..........................................................................&0
'eng4=o%inson &3/1 >'=/1? e9uation of state..................................................&@
=edlich4)wong >=)? and =edlich4)wong4Soave >=)S? e9uations...................&@
Aud6evitch4Boffee >AB?.............................................................................................&/
<dvanced #9uation of state options...................................................................&/
Cu%ic plus association >C'<? model....................................................................-
'C4S<FT e9uation of state....................................................................................
'S=) e9uation of state...........................................................................................4
'S=)48=TL e9uation of state................................................................................4
Lee4)esler >L)? and Lee4)esler4'lCc6er >L)'? e9uations of state..................4
Denedict47e%%4=u%in4Starling >D7=S? e9uation of state................................@
Eulti4reference fluid corresponding states >CSE? model.............................../
'ctivity coefficient e#uations in Multiflash..........................................()
7hen to use activity coefficient models.............................................................!
Ideal solution model................................................................................................!
7ilson e9uation........................................................................................................!!
8=TL e9uation..........................................................................................................!!
U8I"U<C e9uation..................................................................................................!4
U8IF<C group4contri%ution methods.................................................................!4
=egular solution theory..........................................................................................!@
Flory4;uggins theory...............................................................................................!@
Gas phase models for activity coefficient methods.........................................!/
Models for solid phases....................................................................................($
Introduction..............................................................................................................!1
Solid free$e4out model............................................................................................!1
Eodelling hydrate formation and inhi%ition.....................................................!3
Salinity Eodel............................................................................................................4!
Eodelling wa2 precipitation..................................................................................44
Eodelling asphaltene flocculation.......................................................................44
Fther thermodynamic models..............................................................................40
!ransport property models............................................................................&*
Introduction..............................................................................................................4/
Giscosity.....................................................................................................................4/
Thermal conductivity..............................................................................................0-
Surface Tension........................................................................................................0
Hiffusion coefficients..............................................................................................0!
+inary interaction parameters......................................................................
Introduction..............................................................................................................00
8um%er of DI's related to any model..................................................................00
Units for DI's.............................................................................................................0@
DI's availa%le in Eultiflash....................................................................................0/
Model data re#uirements.................................................................................,
Components............................................................................................................-(
Introduction..............................................................................................................@!
8ormal components................................................................................................@!
'etroleum fractions................................................................................................./&
Inde.............................................................................................................................*&
Overview
Introduction
Eultiflash is an advanced software pac6age for performing
comple2 e9uili%rium calculations 9uic6ly and relia%ly. The main
utility is a multiple phase e9uili%rium algorithm that is interfaced
to InfochemIs pac6age of thermodynamic models and a num%er of
physical property data %an6s.
The purpose of this guide is to provide more detailed descriptions
of the models availa%le in Eultiflash than you will find in our main
User Guide. The correlation e9uations for storing pure component
properties in our physical property data%an6s will also %e
descri%ed.
This section defines what a model is in terms of the Eultiflash
nomenclature( what models are availa%le and when you might wish
to use them.
/hat types of model are availa0le1
7ithin the conte2t of Eultiflash( a model is a mathematical
description of how one or more thermodynamic or transport
properties of a fluid or solid will depend on pressure( temperature
or composition.
The 6ey thermodynamic property calculation carried out within
Eultiflash is the determination of phase e9uili%rium. This is %ased
on the fundamental relationship that at e9uili%rium the fugacity of
a component is e9ual in all phases. For a simple vapour4li9uid
system
f f
i
v
i
l

where f
i
v
is the fugacity of component i in the vapour phase and
f
i
l
is the fugacity of component i in the li9uid phase.
The models used in Eultiflash to represent the fugacities from the
phase e9uili%rium relationship in terms of measura%le state
varia%les >temperature( pressure( enthalpy( entropy( volume and
internal energy? fall into two groups( e9uation of state methods

and activity coefficient methods. The %asis of each of these

methods is descri%ed %elow.
7ith an e9uation of state method( all thermal properties for any
fluid phase can %e derived from the e9uation of state. 7ith an
activity coefficient method the vapour phase properties are derived
from an e9uation of state( whereas the li9uid properties are
determined from the summation of the pure component properties
to which a mi2ing term or an e2cess term has %een added.
Eultiflash may also %e used to calculate the phase e9uili%rium of
systems containing solid phases( either mi2ed or pure. These may
occur either when a normal fluid free$es or may %e a particular
solid phase such as a hydrate( wa2 or asphaltene. Eodels used to
represent these solids are discussed %elow.
The transport properties of a phase >viscosity( thermal
conductivity and surface tension? are derived from semi4empirical
models( which will %e discussed later.
"#uation of state methods
<n e9uation of state descri%es the pressure( volume and
temperature >'GT? %ehaviour of pure components and mi2tures.
Eost e9uations of state have different terms to represent the
attractive and repulsive forces %etween molecules. <ny
thermodynamic property( such as fugacity coefficients and
enthalpies( can %e calculated from an e9uation of state relative to
the ideal gas properties of the same mi2ture at the same
conditions.
In the e9uation of state method the partial pressure of a
component i in a gas mi2ture is
p y p
i i

.
The fugacity of a component in an ideal gas mi2ture is e9ual to its
partial pressureJ the fugacity in a real mi2ture is the effective
partial pressure
f y p
i
v
i
v
i

where
i
v
is the fugacity coefficient. For a vapour at moderate
pressures
i
v
is close to unity.
Similarly for a li9uid
f x p
i
l
i
l
i
l

<lthough as a li9uid differs considera%ly from an ideal gas the
fugacity coefficients for a li9uid are very different from unity.
'ctivity coefficient methods
In an ideal li9uid solution the li9uid fugacity of each component in
the mi2ture is directly proportional to the mole fraction of the
component
f x f
i
l
i i
l

*,
-
The ideal solution assumes that all molecules in the li9uid solution
are identical in si$e and are randomly distri%uted. This assumption
is valid for mi2tures made up of molecules of similar si$e and
type( %ut for mi2tures of unli6e molecules you must e2pect varying
degrees of non4ideality. The activity coefficient(
i
( represents the
deviation of the mi2ture from ideality( as defined %y the ideal
solution.
The fugacity coefficients for the activity coefficient e9uations are
calculated from the standard relationship*
ln ln ln ln ln
i i i
sat
i
sat
i
p p + + +
where
i
is the activity coefficient of component i which is
derived from the e2cess Gi%%s energy as follows*
ln

i
E
i
G
n

.
p
i
sat
is the saturated vapour pressure of component i (
i
sat
is the
fugacity coefficient of the pure saturated vapour of component i
>calculated from the gas phase model associated with the activity
coefficient e9uation? and
p
is the total pressure.
The 'oynting correction(
i
( corrects the fugacity coefficient from
the standard state pressure >i.e. the saturation pressure? to the
system pressure. It is evaluated on the assumption of ideality( i.e.
assuming that there is $ero e2cess volume of mi2ing( and that the
li9uid is incompressi%le*

i
i
sat
i
sat
p p v
RT

( )
where v
i
sat
is the saturated li9uid volume of component i .
*
!hermodynamic properties
from an "#uation of State
Introduction
<ny thermodynamic property can %e calculated with an e9uation
of state. This section present the general e2pressions used in
Eultiflash to calculate thermodynamic properties( li6e enthalpy
and fugacity coefficients from e9uations of state. Some properties(
li6e enthalpy and entropy are calculate directly from the e9uation
of state( while others li6e the Gi%%s energy are calculated as
com%inations of other properties.
"nthalpy
In Eultiflash the enthalpy is calculated as
H=H
ref
+H
pg
+H
res
(
where*
H
ref
is the >ar%itrary? enthalpy value in a reference state to %e
defined.
H
pg
is the perfect gas contri%ution to the enthalpy( given %y*
H
pg
=

T
ref
T
C
P , pg
dT (
where C
P , pg
is the perfect gas heat capacityJ
H
res
is the residual enthalpy( which is calculated from the
thermodynamic model specified for thermal properties( using the
standard thermodynamic relation*
H
res
=PV RT+

V
[(
P
T
)
V
P
]
dV
.
The a%solute value of enthalpy has no physical meaning %ut
enthalpy differences are measura%le 9uantities( therefore H
ref
can
$
%e chosen at will. Eultiflash has two possi%le reference states that
are user selecta%le*
&. KCompoundI datum >default?* The enthalpy of each pure
component in the perfect gas state at 31.&0 ) and & atm is set to
$ero. This is done %y setting*
H
ref
=H
pg
298
(
where H
pg
298
is the value of
H
pg
at T L 31.&0 ).
. K#lementsI datum* The enthalpy of each element is set to $ero in
the perfect gas state at 31.&0) and & atm.( which is done %y
setting*
H
ref
=H
f
o
H
pg
298
(
where H
f
o
is the standard enthalpy of formation of the
compounds in the perfect gas state at 31.&0 ) and & atm.
This datum produces enthalpy values that are much larger
numerically than the KcompoundI datum %ut enthalpy differences
%etween two states are the same. 7hen calculating chemical
reaction e9uili%rium the KelementsI datum must %e used %ecause it
is the elemental entities that are conserved rather than the
molecular entities.
The overall enthalpy is o%tained %y multiplying the mole num%ers
of each phase with the enthalpy of each phase( and summing over
all phases*
H=

j
NP
n
j
H
j
.
"ntropy
The entropy is in Eultiflash calculated as*
S=S
ref
+S
pg
+S
res
(
where*
S
ref
is the >ar%itrary? entropy value in a reference state to %e
defined.
S
pg
is the perfect gas contri%ution to the entropy( given %y*
S
pg
=

T
ref
T
C
P , pg
T
dT (
where C
P , pg
is the perfect gas heat capacityJ
S
res
is the residual entropy at specified T and '( which is
calculated from the thermodynamic model specified for thermal
properties( using the standard thermodynamic relation*
S
res
=

0
P
[(
P
T
)
V

R
V
]
dV +Rln Z (
,
where A is the compressi%ility factor*
Z=
PV
n RT
.
<lthough the a%solute entropy can %e argued to have a physical
interpretation( in practise( it is entropy differences that are
e2perimentally accessi%le and S
ref
can %e chosen at will. Eultiflash
has three possi%le reference states that are user selecta%le*
&. KCompoundI datum >default?* The entropy of each pure
component in the perfect gas state at 31.&0 ) and & atm is set to
$ero. This is done %y setting*
S
ref
=S
pg
298
(
where S
pg
298
is the value of S
pg
at 31.&0 ).
. K#lementsI datum* The entropy of each element is set to $ero in
the perfect gas state at 31.&0) and & atm( %y setting*
S
ref
=S
f
o
S
pg
298
(
where S
f
o
is the entropy of formation at 31.&0 ) and & atm.
This datum produces values that are much larger numerically than
the KcompoundI datum %ut entropy differences %etween two states
are the same. 7hen calculating chemical reaction e9uili%rium the
KelementsI datum must %e used.
!. KStandardI datum >sometimes called the Kthird4law or Ka%soluteI
entropy?* The reference entropy is chosen so that the entropy of
each component in the perfect gas state at 31.&0) and & atm is
e9ual to the standard entropy of that component. This is done %y
setting*
S
ref
=S
o
S
pg
298
The standard entropy(
S
o
is relative to a $ero value at a%solute
$ero. The KstandardI datum may also %e used in chemical reaction
analysis since the results are e9uivalent to the KelementsI datum.
The overall entropy is o%tained %y multiplying the mole num%ers
of each phase with the entropy of each phase( and summing over
all phases.
2u3acity coefficients
The fugacity coefficient(

i
is the ratio %etween the fugacity and
the partial pressure of a given component*

i
=

f
i
P x
i
It is calculated as*
ln

i
=
1
RT

V
[(
P
n
i
)
T ,V , n
j

RT
V ]
dV ln Z
%4
Gi00s "ner3y and Internal "ner3y
The internal energy( U is calculated from the enthalpy*
U=HPV
and the Gi%%s free energy( G is calculated from the enthalpy and
entropy
G=HTS
5eat Capacity6 constant pressure
The heat capacity at constant pressure( C
P
is e9ual to the
temperature derivative of the enthalpy at constant pressure*
C
P
=
(
H
T
)
P
.
It is calculated as the sum of a perfect gas and a residual
contri%ution*
C
P
=C
P , pg
+C
P ,res
=C
P , pg
+
(
H
res
T
)
P
(
where H
res
is defined under enthalpy and C
P , pg
is the perfect
gas heat capacity.
< num%er of correlations for the perfect gas heat capacity are
stored in the Infodata data%an6( %ut user4defined correlations may
%e entered . 7hich correlation from the data%an6 is used depends
on the component.
<s for enthalpy the overall heat capacity is o%tained %y multiplying
the heat capacity of each phase with the corresponding mole
num%ers.
5eat Capacity6 constant volume
C
V
is the heat capacity at constant volume( given %y the
temperature derivative of the internal energy at constant volume*
C
V
=
(
U
T
)
V
.
Eore conveniently it can %e calculated from the constant pressure
heat capacity and the temperature and pressure derivatives of G*
C
V
=C
P
+T
(
V
T
)
P
2
(
V
P
)
T
1
.
<s for enthalpy the overall heat capacity is o%tained %y multiplying
the enthalpy of each phase with the corresponding mole num%ers.
%%
Isothermal compressi0ility
The 9uantity isothermal compressi%ility( ( is the response of a
material in terms of volume change when pressure is applied at
constant temperature.
It is determined using the following e2pression*
=
1
V
V
p

T =const
7here V is the volume( p is the pressure and T is the temperature.
The inverse of the compressi%ility is called the %ul6 modulus.
Iso0aric e.pansivity or thermal e.pansion
The 9uantity iso%aric e2pansivity(

( is the response of a material

in terms of volume change when temperature changes at constant
pressure.
It is determined using the following e2pression*
=
1
V
V
T

p=const
7here V is the volume( p is the pressure and T is the temperature.
'ctivity Coefficient
The activity coefficient of a component is defined as the activity of
that component divided %y the mole fraction*

a
i
(T , P , n)
x
i
(
and it is in Eultiflash calculated as the fugacity of the component
in the mi2ture divided %y the pure component fugacity at the same
temperature and pressure*

i
=

i
(T , P , n)

i
(T , P)
.
Speed of Sound
The Speed of Sound of each phase is calculated as*
c=

C
P
V
2
C
V

!
V
P
(
%)
where
!
is the molecular weight of the phase
For multiple phases the overall speed of sound is estimated using
the e9uation of 7allis. =eference* G. D. 7allis* MFne dimensional
two4phase flowM( EcGraw4;ill( &3@3.
c=

j
NP
n
j
(
C
P , j
C
V , j
V
j
P
)
%(
"#uations of state provided in
Multiflash
/hen to use e#uation of state models
#9uations of state can %e used over wide ranges of temperature
and pressure( including the su%4critical and supercritical regions.
They are fre9uently used for ideal or slightly non4ideal systems
such as those related to the oil and gas industry where modelling
of hydrocar%on systems( perhaps containing light gases such as
;S( CF and 8( is the norm. #9uation of state methods do not
necessarily represent highly non4ideal chemical systems( such as
alcohol4water( well. For this type of system( at low pressure( an
activity coefficient approach is prefera%le %ut at higher pressure
you may need to use an e9uation of state with e2cess Gi%%s energy
mi2ing rules( see NEi2ing =ulesO on page &1.
<ll e9uations of state will descri%e any system more accurately
when %inary interaction parameters >DI's? have %een derived from
the regression of e2perimental phase e9uili%rium data. DI's are
adPusta%le factors( which are used to alter the predictions from a
model until these reproduce as closely as possi%le the
e2perimental data.
<s mentioned earlier the thermal properties of any fluid phase can
%e derived from an e9uation of state. ;owever( one property(
which is often poorly represented %y the simpler e9uations of
state( is the li9uid density. Eultiflash offers enhanced versions of
%oth the =edlich4)wong4Soave >=)S? and 'eng4=o%inson >'=? cu%ic
e9uations of state where the e9uation of state parameters can %e
fitted to reproduce %oth the saturated vapour pressure using a
data%an6 correlation and the saturated li9uid density at 31) or
TrL-./ >'enelou2 method?. These are referred to in Eultiflash as the
advanced version of the particular e9uation of state.
Further guidance on the use of specialised e9uations of state is
given in the following sections.
%&
Ideal 3as e#uation of state
The ideal gas e9uation of state is defined as
p=
N RT
V
.
This model is normally used in conPunction with an activity
coefficient method when the latter is used to model the li9uid
phase. It could also %e used to descri%e the %ehaviour of gases at
low pressure.
Pen378o0inson e#uation of state
The 'eng4=o%inson >'=? e9uation is a cu%ic e9uation of state. It is
descri%ed %y
p
NRT
V "
a
V "V "

