User Guide for

Models and Physical Properties

Infochem/KBC Advanced Technologies plc

Version 6.1

June 2016

Infochem/KBC Advanced Technologies plc

42-50 Hersham Road
Walton on Thames
Surrey
KT12 1RZ
UK
T +44 (0) 1932 242 424
F +44 (0) 1932 224 214
e-mail: [email protected]
 This User Guide and the information contained within is the copyright of KBC Advanced Technologies plc

Infochem/KBC Advanced Technologies plc

42-50 Hersham Road
Walton on Thames
Surrey
KT12 1RZ
UK
T +44 (0) 1932 242 424
F +44 (0) 1932 224 214
e-mail: [email protected]

Disclaimer
While every effort has been made to ensure that the information contained in this document is
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. Neither KBC Advanced Technologies plc nor
any of its employees, contractors or agents shall be liable for direct, indirect or consequential
losses, damages, costs, expenses, claims or fee of any kind resulting from any deficiency, defect
or error in this document, the software or the data.
Contents
Overview......................................................................................................................5
Introduction.................................................................................................................5
What types of model are available?........................................................................5

Thermodynamic properties from an Equation of State.....................8

Introduction.................................................................................................................8
Enthalpy........................................................................................................................8
Entropy..........................................................................................................................9
Fugacity coefficients................................................................................................10
Gibbs Energy and Internal Energy........................................................................11
Heat Capacity, constant pressure.........................................................................11
Heat Capacity, constant volume...........................................................................11
Isothermal compressibility....................................................................................12
Isobaric expansivity or thermal expansion........................................................12
Joule Thompson coefficient...................................................................................12
Activity Coefficient..................................................................................................12
Speed of Sound.........................................................................................................13

Equations of state provided in Multiflash..............................................14

When to use equation of state models...............................................................14
Perfect gas equation of state.................................................................................15
Peng-Robinson equation of state..........................................................................15
Peng-Robinson 1978 (PR78) equation of state..................................................16
Redlich-Kwong (RK) equation................................................................................16
Zudkevitch-Joffe (ZJ)...............................................................................................17
Advanced Equation of state options...................................................................18
Cubic plus association (CPA) model....................................................................22
PC-SAFT equation of state.....................................................................................23
PSRK equation of state...........................................................................................25
PSRK-NRTL equation of state................................................................................25
Lee-Kesler (LK) and Lee-Kesler-Plöcker (LKP) equations of state..................25
Benedict-Webb-Rubin-Starling (BWRS) equation of state................................27
Multi-reference fluid corresponding states (CSMA) model............................28
GERG 2008 Model....................................................................................................31

Activity coefficient equations in Multiflash..........................................34

When to use activity coefficient models.............................................................34
Ideal solution model................................................................................................34
Wilson equation........................................................................................................35
NRTL equation..........................................................................................................35
UNIQUAC equation..................................................................................................36
UNIFAC group-contribution methods.................................................................36
Regular solution theory..........................................................................................38
Flory-Huggins theory...............................................................................................38
Gas phase models for activity coefficient methods.........................................39
Models for solid phases....................................................................................40
Introduction..............................................................................................................40
Solid freeze-out model............................................................................................40
Modelling hydrate formation and inhibition.....................................................41
Salinity Model............................................................................................................45
Modelling wax precipitation..................................................................................46
Modelling asphaltene flocculation.......................................................................46
Other thermodynamic models..............................................................................47

Transport property models............................................................................48

Introduction..............................................................................................................48
Viscosity.....................................................................................................................48
Thermal conductivity..............................................................................................51
Surface Tension........................................................................................................54
Diffusion coefficients..............................................................................................56

Binary interaction parameters......................................................................58

Introduction..............................................................................................................58
Number of BIPs related to any model..................................................................58
Units for BIPs.............................................................................................................59
BIPs available in Multiflash....................................................................................60

Model data requirements.................................................................................62

Components............................................................................................................66
Introduction..............................................................................................................66
Normal components................................................................................................66
Petroleum fractions.................................................................................................74

Index............................................................................................................................76
Overview

Introduction
Multiflash is an advanced software package for performing
complex equilibrium calculations quickly and reliably. The main
utility is a multiple phase equilibrium algorithm that is interfaced
to Infochem’s package of thermodynamic models and a number of
physical property data banks.
The purpose of this guide is to provide more detailed descriptions
of the models available in Multiflash than you will find in our main
User Guide. The correlation equations for storing pure component
properties in our physical property databanks will also be
described.
This section defines what a model is in terms of the Multiflash
nomenclature, what models are available and when you might wish
to use them.

What types of model are available?

Within the context of Multiflash, 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 key thermodynamic property calculation carried out within
Multiflash is the determination of phase equilibrium. This is based
on the fundamental relationship that at equilibrium the fugacity of
a component is equal in all phases. For a simple vapour-liquid
system

fiv  fil
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 liquid phase.
The models used in Multiflash to represent the fugacities from the
phase equilibrium relationship in terms of measurable state
variables (temperature, pressure, enthalpy, entropy, volume and
internal energy) fall into two groups, equation of state methods
and activity coefficient methods. The basis of each of these
methods is described below.

5
With an equation of state method, all thermal properties for any
fluid phase can be derived from the equation of state. With an
activity coefficient method the vapour phase properties are derived
from an equation of state, whereas the liquid properties are
determined from the summation of the pure component properties
to which a mixing term or an excess term has been added.
Multiflash may also be used to calculate the phase equilibrium of
systems containing solid phases, either mixed or pure. These may
occur either when a normal fluid freezes or may be a particular
solid phase such as a hydrate, wax or asphaltene. Models used to
represent these solids are discussed below.
The transport properties of a phase (viscosity, thermal
conductivity and surface tension) are derived from semi-empirical
models, which will be discussed later.

Equation of state methods

An equation of state describes the pressure, volume and
temperature (PVT) behaviour of pure components and mixtures.
Most equations of state have different terms to represent the
attractive and repulsive forces between molecules. Any
thermodynamic property, such as fugacity coefficients and
enthalpies, can be calculated from an equation of state relative to
the perfect gas properties of the same mixture at the same
conditions.
In the equation of state method the partial pressure of a
component i in a gas mixture is
pi  yi p .
The fugacity of a component in an perfect gas mixture is equal to
its partial pressure; the fugacity in a real mixture is the effective
partial pressure

f i v   iv yi p
where  iv is the fugacity coefficient. For a vapour at moderate
pressures  i is close to unity.
v

Similarly for a liquid

f i l   il xil p
Although since a liquid differs considerably from an perfect gas
the fugacity coefficients for a liquid are very different from unity.

Activity coefficient methods

In an ideal liquid solution the liquid fugacity of each component in
the mixture is directly proportional to the mole fraction of the
component

f i l  xi f i *,l
The ideal solution assumes that all molecules in the liquid solution
are identical in size and are randomly distributed. This assumption
is valid for mixtures made up of molecules of similar size and
6
type, but for mixtures of unlike molecules you must expect varying
degrees of non-ideality. The activity coefficient,  i , represents the
deviation of the mixture from ideality, as defined by the ideal
solution.
The fugacity coefficients for the activity coefficient equations are
calculated from the standard relationship:
ln i  ln  i  ln pisat  ln isat  ln p   i
where  i is the activity coefficient of component i which is
derived from the excess