+
+
2 2
2

where a and " are derived from functions of pure component
critical temperatures and pressures and acentric factor.
( ) ( )
a a T T
i ci i ci
+ 1 1
2

a
R T
p
ci
ci
ci
0 4!24
2 2
"
and

i i i
+ 0#!4$4 1422$ 0 2$992
2
" " "
e2cept for water when T T
ci
Q -.10 where the following
alternative relation is used*
( ) ( )
a a T T
i ci ci
+ 1008$!! 08214 1
2
" "
The standard >Gan der 7aals &4fluid? mi2ing rules are*
N n
i
i

a a a # n n
i j
ij
ij i j

( ) 1
" " n
i i
i

"
RT
p
i
ci
ci
0 0!!80 "
#
ij
is usually referred to as a %inary interaction parameter( the use
of such parameters is discussed in a later section.
%
Pen378o0inson %,*$ 9P8*$: e#uation of state
The &3/1 revised version of the 'eng4=o%inson e9uation has a
different treatment for the parameter . If the acentric factor
49 " 0 < the same e2pression is used as %efore*

i i i
+ 0#!4$4 1422$ 0 2$992
2
" " "
%ut( if 49 " 0 the following relationship is used*
# 2
01$$$ " 0 1$442# " 0 480# " 1 #!9$42 " 0
i i i i
+ +
The new e2pression removes a defect in the original e9uation
where heavy components with higher acentric factors %ecome
more volatile than components with somewhat lower acentric
factors. ;owever( for any mi2ture containing components with
acentric factors greater than -.43 the '=/1 e9uation will give
different results and must therefore %e treated as a different
model.
8edlich7;won3 98;: and 8edlich7;won37Soave
98;S: e#uations
Li6e 'eng4=o%inson( the =edlich4)wong and =edlich4)wong4Soave
e9uation and its variants are e2amples of simple cu%ic e9uations
of state.
They are descri%ed %y*
p
NRT
V "
a
V V "

+
+ ( )
where for the original =) e9uation*
a a T T
i ci ci

a
R T
p
ci
ci
ci
0 42!48
2 2
"
for the Soave variant >=)S?*
( ) ( )
a a T T
i ci i ci
+ 1 1
2

where*

i i i
+ 048 1!4 01!$
2
" " "
and for the SoaveR<'I variant*
( ) ( )
a a T T
i ci i ci
+ 1 1
2

where*

i i i
+ 04808 11! 01$1#
2
" " "
%-
e2cept for hydrogen( which in the <'I variant is given %y*
a a
T
T
i ci
ci

_
,

1202 0 #0228 " e%p "

The standard >Gan der 7aals &4fluid? mi2ing rules are*
N n
i
i

a a a # n n
i j
ij
ij i j

( ) 1
" " n
i i
i

"
RT
p
i
ci
ci
0 08$$4 "
<ud=evitch7>offee 9<>:
The AB eos is %ased on the original version of =edlic64)wong >=)?
eos.
For the original version of =)( the NaO and N%O parameters are
e2pressed e2plicitly in terms of the critical temperature and
pressure
p
NRT
V "
a
V V "

+
+ ( )
where the a
i
and b
i
for each component are defined as*
"
i
=0"08$$4
RT
c
p
c
a
i
=0"42!48
R
2
T
ci
2
p
ci

T
ci
/ T
For the AB eos( the a
i
and b
i
parameters are defined %y
simultaneously solving the e9uations of fugacity coefficients along
the saturation line and the =)S e9uation for %oth vapour and
saturated li9uid phase( where the re9uired saturation vapour
pressure and saturated li9uid density are o%tained from the
correlation of the pure components.
'dvanced "#uation of state options
The advanced implementation of %oth the 'eng4=o%inson and the
=edlich4)wong4Soave e9uations of state >'=<( '=/1< and =)S<
models? contain additional non4standard features. These include
the a%ility to match stored values for the li9uid density and the
saturated vapour pressure and a choice of mi2ing rule.
%*
!he Penelou. density correction
This correlation is used to match the density calculated from the
e9uation of state to that stored in the chosen physical property
data system. For light gases( the density is matched at a reduced
temperature of -./ and the volume correction is assumed constant.
For li9uid components the volume shift is a function of
temperature.
T c T c c c
i i i i
&
2 1 0
+ +
i i
x c V V
'
The three coefficients may %e stored as part of the pure
component data record.
Eultiflash usually treats the volume shift as a linear function of
temperatureJ the density is matched at 3-./) and !&0./) so as to
reproduce the density and thermal e2pansivity of li9uids over a
range of temperatures centred on am%ient. ;owever( users may
also use the third term and enter the coefficient values directly.
2ittin3 the vapour pressure curve
The function for
i
a
is generalised to the following form*
( )
a a t t t t t
ci i i i i i i i i i i
+ + + + + 1
1 2
2
#
#
4
4

2

where
t T T
i ci
1
.
For each component the constants(
i1
to
i
are fitted %y linear
regression to the vapour pressure over a range of reduced
temperatures corresponding to the stored data. Fewer than 0
coefficients will %e fitted if there is insufficient data or if the
e2trapolation to low temperatures is unrealistic. If the vapour
pressure is undefined( the correlation for a
i
reverts to the
standard e9uation for that component.
Mi.in3 8ules
For highly non4ideal systems it is often useful to %e a%le to use any
Gi%%s energy e2cess model >e.g. U8I"U<C or 8=TL? as part of the
mi2ing rule for the e9uation of state. There are several different
ways in which this can %e doneJ Eultiflash currently provides
options for the E;G type mi2ing rule( the ;uron4Gidal type
mi2ing rule( the 'S=) mi2ing rule and the Infochem modification
%ased on the 8=TL e9uation. The latter is used for modelling the
fluid phases in hydrate calculations.
MHV2-type mixing rules:
N n
i
i

%$
" " n
i
i
i

a
RT"
s
$
s N
$

_
,

1
2
2
( )
( )

$
G
RT
n $
"
N"
E
i
i
i i
i
( ) ( ) ln + +

_
,

_
,

$
s s s
i i
i i
( )
( )

+
1 1
2
2
4
2

For the =)S e9uation
s
1
2 ln
and
s
2
1! 2 "
For the '= e9uation
s
1
1
2 2
2 2
2 2
0 $2#22
+

_
,
ln "
and
s
2
20129 "
.
Huron-Vidal type mixing rules:
N n
i
i

" " n
i
i
i

a "
G
s
n
a
"
E
i
i
i i
+

_
,

_
,

1

For the =)S e9uation
s
1
2 ln
For the '= e9uation
s
1
1
2 2
2 2
2 2
0 $2#22
+

_
,
ln "
PSRK type mixing rules:
N n
i
i

i
i
i
n " "

,
_

,
_

,
_

+

i i
i
i
i i
i
E
"
a
n
"
"
n
s
RT
s
G
" a ln
1 1


$4$$# " 0
1
s
Infochem mixing rules:
These mi2ing rules are similar to the original ;uron4Gidal mi2ing
rules apart from the form of the interaction parameters ij
#
( ji
#

%,
and ij

which gives a different form of temperature dependence.

These rules reduce to the conventional van der 7aals mi2ing rules
when ji ij
# #
and
0
ij

.
N n
i
i

" " n
i
i
i

a " n
n " G
n " G
i
i
j j j ji ji
j j j ji

where*

ji
i j ji
i j
a a #
" "

+
2 1 ( )

and*
G
RT
ji
ji ji ii

_
,
e%p
( )

/hen to use cu0ic e#uations of state
The simple cu%ic e9uations of state( '= and =)S( are widely used
in engineering calculations. They re9uire limited pure component
data and are ro%ust and efficient. Doth '= and =)S are used in gas4
processing( refinery and petrochemical applications. They will
usually give %roadly similar results( although if one model has
%een fitted to e2perimental data and there are no interaction
parameters for the other then the optimised model is always
prefera%le. There is some evidence that =)S gives %etter fugacities
and '= %etter volumes >densities? %ut %oth can %e improved if the
'enelou2 correction is used.
For most applications we would recommend the use of the =)S<
>or '=<( '=/1<? model sets which use the 'enelou2 correction( fit
a to the vapour pressure and use the Gan der 7aals &4fluid mi2ing
rules.
=)S< with the Infochem mi2ing rules is used as part of the hydrate
model and provides e2tra fle2i%ility to represent the highly non4
ideal polar systems. It does( however( re9uire suita%le DI's for such
systems.
The <'I variant of =)S is applica%le to petroleum systems and
mi2tures containing hydrogen( while =) may %e used instead of
ideal gas model for the vapour phase of systems where the li9uid
phase is %eing modelled with an activity coefficient model.
Cu0ic plus association 9CP': model
The C'< model consists of the =edlich4)wong4Soave e9uation plus
an additional term %ased on 7ertheimIs theory that represents the
effect of chemical association.
)4
The form of the model is*
p=

i
n
i
%
i
(
1&
i
)
V0" 4"
+
NRT
V "
+
a
V (V +")
The parameters
ci
a
and
i
" are set for each component to satisfy
the critical conditions 0
2
2

V
p
V
p
at the 6nown critical point
of that component. The parameter
a
is a function of temperature
given %y*
( ) ( )
2

4
4
#
#
2
2 1
1
i i i i i i i i i i ci i
t t t t t a T a + + + + +
where*
t T T
i ci
1
.
For each component the constants(
i 0
to
i
are fitted %y linear
regression to the vapour pressure over a range of reduced
temperatures corresponding to the stored data. Fewer than 0
coefficients will %e fitted if there are insufficient data or if the
e2trapolation to low temperatures is unrealistic.
The model uses the standard >Gan der 7aals &4fluid? mi2ing rules
which are*
N n
i
i

a a a # n n
i j
ij
ij i j

( ) 1
" " n
i i
i

"
RT
p
i
ci
ci
0 08$$4 "
The 7ertheim association term is comple2 and( for a complete
discussion( the user should refer to the scientific literature. In
summary( the terms
i
& are found %y simultaneously solving the
7ertheim e9uations( which in the C'< model have the form*
" V
& % '
&
j
j j ij
i
4 " 0
1
1

where
i
% are the num%er of >donor? %onding sites on component i
and
ij
'
is the association constant for components i and
j
.
The C'< model also uses the 'enelou2 density correction to match
the li9uid density calculated from the e9uation of state to that
stored in the chosen physical property data system. The volume
shift is a linear function of temperature which is set to match the
saturated li9uid density at two different temperatures. For light
)%
gases( a constant volume shift is used that is fitted to the gasIs
li9uid density at a reduced temperature of -./.
/hen to use CP'
The C'< model may %e used for hydrate calculations with
methanol( ethanol( E#G( H#G( T#G and salt inhi%ition( as these are
the only cases for which parameters are currently provided.
'arameters for additional su%stances may %e added in future
versions of Eultiflash.
PC7S'2! e#uation of state
The 'C4S<FT e9uation is a development of the S<FT model that
has %een shown to give good results for a wide range of polar and
non4polar su%stances including polymers. 'olymers are one of the
most important areas of application of 'C4S<FT. The model
appears to %e one of the most accurate and realistic e9uations of
state currently availa%le for modelling polymer systems.
'C4S<FT stands for the 'ertur%ed Chain Statistical <ssociating
Fluid Theory and it incorporates current ideas of how to model
accurately the detailed thermodynamics of fluids within the
framewor6 of an e9uation of state. The mathematical structure is
very comple2 and cannot %e conveniently descri%ed in a manual.
Users are referred to <ppendi2 < of the reference given %elow.
=eference* Perturbed-Chain SAFT: An Equation of State Based on a
Perturbation Theory for Chain Moleules %y Gross and Sadows6i in
Industrial and #ngineering Chemistry =esearch( 4-( &44( >--&?.
The Eultiflash version includes an implementation of the
association term of 'C4S<FT which is discussed in the paper(
Appliation of the Perturbed-Chain SAFT Equation of State to
Assoiatin! Syste"s %y Gross and Sadows6i in Industrial and
#ngineering Chemistry =esearch( 4&( 00&-( >--?. This paper
however does not discuss the mathematical formulation of the
association termJ this can %e found in the following reference.
=eference* #e$ %eferene Equation of State for Assoiatin! &iquids
%y Chapman( Gu%%ins( Bac6son and =odos$ in Industrial and
#ngineering Chemistry =esearch( 3( &/-3( >&33-?.
The Eultiflash implementation follows the same general structure
as the association term in the C'< model.
Eultiflash also has a version of 'C4S<FT with simplified mi2ing
rules as proposed %y researchers at the Hanish Technical
University.
=eference* Co"putational and Physial Perfor"ane of a Modified
PC-SAFT Equation of State for 'i!hly Asy""etri and Assoiatin!
Mi(tures %y von Solms( Eichelsen and )ontogeorgis in Industrial
and #ngineering Chemistry =esearch( 4( &-31( >--!?.
Polymer Components
'olymers are not well4defined chemical compounds %ut rather a
distri%ution of chain molecules of varying molecular weight. In
))
Eultiflash( polymers must %e represented %y one or more pseudo
components( which must %e set up as user4defined components.
Using 'C4S<FT( every pseudo component for a given polymer must
%e assigned the same values of the pure4compound parameters
S<FTSIGE< >in metres( not Sngstrom units? and S<FT#). In
addition( the S<FTE parameter must %e specified. This is normally
9uoted as a ratio to the molecular weight( so it has to %e calculated
for each polymer pseudo component 6nowing the molecular
weight. For polystyrene( for e2ample( Gross and Sadows6i give the
ratio as -.-&3( so for a polystyrene pseudo component of
molecular weight &-----( the S<FTE parameter should %e set to
&------.-&3L&3--( etc.
<dditionally( the user can define association parameters if the
polymer forms hydrogen %onds. These parameters are S<FTD#T<
which defines the volumetric or entropic parameter( and
S<FT#'SILF8 the energy or enthalpy parameter. Eultiflash also
provides an e2tension to the 'C4S<FT definition* the user can also
supply a heat capacity parameter S<FTG<EE< for the association
term. For the association term to %e non4$ero( the user must also
define the parameter S<FTFF which denotes the num%er of donor
%onding sites per segment of polymer.
Galues of 'C4S<FT parameters for polymers can %e found in
Modelin! Poly"er Syste"s )sin! the Perturbed-Chain Statistial
Assoiatin! Fluid Theory Equation of State %y Gross and Sadows6i
in Industrial and #ngineering Chemistry =esearch( 4&( &-14( >--?
and in Modelin! of poly"er phase equilibria usin! Perturbed-Chain
SAFT %y Tuma6a6a( Gross and Sadows6i in Fluid 'hase #9uili%ria(
&344&3/( 04&( >--?.
efining Polymers and !opolymers from their
Segments
Eultiflash also allows the user to define up to four polymer
segments which can %e used to define any num%er of
homopolymers or copolymers following the method of Tuma6a6a(
Gross and Sadows6i descri%ed in the reference a%ove.
For each segment the user must define the molecular weight E7
and the S<FT parameters S<FT#) and S<FTSIGE<. Fptionally( the
association parameters S<FTD#T<( S<FT#'SILF8( optionally
S<FTG<EE< and S<FTFF can %e defined.
Fnce a num%er of segments are defined( the user can then define
polymers in terms of the segments as an alternative to the normal
method of defining a S<FT component. To define polymer
components in this manner( all the user has to do is define the
molecular weight E7 of the polymer and specify the %ond
fractions %etween the segments from which the polymer is
constructed. If the polymer is formed from only one type of
segment( it is a homopolymer of that segmentJ if it is formed of
two or more types of segment( it is a copolymer. The definition of
the %ond fractions is given %y Tuma6a6a( Gross and Sadows6i(
>although their e2amples of actual values of %ond fractions are not
realistic?.
<ll other parameters of the polymer( including the segments
fractions( are then internally calculated %y Eultiflash from the
supplied molecular weight and %ond fractions. The user can define
)(
the DI's %etween normal components andRor segments. 8ote that
in the fluid composition( the amounts of the segments must all %e
set to $ero( as the segments are not real components of the
mi2ture.
PS8; e#uation of state
This model consists of the =)S< e9uation of state with vapour
pressures fitted using Eathias4Copeman parameters >if availa%le?(
the 'enelou2 volume correction and the 'S=) type mi2ing rules.
The e2cess Gi%%s energy is provided %y the 'S=) variant of the
Unifac method. This is the same as the normal GL# Unifac model
e2cept that the group ta%le has %een e2tended to include a large
num%er of common light gases.
/hen to use PS8;
The 'S=) model is an e2tension of the Unifac method. It is
intended to predict the phase %ehaviour of a wide range of polar
mi2tures using the solution of groups concept as em%odied in
Unifac. The main %enefit of 'S=) is that it is a%le to handle
mi2tures containing gases much %etter than Unifac and unli6e a
normal e9uation of state it can handle polar li9uids. This is
%ecause >a? it uses an e9uation of state with an e2cess Gi%%s
energy mi2ing rule there%y avoiding pro%lems of how to handle
supercritical components in an activity coefficient e9uationJ >%? the
Unifac group parameter ta%le has %een e2tended in 'S=) to
include ! common light gases.
PS8;7?8!L e#uation of state
This model is the same as the 'S=) model e2cept that the e2cess
Gi%%s energy is provided %y the 8=TL e9uation. So unli6e the 'S=)
e9uation( the 'S=)48=TL variant re9uires that DI's are provided
for the 8=TL e9uation in order to give accurate results. Its
advantage is that( provided the DI's are fitted to relevant phase4
e9uili%rium data( the model can give more accurate predictions
than the 'S=) e9uation.
Lee7;esler 9L;: and Lee7;esler7Pl@c=er 9L;P:
e#uations of state
The L) and L)' methods are ! parameter corresponding states
methods %ased on interpolating the reduced properties of a
mi2ture %etween those of two reference su%stances. The e9uation
for each property is of the form*
[ ]
( ( ( (
)ix
+
( )
( )
( ) ( ) 0
1
1 0

where
) 0 (
(
and
) 1 (
(
are the compressi%ility factors of the two
reference fluids e2pressed as functions of reduced temperature(
pressure and volume. To apply the method to a mi2ture( therefore(
)&
it is necessary to o%tain averaged critical properties %y the use of
mi2ing rules. The only difference %etween the L) and L)' methods
lies in the value of the parameter

in the mi2ing rules which are

defined as follows. First the critical compressi%ility factor for each
component i is defined from the acentric factor %y*
i ci
Z 08 " 0 290 " 0
and hence the critical molar volumes*
ci ci ci ci
p RT Z v &
The main mi2ing rules have the form*
i
i
i )ix c
Z x Z

,
#
# & 1 # & 1
,
2

,
_

ij
cj ci
j i )ix c
v v
x x v
ij cj ci
ij
cj ci
j i
c
)ix c
# T T
v v
x x
v
T

#
# & 1 # & 1
,
2
1

,
_

)ix c )ix c )ix c )ix c

v Z RT p
, , , ,
&
where
c
T
and
c
p
denote the critical pressure and temperature(
ij
#
denotes the DI' the default value of which is &( and R
denotes the gas constant. Su%script i denotes component i . For
the L) method
1
( whereas for the L)' method
2 " 0
.
In Eultiflash( all the DI's for the L) method are set to the default
value of &. For the L)' method( it is 9uite important to adPust the
DI's in order to get reasona%le phase e9uili%rium predictions.
Eultiflash uses correlations for the DI's proposed %y )napp et al.
In these correlations the DI's are all set to constant values(
although Eultiflash allows the user to use temperature dependent
DI's if re9uired. < complete description of the method can %e
found in Vapor-&iquid Equilibria for Mi(tures of &o$ Boilin! Point
Substanes %y )napp( HCring( Fellrich( 'lCc6er and 'rausnit$(
Chemistry Hata Series Golume GI( Hechema &31.
/hen to use L; or L;P
The methods predict fugacity coefficients( thermal properties and
volumetric properties of a mi2ture. ;owever( they are rather slow
and comple2 compared to the cu%ic e9uations of state and are not
particularly recommended for phase e9uili%rium calculations(
although they can yield accurate predictions for density and
enthalpy. They would normally %e applied to non4polar or mildly
polar mi2tures such as hydrocar%ons and light gases.
)
+enedict7/e0078u0in7Starlin3 9+/8S: e#uation of
state
The D7=S e9uation method is an && parameter non4cu%ic e9uation
of state. It is descri%ed %y

,
_

,
_

,
_

+ + + + +
2
2
2
2
2 2
e%p 1
'
V V V
C
V
*
V
C
V
+
N
V
RT
p

where*

,
_

+ +
4
0
#
0
2
0
0 0
1
T
E
T
*
T
C
,
RT
+ +

,
_

+
T
d
a
RT
" C
#
# #
1

,
_

+
T
d
a
RT
*
#
#
#

#
#
'
RT
c
C
Ei2ing rules are used to calculate the parameters from pure
component properties as follows*
N n
i
i

i
i i
n + +
0 0
( )
j i
ij
ij j i
n n # , , ,

1
0 0 0
( )
j i
ij
ij j i
n n # C C C
#
0 0 0
1

( )
j i
ij
ij j i
n n # * * *
4
0 0 0
1

( )
j i
ij
ij j i
n n # E E E

0 0 0
1

" " n
i i
i

i
i i
n a a

i
i i
n c c
)-

i
i i
n d d

i
i i
n

i
i i
n
where
#
ij
is a %inary interaction parameter. For methane( ethane(
ethylene( propane( propylene( iso%utane( n4%utane( isopentane( n4
pentane( he2ane( heptane( octane( car%on dio2ide( hydrogen
sulphide and car%on dio2ide( the pure component parameters
i
+
0
(
i
,
0
(
i
C
0
(
i
*
0
(
i
E
0
(
i
"
i
a (
i
c (
i
d (
i
and
i
are set to values
recommended %y Starling in his %oo6 KFluid Thermodynamic
'roperties for Light 'etroleum SystemsI( Gulf 'u%lishing Co.(
;ouston( &3/!. For other su%stances the pure component
parameters are estimated using correlations developed %y Starling
and ;an which are given in the same %oo6.
/hen to use the +/8S e#uation
The D7=S e9uation gives much more accurate volumetric and
thermal property predictions for light gases and hydrocar%ons.
Given suita%le interaction parameters it should give reasona%le
vapour4li9uid phase e9uili%rium predictions %ut owing to its
comple2ity( it re9uires more computing time than the cu%ic
e9uations of state.
Multi7reference fluid correspondin3 states 9CSM:
model
The CSE model is %ased on a collection of very accurate e9uations
of state for a num%er of reference fluids. It will provide accurate
values of properties for any of the reference fluids >see %elow for a
list? and it uses a &4fluid corresponding states approach to
estimate mi2ture properties. It is formulated so that mi2ture
properties will reduce to the >accurate? pure component values as
the mi2ture composition approaches each of the pure component
limits.
In Eultiflash 4.&( the G#=G4--1 models for natural gas and other
mi2tures are implemented. The models( %ased on the G#=G
Technical Eonograph &04--/ %y F. )un$ et al( not only have the
accurate reference eos for each su%stance %ut also includes a
departure function ta6ing into account the residual mi2ture
%ehaviour. There are & main and secondary natural gas
components considered in the G#=G models. They are methane
8( CF( ethane( propane( n4%utane( iso4%utane( n4pentane( iso4
pentane( n4he2ane( n4heptane( n4octane( n4nonae( n4decane( ;(
;S( F( CF( water( ;elium and <rgon.
The models ena%le the accurate description of the thermodynamic
properties of mi2tures in the e2tended fluid region for wide range
of temperature( pressure and composition.
)*
The CSE and G#=G model definition can %e considered in two
distinct parts* the definition of pseudo4critical properties for a
mi2ture >mi2ing rules?( and the prescription for com%ining the
properties of the reference su%stances to give the total mi2ture
properties >com%ining rules?.
Mi.in3 rules for critical properties
The mi2ing rule for the CSE and G#=G model is different and the
details are descri%ed as follow.
For the CSE model( the mi2ture >pseudo? critical volume is defined
as
ij ij c
i j
j i )ix c
- V n n
N
V
,
1 1
2 ,
1

where

i
i
n N
is the total mole num%er of the mi2ture(
i
n
is
the mole num%er of component i. ij
-
is a temperature4dependent
%inary interaction parameter for the critical volume( normally close
to & and
( )
#
# & 1
,
# & 1
, ,
8
1
j c i c ij c
V V V +
The mi2ture >pseudo? critical temperature is defined as
)ix c
ij ij c ij c
i j
j i )ix c
V
' V T n n
N
T
,
, ,
1 1
2 ,
1

(here j c i c ij c
T T T
, , ,

)nd ij
'
is a temperature4dependent
%inary interaction parameter >DI'?( normally close to &.-. This DI'
has a significant effect on phase e9uili%rium calculations and must
%e fitted to match e2perimental data.
For the G#=G models in Eultiflash( the mi2ture >pseudo? critical
volume is defined as
( )


+
+

1 1
,
2
,
1
i j
j
V
ji i
V
ij
ij c
V
ij j i j i
)ix c
n n
V n n n n
N
V
c c
c

where
i
n
is the mole num%er of component i*
c
V
ij
is a linear
temperature4dependent %inary interaction parameter for the
critical volume( normally close to & and
( )
#
# & 1
,
# & 1
, ,
8
1
j c i c ij c
V V V +
The
c
V
ij
and
c
V
ji
are the asymmetric constant with and the
values are usually close to &.
The mi2ture >pseudo? critical temperature in G#=G models is
defined as
)$
( )


+
+

1 1
,
2
,
1
i j
j
T
ji i
T
ij
ij c
T
ij j i j i
)ix c
n n
T n n n n
N
T
c c
c

(here j c i c ij c
T T T
, , ,

)nd
c
T
ij

is a linear temperature4
dependent %inary interaction parameter >DI'?.
For the G#=G4--1 models( the DI's for the special selected &
natural gas components are stored in the I8FFDI'S data%an6. If
the DI's are not availa%le in the data%an6( the values are set to &
%y default.
In order to improve the phase e9uili%rium prediction( the DI's that
are not availa%le in the data%an6 for %oth CSE and G#=G models
should %e o%tained %y fitting the e2perimental data.
The mi2ture >pseudo? critical compressi%ility factor is defined as

i
i c i )ix c
Z x Z
, ,
i c
i c i c
j c
RT
V P
Z
,
, ,
,

The mi2ture >pseudo? critical pressure is then defined as
)ix c
)ix c )ix c
)ix c
V
RT Z
P
,
, ,
,

Com0inin3 rule for mi.ture thermodynamic
properties
The total mi2ture reduced Gi%%s energy is o%tained %y com%ining
the pure component reduced properties as follows*
( ) ( )

i
r r i i r r )ix
P T G x P T G
,
0
,
where the reduced properties are defined as
)ix c r
T T T
,

)ix c r
P P P
,

<ll other thermodynamic properties are o%tained from the Gi%%s

energy %y differentiation.
Departure function for mi.tures in G"8G7
)44$ model
<part from the accurate reference e9uations for the pure gases(
the G#=G4--1 model has additional departure functions used for
descri%ing the %ehaviour of nonideal mi2tures. The purpose of
this function is to further improve the accuracy of the multi4
component mi2ture model in the description of thermodynamic
properties.
),
The departure function of the multi4component mi2tures(
additional contri%ution to the total reduced Gi%%s energy is the
sum of all %inary specific and generalised departure functions of
the involved %inary su%systems and is e2pressed %y
( ) ( )



1 1
, ,
2
1
, ,
i j
r r
r
ij r r
r
& P T & P T
with
( ) ( )
r r
r
ij ij j i r r
r
ij
P T % x x & P T , , ,
The parameter ij
%
, the (ei*htin* f)ctor of the component, i )nd j
in the mi%ture, is o+t)ined from fittin* the specific +in)r, mi%tures"
-he v)lues of ij
%
for the n)tur)l *)ses in the ./0.12004 model
)re stored in the I8FFDI'S data%an6. If there is no departure
function for a %inary components( the value of ij
%
is set to 2ero
+, def)ult" The +in)r, dep)rture function,
( )
r r
r
ij
P T ,
is simil)r to
the structure of ) pure su+st)nce e3u)tion of st)te +ut (ith different
e3u)tion coefficients for ) t,pic)l p)ir of +in)r, mi%ture"
8eference fluids
The current model implementation includes reference e9uations of
state for the following su%stances* ammonia( argon( iso4%utane( n4
%utane( CF( CF ( ethane( ethylene( fluorine( helium( heptane(
he2ane( hydrogen( ;S( methane( neon( nitrogen( octane( o2ygen(
n4pentane( propane( propylene( water >I<'S7 30?( Car%onyl
Sulphide( #thanol( Cyclohe2ane( iso4he2ane( )rypton( 8itrogen
Trifluoride( neo4pentane( Sulphur Hio2ide( SF@( Toluene( Tenon(
=&&( =&&!( =&&4( =&&0( =&&@( =&( =&!( =&4( =&0( =&!( =&!4a(
=&4( =&4&%( =&4%( =&4!a( =&0a( =&1( =( =!( =40fa( =C!&1(
=!( =4&( ==/#<( &4%utene( cis44%utene and trans44%utene.
<ny hydrocar%ons that do not have reference eos are modelled %y
the corresponding state model pu%lished %y L.Sun and B.F. #ly(
International Bournal of Thermophysics( vol. @( no. ( p/-0 >--0?.
This model is a three4parameter model that involves two reference
fluids( propane and octane( and the acentric factor of the
hydrocar%ons.
<ll the e9uations of state are ta6en from various sources and do
not all have the same 9uality or range of applica%ility.
'pplica0ility
The models are very accurate for pure su%stances that are
included in the a%ove list of reference su%stances. It is also
applica%le to near4ideal mi2tures such as air %ut for the %est
results it is necessary to fit values of the %inary interaction
parameters to match e2perimental data. The G#=G4--4 models
are the recommended model for natural gases.
(4
/ater
< high4accuracy model for water is availa%le as a separate model
option and is also included as part of the CSE mi2ture model. The
reference e9uation of state is the I<'7S430 formulation* +The
,AP-S For"ulation .//0 for the Ther"odyna"i Properties of
1rdinary -ater Substane for 2eneral and Sientifi )se3( 7.
7agner and <. 'russ( B. 'hys. Chem. =ef. Hata.( Gol. !&( !1/ >--?.
The I<'7S recommended e9uations for transport properties have
also %een implemented.
Car0on Dio.ide
< high4accuracy model for car%on dio2ide is availa%le as a separate
model option and is also included as part of the CSE mi2ture
model The e9uation of state is defined in* +A #e$ Equation of State
for Carbon 4io(ide Co5erin! the Fluid %e!ion fro" the Triple-Point
Te"perature to ..66 7 at pressures up to 866 MPa3( =. Span and 7.
7agner( B. 'hys. Chem. =ef. Hata.( Gol. 0( &0-3 >&33@?. The
viscosity o%tained from the correlation* +The Visosity of Carbon
Hio2ideI( <. Fenghou( 7.<. 7a6eham and G. Gesovic( B. 'hys. Chem.
=ef. Hata.( Gol. /( !& >&331?. The thermal conductivity formulation
is* +A %eferene Multipara"eter Ther"al Conduti5ity Equation for
Carbon 4io(ide $ith an 1pti"i9ed Funtional For"3( G. Scala%rin(
'. Earchi( F. Fine$$o and =. Span( B. 'hys. Chem. =ef. Hata.( Gol.
!0( &043 >--@?.
(%
'ctivity coefficient e#uations
in Multiflash
< num%er of activity coefficient e9uations are availa%le in
Eultiflash and are descri%ed %elow. The nomenclature is to denote
%inary interaction parameters %etween components i and
j
%y
,
ij
.
The 8=TL e9uation has an additional parameter

ij
.
/hen to use activity coefficient models
<ctivity coefficient models are usually used to model any
com%ination of polar and non4polar compounds including those
e2hi%iting very strong non4ideality. If the gas phase model is ideal
then pressures should %e limited to !40 %ar. If =edlich4)wong or
another e9uation of state is used to model the gas phase then the
pressure limit is higher( of the order of &-4- %ar. ;owever( the
mi2ture should %e su%critical. If the mi2ture contains some
components which are a%ove their critical point( such as dissolved
gases( then you should %e aware that the properties of
components( e.g. vapour pressure( will %e e2trapolated.
8=TL( U8I"U<C and U8IF<C may %e used to model GL#( LL# and
GLL# %ut %oth 7ilson models are limited to GL# only.
To o%tain accurate predictions from any of the activity coefficient
models( e2cept U8IF<C( it is necessary to use interaction
parameters. If these are not availa%le in I8FFDI'S for your system
the you need to supply interaction parameters for the missing
values which match the model specification given a%ove and which
are in the correct units. 'arameters in I8FFDI'S are in standard SI
units( Bmol
4&
( e2cept for 7ilson < where the DI's are dimensionless.
The user can introduce DI's in other units provided these units are
set correctly.
Ideal solution model
This is descri%ed %y*
G
RT
E
0
()
The ideal solution model may %e used when the mi2ture is ideal(
i.e. when there are no mi2ing effects. It an also %e used for single
components to calculate some pure component properties from
the physical property data%an6.
/ilson e#uation
/ilson " e#uation
This is defined %y*
G
RT
n
G n
n
E
i
j ij j
j j i

_
,

ln
where*
G
V
V
,
RT
ij
j
i
ij

_
,

*
*
e%p
V
i
*
is the saturated li9uid molar volume of component i
>e2trapolated in the case of supercritical gases? evaluated at a fi2ed
reference temperature of 31.&0).
This model may %e used for vapour4li9uid e9uili%rium calculations
%ut it is not capa%le of predicting li9uid4li9uid immisci%ility. Dinary
interaction parameters are provided in our I8FFDI'S %an6 for
some component pairs. If no DI's are included for your particular
mi2ture then to o%tain accurate predictions you must supply
%inary interaction parameter values in the correct units.
/ilson ' e#uation
G
RT
n
, n
n
E
i
j ij j
j j i

_
,

ln
This model which is a simplified form of the 7ilson # model( may
%e used for vapour4li9uid e9uili%rium calculations %ut it is not
capa%le of predicting li9uid4li9uid immisci%ility. To o%tain accurate
predictions you must supply %inary interaction parameters >DI'?
values( which are dimensionless.
?8!L e#uation
G
RT
n
, G n
n G
E
i
j ij ji j
j j ji i

_
,

ln
where*
G
a ,
RT
ij
ij ij

_
,
e%p
((
The 8=TL model may %e used for vapour4li9uid( li9uid4li9uid and
vapour4li9uid4li9uid calculations >the GL# option should %e used
for GLL#?. <gain if DI' values are not provided in I8FFDI'S they
must %e supplied for accurate predictions. In cases where the user
does not specify any value for the non4randomness factor(

ij
( it is
automatically set to -.! if the GL# version of 8=TL is specified or
to -. if the LL# version is specified. 8ote that

ij ji

so only

ij
need %e supplied.
U?IAU'C e#uation

,
_

,
_

,
_

i
j
j j
j
j j ji
i i
i
j
j j i
j
j j i
i i
i
j
j j
j
j i
i
E
n /
n / G
n /
n / r
n r /
n /
(
n r
n r
n
RT
G
ln ln
2
ln
where*
( 10
and*
G
,
RT
ij
ij

_
,
e%p
The U8I"U<C model may %e used for vapour4li9uid( li9uid4li9uid
and vapour4li9uid4li9uid calculations. In Eultiflash we provide
U8I"U<C GL# and LL# variants as for the 8=TL e9uation. <gain
DI' values must %e supplied for accurate predictions if they are not
included in I8FFDI'S. For GLL# the variant chosen should %e
guided %y the DI's availa%le.
U?I2'C 3roup7contri0ution methods
Ori3inal U?I2'C method
The U8IF<C method is similar to U8I"U<C %ut the interaction
parameters are predicted %ased on the molecular group structure
of the components in the mi2ture. The is completely predictive and
does not re9uire the user to supply DI's.
G
E
RT
=

i
n
i
ln
(
r
i

j
n
j

j
r
j
n
j )
+
(
2

i
/
i
n
i
ln
(
/
i

j
r
j
n
j
r
i

j
/
j
n
j )
+
G
RT

i
n
i
G
(i )
RT
where
i
/
and
i
r
are the U8I"U<CRU8IF<C surface and volume
parameters for component i and 10 ( . For U8IF<C they are
found %y summing the contri%utions from the groups from which
each component is formed.
G
is the residual e2cess Gi%%s energy
of the solution and
) (i
G is the residual e2cess Gi%%s energy of
(&
pure component i according to the principle of solution of
groups. The U8IF<C residual term is given %y*

,
_

#
l
l l
l
l
l l#
# #
N $
N $
$ N
RT
ln
G
The summation is over all groups in the mi2ture >or pure
component?.
#
N
is the total num%er of moles of group # (
#
$

is the surface area parameter for group # and
l#

is the
interaction parameter*

,
_

RT
,
l#
l#
e%p
In original U8IF<C( the two %inary parameters
l#
,
%etween
components l and # are normally ta6en as constants.
Dortmund modified U?I2'C method

,
_

,
_

i
0i1
i
i
j
j j i
j
j j i
i i
i
j
j j
j
j i
i
E
RT
n
RT n / r
n r /
n /
(
n r
n r
n
RT
G G G
ln
2
ln
4 & #
4 & #
where
i
/
and
i
r
are the U8I"U<CRU8IF<C surface and volume
parameters for component i and 10 ( . For U8IF<C they are
found %y summing the contri%utions from the groups from which
each component is formed.
G
is the residual e2cess Gi%%s energy
of the solution and
) (i
G is the residual e2cess Gi%%s energy of
pure component i according to the principle of solution of
groups. The U8IF<C residual term is given %y*

,
_

#
l
l l
l
l
l l#
# #
N $
N $
$ N
RT
ln
G
The summation is over all groups in the mi2ture >or pure
component?.
#
N
is the total num%er of moles of group # (
#
$

is the surface area parameter for group # and
l#

is the
interaction parameter*

,
_

RT
,
l#
l#
e%p
For Hortmund modified U8IF<C( the two %inary parameters
l#
,

%etween components l and # are treated as 9uadratic functions
of temperature.
Hortmund modified U8IF<C is %etter a%le to represent the
simultaneous vapour4li9uid e9uili%ria( li9uid4li9uid e9uili%ria and
e2cess enthalpies of polar mi2tures than the original U8IF<C
(
method. Li6e original U8IF<C( however( it does not allow for the
presence of light gases in the mi2ture.
=eferences* Gmehling and co4wor6ers( A Modified )#,FAC Model. ..
Predition of V&E* h
E
* and

( Industrial and #ngineering Chemistry

=esearch( @( &!/( >&31/?J A Modified )#,FAC Model. :. Present
Para"eter Matri( and %esults for 4ifferent Ther"odyna"i
Properties( i%id.( !( &/1( >&33!?J A Modified )#,FAC ;4ort"und<
Model. =. %e5ision and E(tension( i%id.( !/( 41/@( >&331?J A Modified
)#,FAC ;4ort"und< Model. >. %e5ision and E(tension( i%id.( 4&(
&@/1( >--?.
8e3ular solution theory

i
i i
ij
ij j i j i
E
V n RT
, V V n n
RT
G
where*
( )
ij j i
j i
ij
# ,

2
2
i

and
i
V
are the solu%ility parameters and molar volumes at
0UC of component i .
=egular solution theory can %e used for vapour4li9uid calculations
for mi2tures of non4polar or slightly polar components. The theory
is applica%le to systems which e2hi%it negligi%le entropies and
volumes of mi2ing. ;owever( it has %een largely superseded %y
e9uations of state.
2lory75u33ins theory
The Eultiflash implementation of Flory4;uggins theory includes a
correction term. It is defined %y*

,
_

i
i i
ij
ij j i j i
i
j
j j
j
j i
i
E
V n RT
, V V n n
V n
n V
n
RT
G
2
ln
The Eultiflash e2pression reduces to the standard Flory4;uggins
theory if all interaction parameters ij
,
are set to $ero. ;owever(
to o%tain reasona%le results it is usually necessary to adPust the
values of the interaction parameters to fit the data.
Flory4;uggins theory is a%le to descri%e systems which include
some long chain molecules. It has conse9uently applied to model
polymer systems %ut it has %een to some e2tent superseded %y
other models such as 'C4S<FT. ;owever( Flory4;uggins theory still
offers the advantages of simplicity( and hence speed.
(-
Gas phase models for activity coefficient methods
The 9uantity ln
i
sat
can %e calculated from any of the gas phase
models in Eultiflash. The normal choices would %e the perfect gas
e9uation( the =) e9uation of state or a virial e9uation of state.
The first two are descri%ed in the section on e9uations of state and
the ;FC second virial model is descri%ed %elow.
!he 5ayden7OBConnell 95OC: model
The Eultiflash implementation of the ;FC model treats each
component in the gas phase as forming a monomer4dimer
e9uili%rium. For most components that deviate only slightly from
ideal %ehaviour( the model reduces to the volume4e2plicit virial
e9uation*
+
p
RT
V +
The second virial coefficient B is estimated for each component
from a generalised correlation >B.G. ;ayden and B.'. FIConnell( Ind.
#ng. Chem. 'roc. Hes. Hev( &4( -3 >&3/0??. This correlation
accounts for non4polar( polar and chemical association effects. The
pure component properties re9uired %y the model are* critical
temperature( critical pressure( radius of gyration( dipole moment
and an empirical association parameter. Galues for these 9uantities
are stored in the Infodata data%an6.
< second virial coefficient model such as ;FC can account for gas
phase non4idealities up to pressures of a%out 0 to &- %ar. The
implementation of the ;FC model in Eultiflash allows the vapour
phase association of su%stances such as acetic acid to %e
represented.
(*
Models for solid phases
Introduction
Eultiflash may also %e used to calculate the phase e9uili%rium of
systems containing solid phases( either mi2ed or pure. These may
occur either when a normal fluid free$es or may %e a particular
type of solid phase such as a hydrate.
Solid freeCe7out model
This model is used to calculate the thermodynamic properties of
solid phases formed %y free$ing one or more of the components in
the fluid mi2ture. It may %e applied to any component where this
may %e a consideration. The free$e4out model in general is defined
%y*
ln 2
i
=3ln 2
i
li/

(
4HT
ref
4C
p
R
)
(
1
T

1
T
ref
)
+
S
corr
R
+
4C
p
R
ln
(
T
T
ref
)

( pp
at)
) 4V
RT
For the free$e4out of pure solids( the parameters are as follows*

i
is the fugacity coefficient of pure solid component i (
i
li/
is
the fugacity coefficient of the same component as a pure li9uid at
the same pressure
p
and temperature T >calculated from the
li9uid phase model associated with the free$e4out model?( 1 (
H (
C
p and V are the changes in molar enthalpy( molar
heat capacity and molar volume respectively on fusion at the
melting point( ref
T
is a reference temperature which corresponds
to the normal melting point when
0
corr
S
which is assumed in
this case. p
at)
is atmospheric pressure. H (
C
p and V
are constants( which are normally o%tained from the chosen data
source.
Solid free$e4out can %e used to model the solidification of
compounds such as water( car%on dio2ide or methane( for e2ample
in natural gases. It can also %e used to model eutectics.
($
Scalin3 and 3eneral freeCe7out model
In its general form( the free$e4out model can %e applied to any
solid phase of fi2ed composition( which must %e defined. The
model can for e2ample %e applied to hydrated salts such as
monoethylene glycol >E#G? monohydrate or to crystalline mineral
salts( i.e. scales. If 1 ( the solid fugacity coefficient is defined
relative to the li9uid phase of the same composition whereas( if
0 ( the solid fugacity coefficient is an a%solute value.
corr
S
is
a molar enthalpy correction factor that allows the reference
temperature ref
T
to %e different from the normal melting point.
For solid phases that are not pure su%stances( the parameters
H (
C
p V (
corr
S
and ref
T
must %e defined specifically
for the phase in 9uestion.
Modellin3 hydrate formation and inhi0ition
8atural gas hydrates are solid ice4li6e compounds of water and the
light components of natural gas. They form at temperatures a%ove
the ice point and are therefore a serious concern in oil and gas
processing operations. The phase %ehaviour of systems involving
hydrates can %e very comple2 %ecause up to seven phases must
normally %e considered. The %ehaviour is particularly comple2 if
there is significant mutual solu%ility %etween phases( e.!. when
inhi%itors or CF

are present. Eultiflash offers a powerful set of

thermodynamic models and calculation techni9ues for modelling
gas hydrates.
5ydrate model
The original Infochem model uses a modification of the =)S
e9uation of state for the fluid phases plus the van der 7aals and
'latteeuw model for the hydrate phases. <n alternative model uses
the C'< model for the fluid phases. The hydrate models have also
%een e2tended to include hydrate structure ; in addition to
structures I and II. The model can e2plicitly represent all the
effects of the presence of inhi%itors( although parameters for the
C'< model are only provided for methanol( ethanol( E#G( H#G(
T#G and salt.
The main features of the models are*
Fur description of hydrate phase %ehaviour uses a
thermodynamically consistent set of models for all
phases present including hydrate structures I( II and ;(
ice( water( li9uid and gas. The vapour pressures of pure
water and su%limation pressures of ice are very
accurately reproduced.
The following natural gas hydrate formers are included*
methane( ethane( propane( iso%utane( %utane( nitrogen(
CF

and ;

S.
Fther hydrate formers that are not usually present in
natural gas %ut which form structure I or II are also
(,
included. These compounds are* SF
@
( ethylene(
propylene( cyclopropane( o2ygen( argon( 6rypton and
2enon.
'arameters are provided for the following compounds
that form hydrate structure II in the presence of small
Khelp4gasesI such as methane or nitrogen* cyclopentane(
%en$ene and neopentane. These compounds and the
structure ; formers listed %elow may %e present in
condensate and oil systems.
Structure ; hydrates form in the presence of small
Khelp4gasesI such as methane or nitrogen %ut the
formation temperatures are significantly higher >a%out
&- )? than pure methane or nitrogen hydrate. In
practice it seems that structure II hydrates form %efore
structure ; %ut( if there is enough water( structure ;
may %e formed too. The structure ; model includes
parameters for*
isopentane
neohe2ane
(!4dimethyl%utane
((!4trimethyl%utane
(4dimethylpentane
!(!4dimethylpentane
methylcyclopentane
methylcyclohe2ane
cis4&(4dimethylcyclohe2ane
(!4dimethyl4&4%utene
!(!4dimethyl4&4%utene
cycloheptene
cis4cyclooctene
adamantane
ethylcyclopentane
&(&4dimethylcyclohe2ane
ethylcyclohe2ane
cyclohe2ane
cycloheptane
cyclooctane
The thermal properties >enthalpies and entropies? of the
hydrates and ice are included permitting isenthalpic
and isentropic flashes involving these phases.
Calculations can %e made for any possi%le com%ination
of phases including cases without free water. 8o
modification of the phase models is re9uired to do this.
The properties of the hydrates have %een fi2ed %y
investigating data for natural gas components in %oth
simple and mi2ed hydrates to o%tain relia%le
predictions of structure I( structure II and structure ;
hydrates.
The properties of the empty hydrate lattices have %een
investigated and the most relia%le values have %een
adopted.
&4
'roper allowance has %een made for the solu%ilities of
the gases in water so that the model parameters are not
distorted %y this effect. This is particularly important
for car%on dio2ide and hydrogen sulphide which are
relatively solu%le in water.
Correct thermodynamic calculations of the most sta%le
hydrate structure have %een made.
The model is used to calculate the hydrate e9uili%rium formation
temperature at a given pressure or pressure at a given temperature
where the first very small 9uantity of hydrate appears after a
sufficiently long time. This point corresponds to the
thermodynamic formation point( also 6nown as the hydrate
dissociation point. Defore the thermodynamic formation point is
reached hydrate annot form 4 this point is also called the sta%ility
limit. Deyond the sta%ility limit hydrate an form %ut may not do
so for a long time.
The model has %een tested on a wide selection of open literature
and proprietary e2perimental data. In most cases the hydrate
dissociation temperature is predicted to within V&).
5ydrates in water su07saturated systems
;ydrates can form even in systems where there is no free water
present. Fur hydrate model( with %oth =)S<I8FF and C'< used to
model the fluid phase( is capa%le of modelling this( although the
data availa%le for validating the results are very limited. 7hat we
have noticed is that for systems with very little water and at high
pressures the predicted hydrate dissociation temperatures using
=)S<I8FF and C'< tend to diverge with increasing pressure( with
C'< predicting lower hydrate dissociation temperatures than
=)S<I8FF. There are no data presently availa%le to confirm which
is correct. If this causes any difficulty it is possi%le to reproduce
the C'< predictions with =)S<I8FF %y using parameters which
reduce the Infochem mi2ing rule to van der 7aals. These
parameters( for methane( ethane and propane with water( are
stored in the file vdw%ip.mfc. They can %e used to overwrite the
e2isting DI's for these %inaries %y loading this file after you have
defined the hydrate model %ased on =)S<I8FF as the fluid model.
7hen compared to the availa%le data all three possi%le variants
>C'<( =)S<I8FF with standard and vdw DI'? give hydrate
dissociation results within e2perimental error.
?ucleation model
The nucleation model was developed in colla%oration with D' as
part of the #UC;<=IS Point venture. This model is an e2tension of
the e2isting thermodynamic model for hydrates descri%ed a%ove.
In order to e2tend the nucleation model into the Eultiflash
program( the following enhancements to the nucleation model
were made*
The model was e2tended to cover the homogeneous
nucleation of ice and fitted to availa%le ice nucleation
data.
&%
The model was generalised to cover in principle
nucleation from any li9uid or gas phase.
< correction for heterogeneous nucleation was included
that was matched to availa%le hydrate nucleation data.
<n improved e2pression was adopted for fluid
diffusion rates.
Eore ro%ust numerical methods were introduced into
the program.
The nucleation model provides an estimate of the temperature or
pressure at which hydrates can %e realistically e2pected to form.
The model is %ased on the statistical theory of nucleation in
multicomponent systems. <lthough there are limitations and
appro2imations involved in this approach it has the maPor %enefit
that a practical nucleation model can %e incorporated within the
framewor6 of a traditional thermodynamic hydrate modelling
pac6age.
Eany of the comparisons of model predictions with e2perimental
data have %een made. In general measurements of hydrate
nucleation result in an e2perimental error of t WC and predictions
are usually within this error %and.
7ith the e2isting Infochem hydrate model and the nucleation
model( the hydrate formation and dissociation %oundaries can %e
predicted %etween which is the hydrate formation ris6 area.
Inhi0itor modellin3
Thermodynamic hydrate inhi%itors decrease the temperature or
increase the pressure at which hydrates will form from a given gas
mi2ture. The original Infochem hydrate model includes parameters
for the commonly used inhi%itors* methanol( salts( and the glycols
E#G( H#G and T#G and for the less well4tested inhi%itors ethanol(
iso4propanol( propylene glycol and glycerol. < new mi2ing rule was
developed for the S=) e9uation of state to model the effects of the
inhi%itors on the fluid phases.
The hydrate model using C'< to model the fluid phases is limited
in the current version of Eultiflash to hydrate calculations with
pure water or with methanol( ethanol( E#G( H#G( T#G and salt.
<dditional parameters to e2tend the C'< model to cover the full
range of thermodynamic inhi%itors listed a%ove may %e included in
future versions.
The treatment of hydrate inhi%ition has the following features*
The model can e2plicitly represent all the effects of
inhi%itors including the depression of the hydrate
formation temperature( the depression of the free$ing
point of water( the reduction in the vapour pressure of
water >i.e. the dehydrating effect? and the partitioning
of water and inhi%itor %etween the oil( gas and a9ueous
phases.
The model has %een developed using all availa%le data
for mi2tures of water with methanol( ethanol( E#G( H#G
and T#G. This involves representing simultaneously
&)
hydrate dissociation temperatures( depression of
free$ing point data and vapour4li9uid e9uili%rium data.
Two salt inhi%ition models are availa%le. The older
model is %ased on a salt component. The new model is
a >restricted? electrolyte model. < salinity calculator tool
is provided( see User Guide for Eultiflash for 7indows(
which allows the salt composition to %e entered in a
variety of ways. The salt component model e2presses
the salt composition in terms of an e9uivalent Nsalt
componentO present in I8FFH<T< with the properties
of sodium chloride. The #lectroyte model in versions of
Eultiflash to !.4 calculated the e9uivalent amount of
8a+ and Cl4 in the mi2ture. In EF!.0 the #lectrolyte
model has %een e2tended to include )+ and Ca++ ions.
This does not affect the e9uivalence calculations if the
salt composition is entered as THS >Total Hissolved
Solid?. If an Ion <nalysis or Salt <nalysis is supplied
then any values entered for )+ or Ca++ will %e allocated
to those ions in the Composition ta%le and the
e9uivalence for any ions other than 8a+( )+( Ca++ or Cl4
will %e e2pressed in terms of all these four ions. The
e9uivalent composition is %ased on e2perimental data
for the free$ing point depression and hydrate inhi%ition
effect of salts.
The solu%ilities of hydrocar%ons and light gases in
waterRinhi%itor mi2tures have also %een represented.
The original %inary interaction parameters for the =)S< fluid
model stored for al6anes with E#G correctly reproduce all the
reported data for al6ane solu%ility in E#G( for E#G solu%ility in
heptane and the inhi%ition effect of E#G on hydrate dissociation
temperatures. ;owever( the measured data for E#G solu%ility in
al6anes is limited to a single data set for the solu%ility of E#G in
heptane. For mi2tures containing hydrocar%ons greater than C/
the parameters in versions prior to .3 predicted an increasing
E#G solu%ility with increasing car%on num%er. This may have led
to over prediction of the amount of E#G re9uired to inhi%it
hydrates for heavy crude oils.
Later versions of Eultiflash include new parameters for al6anes
with E#G which sta%ilise the solu%ility of E#G in higher al6anes
and correctly reproduce the E#G inhi%ition effect on hydrates.
;owever( they fail to predict the correct solu%ility of al6anes in
E#G. The new parameters were included in the DI' data%an6(
oilandgas4( which is still the current version.. If( for any reason(
you wish to use the original parameters you can still retrieve these
from the DI' data%an6( oilandgas!.
Salinity Model
The original salt model operates only on a sodium chloride
e9uivalent %asis. The model represents the effect of sodium
chloride in a9ueous solution %y a special e9uation of state
component called Nsalt componentO or NsaltcompO. This model is
designed to operate with the <dvanced =)S e9uation although it is
also usa%le with the <dvanced '= e9uation. The salt component
&(
model cannot %e used with the C'< model or any other e9uation
of state.
The electrolyte salt model is designed to %e added on to any
e9uation of state. The models selection form allows it to %e
selected for use with the <dvanced =)S e9uation and the C'<
model. From Eultiflash version !.1 it represents the salt as a
com%ination of sodium( potassium( calcium( chloride and %romide
ions. Future versions of Eultiflash may e2tend this to other ions
Modellin3 wa. precipitation
7a2es are comple2 mi2tures of solid hydrocar%ons that free$e out
of crude oils if the temperature is low enough. Under conditions of
interest to the oil industry( wa2es consist mainly of normal
paraffins. 7a2es are thought to consist of many crystals each of
which is a solid solution of n4paraffins of a fairly narrow range in
molecular weight.
The availa%le wa2 model in Eultiflah 4.& is the Coutinho model.
The features of the model are*
The Coutinho model represents wa2 as a solid solution.
There are two versions of the model( the 7ilson and Uni9uac
variants. The version normally selected in Eultiflash is the
7ilson model which appro2imates the wa2 as a single solid
solution. This approach is relatively simple to apply and
gives a good representation of the data( so it is
recommended for general engineering use. The more
comple2 Uni9uac variant models the tendency of wa2es to
split into several separate solid solution phases. The Uni9uac
variant can %e activated %y configuration files that can %e
supplied %y Infochem for users who wish to simulate the
detailed physical chemistry of wa2 precipitation.
The model gives good predictions of wa2ing %ehaviour( %oth
wa2 appearance temperature and the amount of wa2
precipitated at different temperatures. The method is
applica%le to %oth live and dead oils.
The model re9uires that the normal paraffins are e2plicitly
present in the fluid model( as these are the wa2 forming
components. The user must therefore use the 'GT <nalysis
either to enter the measured n4paraffin concentrations or
else to estimate the n4paraffin distri%ution. The composition
of the wa2 phase is determined %y the 6nown thermal
properties >normal melting point( enthalpy of fusion( etc.? of
the n4paraffins com%ined with their solution %ehaviour in
%oth oil and wa2 phases.
In principle the wa2 model can %e used in conPunction with
any conventional cu%ic e9uations of state. The default
options in the Eultiflash implementation is =)S<.
Modellin3 asphaltene flocculation
<sphaltenes are polar compounds that are sta%ilised in crude oil
%y the presence of resins. If the oil is diluted %y light
&&
hydrocar%ons( the concentration of resins goes down and a point
may %e reached where the asphaltene is no longer sta%ilised and it
flocculates to form a solid deposit. Decause the sta%ilising action
of the resins wor6s through the mechanism of polar interactions(
their effect %ecomes wea6er as the temperature rises( i.e.
flocculation may occur as the temperature increases. ;owever( as
the temperature increases further the asphaltene %ecomes more
solu%le in the oil. Thus( depending on the temperature and the
composition of the oil( it is possi%le to find cases where
flocculation %oth increases and decreases with increasing
temperature.
The asphaltene model is %ased on the =)S cu%ic e9uation of state
with additional terms to descri%e the association of asphaltene
molecules and their solvation %y resin molecules. The interactions
%etween asphaltenes and asphaltenes4resins are characterised %y
two temperature4dependent association constants*
,,
' and
,R
' .
The remaining components are descri%ed %y the van der 7aals &4
fluid mi2ing rule with the usual %inary interaction parameters ij
#

so the asphaltene model is completely compati%le with e2isting
engineering approaches that are ade9uate for descri%ing vapour4
li9uid e9uili%ria. The model is a computationally efficient way of
incorporating comple2 chemical effects into a cu%ic e9uation of
state.
Other thermodynamic models
Eultiflash also incorporates a corresponding states method for
estimating the density of li9uid mi2tures( the CFST<LH model.
COS!'LD li#uid density model
The volume of a li9uid on the saturation line is defined %y*
[ ]
V
V
V V
sat
R R
*
( ) ( )

0 1
1
where
V
sat
is the saturated li9uid volume(
V
*
is a characteristic
volume for each su%stance(

is the acentric factor and V

R
( ) 0
and
V
R
( ) 1
are generalised functions of reduced temperature. In the
Infochem implementation
V
*
is o%tained %y matching the
saturated li9uid volume stored in the data%an6 at 31 ) or a
reduced temperature of -./( whichever is the lower.
The volume of a compressed li9uid is given %y*
V
V
C
+ p
+ p
sat sat

+
+

_
,

1
]
1
1 ln
where + is a generalised function of reduced temperature and

( C is a generalised function of

( and p
sat
is the saturation
pressure at the given temperature.
&
The CFST<LH method can provide very accurate volumes for pure
su%stances and simple mi2tures( such as L8G. It is valid for li9uids
on the saturation line and compressed li9uids up to a reduced
temperature of -.3. It is not necessarily accurate for heavy
hydrocar%on mi2tures with dissolved gases.
&-
!ransport property models
Introduction
For each of the transport properties( viscosity( thermal
conductivity and surface tension( Eultiflash offers two approaches
to o%taining values for mi2tures. Fne route is to calculate the
property for a mi2ture %y com%ining the property values for the
pure components of which it is composedJ the mi2ing rule
approach. The other is to use a predictive method suita%le for the
property in 9uestion.
Discosity
Super!8'PP viscosity model
The SuperT=<'' method is a predictive e2tended corresponding
states model that uses propane as a reference fluid. It can predict
the viscosity of petroleum fluids and well4defined components
over a wide range of thermodynamic states from the dilute gas to
the dense fluid. The %asic idea %ehind this model is that the
viscosity of a mi2ture can %e e9uated to the viscosity of a
hypothetical pure fluid which is then related to the viscosity of a
reference fluid at a corresponding4state point >4- (T-?. In order to
improve the viscosity prediction for cycloal6anes and highly
%ranched al6anes( the concept of mass shape factor in introduced
in this method. In order to apply the method( the following are
re9uired*
<n e9uation of state for the reference fluid(
Correlation for the viscosity of the reference fluid
The critical parameters( acentric factor and molecular
weight of the fluid of the interest or for each component of
the mi2ture of the interest.
The original method is not applica%le to a9ueous mi2tures of
alcohols( glycols or salts. The Infochem implementation of Super
T=<'' model includes modification to ensure that the viscosity of
a9ueous solutions of methanol( ethanol E#G( H#G and T#G or salts
and ions are predicted reasona%ly well.
&*
Two variants of the SuperT=<'' model are implemented*
Standard Super T=<'' model as descri%ed a%ove.
Li9uid viscosity fitting. <n internal model parameter is
adPusted to match the e2perimental measurements.
Fverall the SuperT=<'' method is the most versatile method for
viscosity predictions and its performance is generally %etter than
the other methods availa%le in Eultiflash. 7e would recommend
this method for oil and gas application. It is the default viscosity
model for use with e9uations of state.
=eference* ;u%er( E. L. X ;anley( ;.B.E. >&33@? The corresponding4
states principle* Hense Fluids. In B. Eillat( B. ;. Hymond X C. <.
8ieto >#ds.?( Transport properties of Fluids: Their orrelation*
Predition and Esti"ation. Cam%ridge University 'ress.
Pedersen Model
This is a predictive corresponding states model originally
developed for oil and gas systems. It is %ased on accurate
correlations for the viscosity and density of the reference
su%stance which is methane. The model is applica%le to %oth gas
and li9uid phases. The Infochem implementation of the 'edersen
model includes modifications to ensure that the viscosity of li9uid
water( methanol( ethanol( E#G( H#G and T#G and a9ueous
solutions of these components or salt are predicted reasona%ly
well.
=eference* 'edersen( Fredenslund and Thomassen( Properties of
1ils and #atural 2ases( Gulf 'u%lishing Co.( >&313?.
!wu Model
This is a predictive model suita%le for oils. It is %ased on a
correlation of the <'I nomograph for 6inematic viscosity plus a
mi2ing rule for %lending oils. It is only applica%le to li9uids.
=eference* Twu( 2eneralised "ethod for preditin! 5isosities of
petroleu" frations( <ICh# Bournal( !( -3&( >&31@?.
LohrenC7+ray7Clar= method
This model is a predictive model which relates gas and li9uid
densities to a fourth degree polynomial in reduced density

r c
*
( )
[ ]
+ + + + +
*
&
10
4
1 4
1 2 #
2
4
#

4
a a a a a
r r r r
where a
1
( a
2
( a
#
( a
4
and a

are constants. For pure components

the viscosity reducing parameter is defined %y
T 5 p
c c
1 $ 1 2 2 # & & &
where T
c
and p
c
are respectively the critical temperature and
critical pressure and 5is the component molecular weight. For
&$
a mi2ture these properties are calculated using mole fraction
averages.
In Eultiflash the fluid densities are derived from any chosen
e9uation of state( rather than the correlations proposed %y
Lohrent$ et al. This has the advantage that there is no
discontinuity in the dense phase region when moving %etween
li9uid4li6e and gas4li6e regions.
Eultiflash also allows two variants of the LDC model. The first uses
the original LDC method to estimate the critical volume of
petroleum fractions and ta6es the critical volume of other
components from the chosen data source. The second variant fits
the critical volume of each component to reproduce the li9uid
viscosity at the %oiling point.
The method is mainly applica%le to the types of components found
in oil and gas processing %ut we would recommend that the
SuperT=<'' method is normally used in these cases.
=eference* Lorent$( Dray and Clar6( Calulatin! 5isosities of
%eser5oir Fluids fro" their Co"positions( Trans. Soc. 'et. #ngs. Ff
the <EE'# !& &&/& >&3@4?
Li#uid viscosity mi.in3 rule
This method o%tains the li9uid mi2ture viscosity %y applying a
simple mi2ing rule to the pure component saturated li9uid
viscosities generated from a data%an6. #ach component in the
mi2ture must have a li9uid viscosity correlation stored in the
data%an6.
ln
ln

i i i
i i
n
n
Dapour viscosity mi.in3 rule
The viscosity of a gas mi2ture at low density is calculated from the
data%an6 correlations for the $ero pressure gas viscosities of the
pure components. #ach component in the mi2ture must have a
vapour viscosity correlation stored in the data%an6.

i i i i
i i i
n
n
where
i
and
i
are the molecular weight and pure gas viscosity
for component i .
&,
!hermal conductivity
Chun37Lee7Starlin3 thermal conductivity
method
This is a predictive method for %oth gas and li9uid mi2ture
thermal conductivities. It re9uires the critical properties( T
ci
( V
ci

and
ci
for non4polar components. For polar and associating fluids
the dipole moment and an association parameter are also re9uired.
<ssociation parameters for water( acetic acid and the lower
alcohols are provided. The fluid density is re9uired as part of the
calculation and this 9uantity may %e o%tained from any of the
thermodynamic models in Eultiflash.

+
p

1
]
1 0
2
1
H
+ 6
i
where
0
is a generalised function of reduced temperature( +
i
is a
generalised function of

( H
2
is a generalised function of
r

and 6 is a function of volume.
This method can %e used for oil and gas processing and also for
polar mi2tures.
=eference* =eid( 'rausnit$ and 'oling( The Properties of 2ases and
&iquids( EcGraw4;ill.( >&31/?.
Super!8'PP thermal conductivity method
The SuperT=<'' >ST=<''? method is an e2tended corresponding
states model that can %e used for petroleum fluids( well4defined
components and pure su%stances.
In general the thermal conductivity is defined as the sum of the
internal contri%ution and the translational contri%ution. The
translational contri%ution can %e defined as three parts* the dilute gas
contri%ution( the residual and critical enhancement contri%ution. In
the current version of ST=<'' in Eultiflash !.3( the critical
enhancement term(
Crit
x
is omitted since the critical enhancement
for mi2tures is usually very small.
5) 6 , , ( 5) 6 , , ( 5) 6 , ( 5) 6 , ( 5) 6 , , (
int
x T x T x T x T x T
Crit
x
res
x
gas dil7te
x x x
+ + +

For a mi2ture( the internal contri%ution
int
x
can %e estimated from
the empirical mi2ing and com%ining rules using the modified #uc6en
correlation for the individual components.
For the dilute gas term( the e2pression for the translational
contri%ution is formulated as
x
o
x gas dil7te
x

T R
x T
4
) ( 1
5) 6 , (

4
in units of "-?"?7. R is the molar gas constant in units of
' )ol 8 & & and
x
is the molecular weight for the mi2ture in
unit of gRmol and the e2pression of ) (T
o
x
for a mi2ture is given
as follows.

n
i
i x
n
i
i
o
i i
o
x
x
T x
T
1
2 & 1
1
2 & 1
) (
) (

and

n
i
i i x
x
1
7here
o
i
is the dilute gas viscosity given %y Lucas correlation in
unit of
P
.
The e2pression of the residual contri%ution term is evaulated using
the e2tended corresponding state method and is related to the
thermal conductivity of a reference fluid of propane at a
corresponding state( ) , (
o o
T .

% T T
o o
res
o
res
x
) , ( ) , (
where the

%
calculation re9uires mi2ing and com%ining rules for
the mi2tures.
=eferences*
Bames F. #ly and ;.B.E. ;anley ( N'rediction of transport properties. .
Thermal conductivity of pure fluids and fluid mi2tures. Ind. #ng.
Chem. Fund.( ( 3-43/ > &31!?.
E.L. ;u%er and ;.B.E. ;anley( N The Corresponding4States 'rinciple*
Hense FluidsO( p1!( edited %y B rgen Eillet( Bohn ;. Hymond and
C.<. 8ieto de Castro( NTransport 'roperties of FluidsO( I'U<C( >&33@?.
E.#. Daltatu( =.<. Chong( E.L. ;u%ler( NThermal conductivity of
defined and undefined hydrocar%on li9uids with an e2tended
corresponding states modelO( The fourth <sian Thermophysical
'roperties Conference( To6yo( Sept. &330.
E.#. Daltatu( =.<.Chong et al( NTransport 'roperties of 'etroleum
FractionsO( International Bournal of Thermophyics( Gol. -( 8o. &( p104
30 >&333?.
;u%er>&33@?( p&-.4( NThe 'roperties of Gases and Li9uidsO( edited %y
Druce #. 'oling( Bohn E. 'rausnit$ and Bohn '. Fconnell( fifth edition(
--&.
Li#uid thermal conductivity mi.in3 rule
This method o%tains the li9uid mi2ture thermal conductivity %y
applying a simple mi2ing rule to the pure component saturated
li9uid thermal conductivities generated from a data%an6. #ach
component in the mi2ture must have a li9uid thermal conductivity
correlation stored in the data%an6.
1
1
2
2

i i i
i
i i i
n
n
%
where
i
and
i
are the molecular weight and pure saturated
li9uid thermal conductivity of component i .
Dapour thermal conductivity mi.in3 rule
The thermal conductivity of a gas mi2ture at low density is
calculated from the correlations for $ero density gas thermal
conductivity of the pure components at the same temperature.

i i i i
i i i
n
n
Surface !ension
Linear Gradient !heory method
This method predicts the interfacial tension %etween two phases.
The possi%le pairs of phases are* Li9uid R Gas and Li9uid R Li9uid.
The predition of interfacial tension %etween Li9uid R Solid and
Gas R Solid phases is not yet possi%le.
The model uses the difference in densities %etween the two phases
and the energy gradient that arrives from the fact that the phases
are immisci%le to predict the interfacial tension.
( ) ( ) ( ) ( )
ref
99
ref
:
ref
9
e/ e/
i i
i
i
d: P : P ; : ; : <



,
_

2c
The varia%le is characteristic of the mi2ture and varies with
temperature. The mi2ing rule used for this parameter is of the
following type*
( )
ij jj ii ij
l c c < c 1
The parameter ij
l
is the %inary interaction parameter >DI'?.
<nd the parameter has to %e calculated along the interface
gradient*
ref
j
ref
i
Nc
< i
Nc
< j
ij
4:
4:
4:
4:
c < c

1 1
<s the Linear Gradient Theory model is defined in this particular
way( an #9uation of State that can descri%e the interface %etween
the two phases is necessary. The supported #9uations of State in
Eultiflash are S=)><?( '=><?( C'<( D7=S and S<FT.
This method has more relia%le results with components present in
the oil and gas processing( while using the S=)( '= or C'<
#9uations of State.
=eference* Auo( Y. T. and Sten%y( #. ;.( A &inear 2radient Theory
Model for Calulatin! ,nterfaial Tensions of Mi(tures( Bournal of
Colloid X Interface Science( &1 p&( #lsevier >&33@?
)
Macleod7Su3den method
This method predicts the surface tension of a li9uid mi2ture %ased
on the pure component parachors stored in a data%an6.

1 4 &
( )

P x y
i l i v i
where*
P
i
is the parachor for component i

l
is the li9uid molar density

v
is the vapour molar density
x
i
is the li9uid mole fraction
y
i
is the vapour mole fraction.
It is mainly applica%le to the types of component found in oil and
gas processing.
=eference* 'edersen( Fredenslund and Thomassen( Properties of
1ils and #atural 2ases( Gulf 'u%lishing Co.( >&313?.
Surface tension mi.in3 rule
The surface tension for a li9uid mi2ture may %e calculated from
the correlations for the surface tension of the pure saturated
li9uids at the same temperature and pressure using a power law
model.
1
1

i i
i
i i
n
n
where
i
is the surface tension of the pure saturated li9uid for
component i .
=eference* 'edersen( Fredenslund and Thomassen( Properties of
1ils and #atural 2ases( Gulf 'u%lishing Co.( >&313?.
Diffusion coefficients
2uller method
The Fuller method calculates gas diffusion coefficients. It is an
empirical modification of Chapman4#ns6og theory. The Fuller
e2pression for the diffusion coefficient for components i and
j

in SI units is*
( )
2 & 1
2
# & 1 # & 1
! " 1 22
1 1
10 0112 " 1

,
_

+
+

j i
j i
ij
ij

p
# T
*
(
T is the temperature(
p
is the pressure(
i

is the relative
molecular weight of component i >in g mol
4&
? and
i

is a
characteristic volume that is found for each component using
FullerIs ta%les. ij
#
is an empirical adPustment factor for the user
to match the Fuller method to e2perimental data if availa%leJ to
o%tain the standard result from FullerIs method( ij
#
should %e set
to unity.
=eference* Chapter && of The Properties of 2ases and &iquids( 0th.
#d. %y 'oling( 'rausnit$ and FIConnell( EcGraw4;ill( 8ew Yor6(
--&.
5aydu=7Minhas method
The ;aydu64Einhas method calculates li9uid diffusion
coefficients. It consists of a num%er of empirical correlations for
different classes of mi2ture. For e2ample for normal paraffins the
diffusion coefficient of a trace amount of component i in
component
j
in SI units is*
( )
!91 " 0
10 02 " 1
1000 10 #09 " !

!1 " 0
4! " 1 1$
0

i
i
j
ij
V
V
T
*

T is the temperature(
i
V
is the molar volume of component i
and j

is the li9uid viscosity of component

j
. The viscosity is
calculated from the li9uid viscosity model specified %y the user.
Hetails of the other correlations that form the ;aydu64Einhas
method are descri%ed in the =eference. Eultiflash actually returns
effective diffusion coefficients for a li9uid of defined composition.
The e2pression used is*
( ) ( )
j
j
j
i
i
i
ij
x
ji
x
ij ij
x
x
x
x
# * * *
i j

ln
1
ln
1
0 0
where
i
x
and
i

are the mole fractions and activity coefficients

of component i in the %inary mi2ture. For the sa6e of efficiency(
the activity coefficients are calculated from the Eargules
e2pression which in turn is fitted to the activity coefficients for an
e9uimolar %inary mi2ture calculated with the thermodynamic
model for the li9uid phase specified %y the user. ij
#
is an
empirical adPustment factor for the user to match the calculated
result to e2perimental data if availa%leJ to o%tain the standard
result( ij
#
should %e set to unity.
=eference* Chapter && of The Properties of 2ases and &iquids( 0th.
#d. %y 'oling( 'rausnit$ and FIConnell( EcGraw4;ill( 8ew Yor6(
--&.
&
+inary interaction parameters
Introduction
Dinary interaction parameters >DI's? are adPusta%le factors which
are used to alter the predictions from a model until these
reproduce as closely as possi%le the e2perimental data. DI's are
usually generated %y fitting e2perimental GL# or LL# data to the
model in 9uestion( with the e2ception of U8IF<C and 'S=) DI's
which are predicted %y group contri%ution. DI's apply %etween
pairs of components. ;owever( the fitting procedure may %e %ased
on %oth %inary and multi4component phase e9uili%ria information(
the former %eing the most common.
?um0er of +IPs related to any model
Hifferent models re9uire differing num%ers of DI's and these may
or may not have physical significance. The cu%ic e9uations of state
>=)( =)S( '=? re9uire only a single DI'. The closer the %inary
system is to ideality the smaller the si$e of the DI'( which will %e
$ero for ideal systems. It is unli6ely that the value of the DI' will
%e greater than &( although it is possi%le for it to %e negative. For
the L) and L)' models the default value of the interaction
parameter is &.
7hen non4standard mi2ing rules are used( e.g. when using
=)S<>Infochem?( then the num%er of DI's increases. For the e2cess
Gi%%s energy type mi2ing rules >E;G4type and ;uron4Gidal4type?
the num%er of DI's will %e determined %y the activity coefficient
model used to descri%e the li9uid phase. For the Infochem mi2ing
rule ! DI's are needed.
'C4S<FT re9uires two symmetric DI's( in addition to the pure
component model parameters. The default value for %oth is $ero.
C'< uses the same interaction parameters as =)S< with the
addition of three association parameters to descri%e cross
association and self association where this occurs.
The 7ilson < and U8I"U<C models re9uire two DI'sJ 7ilson #
needs the same num%er of DI's( %ut these are not interchangea%le
with 7ilson <. 8=TL needs two %inary energy interaction
parameters and a non4randomness factor(

. 7ith the e2ception

of

( these DI's may ta6e a wide range of numerical values and

more that one set may ade9uately represent the same

e2perimental data. The DI's for the activity models are asymmetric
and it is important to define the %inary pair of components i and
j
in the correct order to agree with the fitted or reported DI's.
The 8=TL

parameter defaults to -.! for GL# calculations and

-. for LL# calculations. Galues derived from fitting to
e2perimental data will vary %ut are unli6ely to %e much greater
than -.@.
The =egular Solution and Flory ;uggins models %oth use a DI's
that are symmetrical( dimensionless and with a default value of
$ero.
Units for +IPs
The DI's for e9uation of state methods are dimensionless( with the
e2ception of two of the C'< association parameters. For some of
the activity coefficient models they are dimensioned with the
e2ception of 7ilson <( =egular Solution and Flory ;uggins. The
dimensions used in Eultiflash are BRmole. If DI's from e2ternal
sources are used in Eultiflash it is important that either the DI'
units are changed to match the input values or the numeric values
of the DI's are changed to BRmole.
The choice of units appears once the Units %utton is selected in the
DI' display. BRmol is the Eultiflash standard for the dimensioned
activity model DI's. CalRmol and ) are the values used in the
Hechema Hata Series for activity GL# and LL# DI's. The N<spenO
format allows you to transfer the DI' values for the 8=TL e9uation
produced from <spen 'lus without further change.
!emperature dependence of +IPs
In most of the open literature sources the reported %inary
interaction parameters will %e temperature independent( i.e.
constants. ;owever( Eultiflash allows for any DI' to %e
temperature dependent with either a linear or a 9uadratic
dependence( although we do not recommend this for the 8=TL

parameter. The DI's can in general %e defined as
2
T c T " a ,
ij ij ij ij
+ +
where T is the a%solute temperature in ). The user can enter the
three coefficients a
i@
( b
i@
and
i@
.
Chan3in3 units
For activity coefficient DI's( it is possi%le to change units. The
e9uation a%ove is valid for the default units of BRmol. To convert
to calories the coefficients are divided %y 4.&1BRcal. To convert to
)( the coefficients are divided %y the gas constant( % L
1.!&44&BRmol ). To convert to the dimensionless form( the
e2pression for <iP is divided %y =T and the first two terms are
reordered to give
,
ij
/ RT=d
ij
+e
ij
/ T+ f
ij
T
-
where
d
ij
="
ij
/ R
e
ij
=a
ij
/ R
f
ij
=c
ij
/ R
The 8=TL parameter is dimensionless so it is given %y
3
ij
=a
ij
+"
ij
T+c
ij
T
2
for all units e2cept the <spen units when it is e2pressed as
3
ij
=d
ij
+e
ij
t + f
ij
t
2
where t is the temperature in C. The conversion factors are
d
ij
=a
ij
+"
ij
2!#"1+c
ij
2!#" 1
2
e
ij
="
ij
+2c
ij
2!#"1
f
ij
=c
ij
+IPs availa0le in Multiflash
Fur main DI' %an6 is applica%le to oil and gas processing
operations and called appropriately( FIL<8HG<S. This contains
DI's for the cu%ic e9uation of state models '=( '=<( '=/1( '=/1<(
=)S( =)S< and =)S< >Infochem? for hydrocar%ons( water(
methanol( glycols( ;S( CF and 8( and for the C'< model. The
correlations have %een e2tended to include DI's for the L)' model
for hydrocar%on and light gas mi2tures. Eultiflash also provides
methods for estimating DI's for the '=( =)S and C'< e9uations for
mi2tures that include petroleum fractions.
The I8FFDI'S DI' %an6 includes DI's for the 7ilson# and the GL#
variants of 8=TL and U8I"U<C( %ased on the data reported in the
Hechema Chemistry Hata Series. Some DI's are also availa%le for
e9uations of state such as D7=S( L)' and the cu%ics for systems
not covered %y the normal correlations( e.g. %inaries including
ammonia. The I8FFDI'S data%an6 is updated as data are availa%le.
< DI' %an6( I8FFLLDI'S( stores DI's for use with the LL# variants
of 8=TL and U8I"U<C.
For the U8IF<C model( DI's are predicted from group
contri%utions. The data records for pure components in the
I8FFH<T< data%an6 contain information on U8IF<C groups(
where applica%le( ena%ling the DI's to %e generated. Groups for use
with the 'S=) and Hortmund Eodified U8IF<C models are also
stored as part of the pure component U8IF<C record. 7here the
groups vary( Eultiflash applies the correct group structure to
match the chosen model. 7e have created an Infochem version of
HI''= that includes the same group information. You will see a
warning message if the group contri%utions are missing for any
chosen component.
It is possi%le to have two DI' %an6s in force for any pro%lem. <ll
the .mfc model descriptions for the e9uations of state define %oth
I8FFDI'S and FIL<8HG<S. 7hen the model is defined Eultiflash
will first search I8FFDI'S for any specific %inary DI'S( then define
DI's from the correlations in FIL<8HG<S and if any are still
*
missing they will %e set to default values. The GL# variants of the
activity methods only access I8FFDI'S( %ut the LL# variants access
I8FFLLDI'S( followed %y I8FFDI'S.
Detween releases of Eultiflash we may amend( or add to( the DI's
stored. For the FIL<8HG<S data%an6 we will supply a copy of the
previous %an6s in order to maintain %ac6ward compati%ility. The
current version will still %e 6nown as FIL<8HG<S4( and also the
default( FIL<8HG<S. 'revious versions such as FIL<8HG<S! can
%e recalled if you wish. For I8FFDI'S we intend only to issue the
latest version( if users wish to maintain access to earlier versions
they should retain a copy of the relevant file.
$
Model data re#uirements
#ach model re9uires a certain amount of pure component data.
These are listed in the following ta%le.
1odel 1inimum input
Thermod2namic
07S critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
ide)l *)s Cp (C8I=/9L)
07S98I critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
ide)l *)s Cp (C8I=/9L)
07S9 critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S), ide)l *)s Cp (C8I=/9L)
07S9I:;< critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S), ide)l *)s Cp (C8I=/9L)
80 critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
ide)l *)s Cp (C8I=/9L)
80!8 critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
ide)l *)s Cp (C8I=/9L)
809 critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S), ide)l *)s Cp (C8I=/9L)
80!89 critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S), ide)l *)s Cp (C8I=/9L)
8S07 critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S), ide)l *)s Cp (C8I=/9L) ), >:I;9C
su+*roup structures (>:I;9C)
8S071:0-L critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
v)pour pressure (8S9-), s)tur)ted li3uid densit,
,
(L=/:S), ide)l *)s Cp (C8I=/9L) )"
L7 critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
ide)l *)s Cp (C8I=/9L)
L78 critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
ide)l *)s Cp (C8I=/9L)
?@0S critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), critic)l volume (AC0I-) )nd )centric
f)ctor (9C/:-0IC;9C-<0) for co)ponents
not in )odel data"ase, ide)l *)s Cp (C8I=/9L)
CSB critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), critic)l volume (AC0I-), ide)l *)s Cp
(C8I=/9L)
C89 critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S), )ssoci)tion p)r)meters (9SS?/,
9SS/8, 9SS.9), ide)l *)s Cp (C8I=/9L)
CD critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
ide)l *)s Cp (C8I=/9L)
8C1S9;- critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
8C1S9;- p)r)meters (S9;-/7, S9;-SI.B9,
S9;-B, S9;-79889, S9;-/8SIL<:,
S9;-;;), ide)l *)s Cp (C8I=/9L)"
:ote (1) -C0I-, 8C0I- )nd
9C/:-0IC;9C-<0 )re necess)r, to *ener)te
st)rtin* v)lues for fl)sh c)lcul)tions +ut do not
)ffect the computed results from 8C1S9;-" (2)
S9;-79889, S9;-/8SIL<: )nd S9;-;; )re
onl, needed for )ssoci)tin* components"
Ide)l solution v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S)
:0-L v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S)
@ilson v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S)
>:IE>9C v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S), surf)ce )nd volume p)r)meters
(>:IEE, >:IE0)
>:I;9C v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S), >:I;9C su+*roup structures
(>:I;9C)
=ortmund Bodified
>:I;9C
v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S), >:I;9C su+*roup structures
(>:I;9C)
0e*ul)r Solution v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S), solu+ilit, p)r)meter (S<L>890) )nd
mol)r volume )t 2FC (A2)"
;lor,1Gu**ins v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S), solu+ilit, p)r)meter (S<L>890) )nd
mol)r volume )t 2FC (A2)"
-4
Ide)l *)s ide)l *)s Cp (C8I=/9L)
07 critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), ide)l *)s Cp (C8I=/9L)
G),den <HConnell critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), r)dius of *,r)tion (09=.I0), dipole
moment (=I8<L/B<B/:-), G),den1
<HConnell )ssoci)tion p)r)meter (G<C9SS),
ide)l *)s Cp (C8I=/9L)
;ree2e1out meltin* point (-B/L-), enth)lp, of fusion
(GB/L-), he)t c)p)cit, ch)n*e on fusion
(C8B/L-), volume of fusion (AB/L-)
G,dr)te potenti)l p)r)meters (GI=1, GI=2, GI=#),
c)vit, occup)tion code (GI=<C)
@)% meltin* point (-B/L-), enth)lp, of fusion
(GB/L-), he)t c)p)cit, ch)n*e on fusion
(C8B/L-), volume of fusion (AB/L-)
9sph)ltene critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
v)pour pressure (8S9-), s)tur)ted li3uid densit,
(L=/:S),
Transport properties
8edersen critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), molecul)r (ei*ht
(B<L/C>L90@/I.G-)
-(u molecul)r (ei*ht (B<L/C>L90@/I.G-),
+oilin* point (-?<IL), v)pour pressure (8S9-),
s)tur)ted li3uid densit, (L=/:S)
L?C
Lohrent21?r),1Cl)rJe
critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), critic)l volume (AC0I-), dipole
moment (=I8<L/B<B/:-), molecul)r (ei*ht
(B<L/C>L90@/I.G-)
CLS
Chun*1Lee1St)rlin*
critic)l temper)ture (-C0I-), critic)l volume
(AC0I-), dipole moment (=I8<L/B<B/:-),
molecul)r (ei*ht (B<L/C>L90@/I.G-)
S-0988
Super-0988 method
critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
critic)l volume (AC0I-), dipole moment
(=I8<L/B<B/:-), molecul)r (ei*ht
(B<L/C>L90@/I.G-)
Line)r .r)dient -heor, surf)ce tension (S-/:SI<:), critic)l
temper)ture (-C0I-)
B)cleod1Su*den p)r)chor (8909CG<0)
Cost)ld critic)l temper)ture (-C0I-), critic)l pressure
(8C0I-), )centric f)ctor (9C/:-0IC;9C-<0),
s)tur)ted li3uid densit, (L=/:S)
Li3uid viscosit, mi%in*
rule
li3uid viscosit, (LAISC)
A)pour viscosit, mi%in*
rule
v)pour viscosit, (AAISC)
Li3uid therm)l
conductivit, mi%in* rule
li3uid therm)l conductivit, (L-GC<:=)
A)pour therm)l
conductivit, mi%in* rule
v)pour therm)l conductivit, (A-GC<:=)
-%
Surf)ce tension mi%in*
rule
surf)ce tension (S-/:SI<:)
=iffusivit, K ;uller's
method
molecul)r (ei*ht (B<L/C>L90@/I.G-),
chemic)l formul) (;<0B>L9), >:I;9C
su+*roup structures (>:I;9C)"
=iffusivit, 1 G),duJ1
Binh)s method
critic)l temper)ture (-C0I-), critic)l mol)r
volume (AC0I-), norm)l +oilin* point (-?<IL),
p)r)chor (8909CG<0) dipole moment
(=I8<L/B<B/:-), s)tur)ted li3uid densit,
(L=/:S), chemic)l formul) (;<0B>L9),
>:I;9C su+*roup structures (>:I;9C)"
-)
Components
Introduction
Eultiflash recognises three types of component. 8ormal
components are pure compounds such as hydrocar%ons(
petrochemicals and chemicals( which may e2ist as gas( li9uid or
solid depending on conditions of temperature and pressure. <
petroleum fraction is a pseudo component( usually a comple2
mi2ture of hydrocar%ons( whose aggregate properties are
characterised %y standard tests( the results of which may %e found
in 'GT la%oratory reports.
The physical properties for each type of component are stored or
defined differently.
?ormal components
The physical properties of normal components are usually stored
in data%an6s. Eultiflash offers two( I8FFH<T< and HI''=
TE
.
I8FFH<T< is the Infochem fluids data%an6( which contains data
on a%out -- compounds and is always supplied as part of
Eultiflash. HI''=( produced under the auspices of <ICh#( currently
has data for over &/-- compounds( %ut is e2tended annually.
Properties of normal components
Doth I8FFH<T< and HI''= store data for each varia%le property
>e.g. vapour pressure( li9uid density? of a component as a function
of temperature. 'roperties that are not temperature dependent are
stored as constant values. < list of the properties availa%le in
HI''= and I8FFH<T< is shown %elow. Some properties may %e
missing for individual components.
Constant properties
Eolecular 7eight
Critical Temperature
Critical 'ressure
Critical Golume
Critical Compressi%ility Factor
Eelting 'oint
Triple 'oint Temperature
-(
Triple 'oint 'ressure
8ormal Doiling 'oint >at & atm?
Li9uid Eolar Golume at 31.&0)
Standard Ideal Gas #nthalpy of
Formation at 31.&0)
Standard Ideal Gas Gi%%s #nergy of
Formation at 31.&0)
Standard Ideal Gas #ntropy at 31.&0)
#nthalpy of Fusion at Eelting 'oint
#ntropy of Fusion at Eelting 'oint
;eat capacity change on fusion
Golume change on fusion
Standard 8et #nthalpy of Com%ustion at 31.&0)
<centric Factor
=adius of Gyration
'arachor
Solu%ility 'arameter at 31.&0)
Hipole Eoment
van der 7aals Golume >U8I"U<C r?
van der 7aals <rea >U8I"U<C 9?
=efractive Inde2
Flash 'oint
Lower Flamma%ility Limit
Upper Flamma%ility Limit
<utoignition Temperature
plus some model specific parameters.
<dditionally there is a group of properties that allow uni9ue
identification of the name and type of the component. These are
TY'#
C<S num%er
FF=EUL<
F<EILY code
8ormal data%an6 components will %e TY'# &.
Temperature Hependent 'roperties
Solid Hensity
Li9uid density
Gapour 'ressure
#nthalpy of vaporisation
Solid ;eat Capacity
Li9uid ;eat Capacity
Ideal Gas ;eat Capacity
Second Girial Coefficient
Li9uid Giscosity
Gapour Giscosity
Li9uid Thermal Conductivity
Gapour Thermal Conductivity
Surface tension
=elative permittivity >dielectric constant?
Doth data%an6s( in addition to the properties a%ove( also contain
the U8IF<C and 'S=) group structures( where applica%le. For
some components( coefficients will also %e stored for the second
-&
virial coefficient and relative permittivity( %oth used for model
calculations.
I8FFH<T< contains only a limited range of components( a%out
4/( mainly suita%le for oil and gas processing. <lthough every
effort has %een made to ensure that the data stored are correct we
do not offer I8FFH<T< as a 9uality assured data%an6.
HI''= is developed under the auspices of the <merican Institute of
Chemical #ngineers. The data%an6 contains a %road range of
components including hydrocar%ons( petrochemicals( chemicals
and some metals. The correlations used in Eultiflash are the
recommended set for each property and component. "uestions
concerning 9uality codes and sources of data for the HI''=
data%an6 should %e referred to Infochem.
#ach temperature dependent property may %e stored %y a variety
of correlations
The temperature dependent properties are stored as coefficients of
designated correlation e9uations. For each property there is a
choice of correlation e9uationsJ each is assigned an e9uation
num%er and it is this plus the property IH code and coefficients
that is displayed through the ToolsR'ure Component menu.
The correlation e9uations for each property are shown in the
following ta%le.
Pure component temperature7dependent
properties
The form of each correlation is defined %elow. 'roperty units are
given in parentheses. They are fi2ed and are not affected %y the
UNITS or INPUTUNITS command.
The format re9uire for each property correlation is
property_name equation_number coefficients Tmin Tmax;
property_name is one of the 6eywords from the following ta%le.
equation_number identifies the correlation.
coefficients are the numerical values of the correlation
coefficients. The num%er of coefficients re9uired depends on the
e9uation num%er.
For temperature dependent properties %oth data%an6s contain
information on the upper and lower temperature limits for the
correlation used for each component. #2trapolation routines are
included in Eultiflash so that pure component properties from
either %an6 %ehave sensi%ly %eyond the temperature limits of the
stored correlation.
Keyword "#uation
num0er
'dditional information
Cpideal ideal gas Cp correlation >BRmol )?
- data un6nownJ - coefficients
& ;armens method( 3 coefficients
a!( a4( a0( a@( a/( a1( a3( Tmin( Tma2
-
( ) ( ) ( )
C R a a a y y % y
p
& ( ) + +
# 4 #
2
1 1
where % y a a y a y a y ( ) + + +
$ ! 8
2
9
#
(
y
T
T a

HI''= e9uation &-/( / coefficients

a!( a4( a0( a@( a/( Tmin( Tma2
( ) ( )
C a a
a T
a T
a
a T
a T
p
+

_
,
+

_
,

# 4

2
$
!
!
2
&
sinh &
&
cosh &
0 HI''= e9uation &--( / coefficients
a!( a4( a0( a@( a/( Tmin( Tma2
C a a T a T a T a T
p
+ + + +
# 4
2
$
#
!
4
Cpliquid li9uid Cp correlation >BRmol )?
- data un6nown( - coefficients
& HI''= e9uation &&4( 3 coefficients
a&( a( a!( a4( a0( a@( a/( Tmin( Tma2
C a a a a a a a
p
+ + + + + +
1 2 # 4
2

#
$
4
!

&
where 1 T T
c
&
0 HI''= e9uation &--( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
C a a T a T a T a T
p
+ + + +
1 2 #
2
4
#

4
Cpsolid solid Cp correlation >BRmol )?
- data un6nown( - coefficients
0 HI''= e9uation &--( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
C a a T a T a T a T
p
+ + + +
1 2 #
2
4
#

4
psat saturated vapour pressure >'a?
- data un6nown( - coefficients
& 7agner >form &? 0 coefficients
a&( a( a!( Tmin( Tma2
ln ln p p
a a a
T
c
r
+
+ +
1 2
2
#
#

where T T T
r c
& ( 1 T
r
<ntoine e9uation( 3 coefficients
a&( a( a!( a4( a0( a@( a/( Tmin( Tma2
ln ln p a
a
T a
a T a T
a
T
a
+
+
+ + +
1
2
#
4
!
2
$
8ote that if the third term is unused a4 should %e set to - and
a@ must %e set to a positive value such as &.-.
! 7agner >form ?( @ coefficients
a&( a( a!( a4( Tmin( Tma2
ln ln p p
a a a a
T
c
r
+
+ + +
1 2
#
2
#
#
4
$

where T T T
r c
& ( 1 T
r
4 7agner >form !?( @ coefficients
a&( a( a!( a4( Tmin( Tma2
--
ln ln p p
a a a a
T
c
r
+
+ + +
1 2
#
2
#

2
4

where T T T
r c
& ( 1 T
r
0 HI''= e9uation &--( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
p a a T a T a T a T + + + +
1 2 #
2
4
#

4
/ I<'7S e9uation
ln p=ln p
c
+(a
1
=+a
2
=
#
2
+a
#
=
#
+a
4
=
!
2
+a

=
4
+a
$
=
1
2
)/ T
r
where T T T
r c
&
(
1 T
r

T>T
c
Lln p=ln p
c
+(a
1
= )/ T
r
T<T
min
Lln p=ln p
c
+("
1
+"
2
/T
r
)
hvap enthalpy of vaporisation correlation >BRmol?
- data un6nown( - coefficients
& 7atsonRHI''= &-@ e9uation( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
H a
6

where 6 a a T a T a T
r r r
+ + +
2 # 4
2

#
( T T T
r c
& (
T T T
r c
& ( 1 T
r
7agner type e9uation for enthalpy of
vaporisation( 3 coefficients
a&( a( a!( a4( a0( a@( a/( Tmin( Tma2
4H / RT
c
=a
1
=
1/ #
+a
2
=
2/ #
+a
#
=+a
4
=
4/ #
+a

=
/ #
+a
$
=
2
+a
!
=
$
where 1 T T
c
&
0 HI''= e9uation &--( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
H a a T a T a T a T + + + +
1 2 #
2
4
#

4
ldens saturated li9uid density correlation >molRm!?
- data un6nown( - coefficients
& Infochem e9uation( 0 coefficients
a&( a( a!( Tmin( Tma2
:=a
1
+a
2
=
a
#
where 1 T T
c
&
;an6inson and Thompson e9uation
>modified?( @ coefficients
a&( a( a!( a4( Tmin( Tma2
+ + + + 1
1
1
#
2
2
#
# 4
4
#
& V a a a a
c
where 1 T T
c
&
8ote that in the a%ove e9uation : is the "ass density and Gc
is the critical volume per unit "ass
! =ac6ett e9uation >modified?( 0 coefficients
a&( a( a!( Tmin( Tma2
-*
( ) 1
1 2 #
& + a a a
6
where
6 + 1
2
!

( 1 T T
c
&
4 HI''= e9uation &-0( @ coefficients
a&( a( a!( a4( Tmin( Tma2
1
2 1
& & a a
6
where
( ) 6 T a
a
+ 1 1
#
4
&
0 HI''= e9uation &--( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
+ + + + a a T a T a T a T
1 2 #
2
4
#

4
/ I<'7S e9uation
:
:
c
=1+a
1
=
1
#
+a
2
=
2
#
+a
#
=

#
+a
4
=
1$
#
+a

=
4#
#
+a
$
=
110
#
7here :
c
is the critical density and
1 T T
c
&
T>T
H
* hyper%olic e2trapolation
T<T
min
* LinearR9uadratic e2trapolation
sdens solid density correlation >molRm!?
- data un6nown( - coefficients
0 HI''= e9uation &--( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
+ + + + a a T a T a T a T
1 2 #
2
4
#

4
lthcond li9uid thermal conductivity correlation >7Rm )?
- data un6nown( - coefficients
& Bamieson e9uation( @ coefficients
a&( a( a!( a4( Tmin( Tma2
+ + +

_
,
a a a a
1 2
1
#
#
2
#
4
1
where 1 T T
c
&
HI''= e9uation &-&( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
ln & ln + + + a a T a T a T
a
1 2 # 4

0 HI''= e9uation &--( / coefficients

a&( a( a!( a4( a0( Tmin( Tma2
+ + + + a a T a T a T a T
1 2 #
2
4
#

4
vthcond vapour thermal conductivity correlation >7Rm )?
- data un6nown( - coefficients
& HI''= e9uation &-( @ coefficients
a&( a( a!( a4( Tmin( Tma2

+ +
a T
a T a T
a
1
# 4
2
2
1 & &
=educed correlation( @ coefficients
a&( a( a!( a4( Tmin( Tma2
-$

+ + +
T
a a T a T a T
r
r r r 1 2 #
2
4
#
where T T T
r c
&
! Eonatomic ideal gas( coefficients( Tmin( Tma2
#!0
0
R &
0 HI''= e9uation &--( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
+ + + + a a T a T a T a T
1 2 #
2
4
#

4
lvisc li9uid viscosity correlation >'a s?
- data un6nown( - coefficients
& =eid( 'rausnit$ and 'oling e9uation &(
4 coefficients a&( a( Tmin( Tma2
a T
a
1
2
HI''= e9uation &-&( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
ln & ln + + + a a T a T a T
a
1 2 # 4

! =educed correlation( / coefficients

a&( a( a!( a4( a0( Tmin( Tma2
( ) ln & a a & a &
1
1
#
2
4
#
+
where
&
a a
T a

# 4
4
1
4 =eid( 'rausnit$ and 'oling e9uation R!( @
coefficients a&( a( a!( a4( Tmin( Tma2
ln & + + + a a T a T a T
1 2 # 4
2
0 HI''= e9uation &--( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
+ + + + a a T a T a T a T
1 2 #
2
4
#

4
vvisc vapour viscosity correlation >'a s?
- data un6nown( - coefficients
& HI''= e9uation &-( @ coefficients
a&( a( a!( a4( Tmin( Tma2

+ +
a T
a T a T
a
1
# 4
2
2
1 & &
=eichen%erg e9uation( 0 coefficients
a&( a( a!( Tmin( Tma2
( ) ( )

+
a T
a T T
r
r
a
r
1
2
1
$
1 1
#
where T T T
r c
&
! Chapman4#ns6og e9uation( 0 coefficients
a&( a( a!( Tmin( Tma2
( )
( )



2$$9 10
!
1
2
1
2 2 2
#
"
,
, *
T
a T a
-,
where
( ) ( )

2 2
#
2
0 2
, * * * *
e%p e%p " & + + +

,T C *T E %T a T
+
T T a
*
&
2
( , 11$14 " ( + 0148!4 " ( C 0248! " (
* 0 !!#20 " ( E 21$1!8 " ( % 2 4#!8! "
0 HI''= e9uation &--( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
+ + + + a a T a T a T a T
1 2 #
2
4
#

4
stension surface tension correlation >8Rm?
- data un6nown( - coefficients
& HI''= e9uation &-@( / coefficients
a&( a( a!( a4( a0 Tmin( Tma2
( ) a T
r
6
1
1
where 6 a a T a T a T
r r r
+ + +
2 # 4
2

#
( T T T
r c
&
#2tended Sprow and 'rausnit$ e9uation( 0
coefficients a&( a( a!( Tmin( Tma2
( ) + a a
a
1 #
2
1
where 1 T T
c
&
0 HI''= e9uation &--( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
+ + + + a a T a T a T a T
1 2 #
2
4
#

4
virialcoeff second virial coefficient correlation >m!Rmol?
- data un6nown( - coefficients
& HI''= e9uation &-4( / coefficients
a&( a( a!( a4( a0 Tmin( Tma2
+ a a a a a + + + +
1 2 #
#
4
8

9

where T T
c
&
0 HI''= e9uation &--( / coefficients
a&( a( a!( a4( a0( Tmin( Tma2
+ a a T a T a T a T + + + +
1 2 #
2
4
#

4
dielectric relative permittivityRdielectric constant correlation
- data un6nown( - coefficients
& Earyott4Smith e9uation &( @ coefficients
a&( a( a!( a4( Tmin( Tma2
>=a
1
+a
2
T +a
#
T
2
+a
4
T
#
Earyott4Smith e9uation ( 4 coefficients
a&( a( Tmin( Tma2
>=e%p
(
a
1
+a
2
T
)
! Infochem e9uation( @ coefficients
a&( a( a!( a4( Tmin( Tma2
>=1+a
1
e%p
(
a
2
Ta
#
T
2
a
4
T
#
)
*4
Petroleum fractions
To define a single petroleum fraction the program re9uires certain
characteristic properties and Eultiflash will then estimate the
other properties needed to support the range of calculations
availa%le in the program.
The list of possi%le properties to support characterisation of the
fraction are*
Car%on num%er
Eolecular weight >gRmol?
Specific gravity at @-
o
F relative to water at @-
o
F
8ormal %oiling point
Critical temperature
Critical pressure
'it$erIs acentric factor
;owever( not all of these are necessary. The minimum input sets
are molecular weight( molecular weight and specific gravityJ
molecular weight and %oiling pointJ %oiling point and specific
gravityJ critical temperature( critical pressure and acentric factor.
<lternatively( the %oiling point can %e used instead of the acentric
factor.
The properties that are estimated( if they have not %een provided(
are*
Car%on num%er
Eolecular weight
8ormal %oiling point
Critical temperature
Critical pressure
Critical volume
<centric factor
'arachor
Hipole moment
#nthalpy of formation
Standard entropy
'erfect gas Cp
Saturated li9uid density
Saturated vapour pressure
#nthalpy of evaporation
Li9uid viscosity
'etroleum fractions will normally %e designated as TY'# &.
*%
Property Calculation
The order in which properties are calculated depends on the
amount of input data provided. In general the following references
are used as a %asis for the calculations*
Eolecular weight =ia$i( E.=. and <l4Sahhaf( T.<.( Fluid Phase
Equilibria &&/ &/44 >&33@?
Doiling point #dmister( 7.C. Pet. %efiner !/ &04 >&301?
Drule( E.=. and 7hitson( C.;.( S'#
Eonograph - >---?
=ia$i( E.=. and <l4Sahhaf( T.<.( ,nd. En!.
Che". %esearh* !4 4&40 >&330?
Specific gravity =ia$i( E.=. and <l4Sahhaf( T.<.( ,nd. En!.
Che". %esearh* !4 4&40 >&330?
Tc( 'c( )esler( E.G. and Lee( D.I.( 'ydroarbon
Proessin! 00>!? &0! >&3/@?
Drule( E.=. and 7hitson( C.;.( S'#
Eonograph - >---?
=ia$i( E.=. and <l4Sahhaf( T.<.( ,nd. En!.
Che". %esearh* !4 4&40 >&330
Gc =ia$i( E.=.( Hau%ert( T.#.( 'ydroarbon
Proessin!( 03( &&0 >&31-?
Lira4Galeana( C.( Firoo$a%adi( <. and
'rausnit$( B.E.( A,ChE A.( 4>&? !3
>&33@?=ia$i( E.=. and <l4Sahhaf( T.<.( ,nd.
En!. Che". %esearh* !4 4&40 >&330?
#nthalpy of Formation and Standard #ntropy
=eid( =.C.( 'rausnit$( B.E. and 'oling( D.#.J
BThe Properties of 2ases and &iquidsB* Gulf(
;ouston >&31/?
Ideal Cp )esler( E.G. and Lee( D.I.( 'ydroarbon
Proessin! 00>!? &0! >&3/@? and
;armens( <.( BChe"ial Ther"odyna"is
4ata on Fluids and Fluid Mi(turesB* I'C
Science and Technology 'ress >&3/3?
Eelting 'oint 7on( ).7.( Fluid Phase Equilbria( !- @0
>&31@?
Lira4Galeana( C.( Firoo$a%adi( <. and
'rausnit$( B.E.( A,ChE A.( 4>&? !3 >&33@?
Fusion properties Eorgan( H.L. and )o%ayashi( =.( Fluid Phase
Equilibria( @! !&/ >&33&?
7on( ).7.( Fluid Phase Equilbria( !- @0
>&31@?
Drown( T.S.( 8iesen( G.G. and #ri6son( H.H.(
SPE 8060 >&334?
Lira4Galeana( C.( Firoo$a%adi( <. and
'rausnit$( B.E.( A,ChE A.( 4>&? !3 >&33@?
Solu%ility 'arameter 'edersen( ).S.( et al( Ener!y and Fuels. 0 34
>&33&?
Surface Tension "uale( F.=.( Che". %e5.( 0! 4!3 >&301?
*)
Li9uid Giscosity Fr%ey( ;. and Sandler( S.I.( Canadian A. Che.
En!.( /4 4!/ >&33!?
*(
Inde.
9
<ctivity coefficient models
<ctivity coefficient e9uations in Eultiflash
!
Flory4;uggins theory !@
Gas phase models for activity coefficient
methods !/
Ideal solution model !
8=TL e9uation !!
=egular solution theory !@
U8IF<C group4contri%ution methods !4
U8I"U<C e9uation !4
7ilson e9uation !!
C
Cu%ic plus association >C'<? model -
/
#9uations of state
Denedict47e%%4=u%in4Starling >D7=S?
e9uation of state e9uation of state @
Cu%ic plus association >C'<? model -
#9uations of state provided in Eultiflash
&4
Ideal gas e9uation of state &0
'C4S<FT e9uation of state
'eng4=o%inson &3/1 >'=/1? e9uation of
state &@
'eng4=o%inson e9uation of state &0
'S=) e9uation of state 4
'S=)48=TL e9uation of state 4
Lee4)esler >L)? and Lee4)esler4'lCc6er
>L)'? e9uation of state 4
=edlich4)wong >=)? and =edlich4)wong4
Soave >=)S? e9uations &@
G
;ydrates
;ydrate inhi%itor model 4
B
Eodels 00
@
7ilson < e9uation !!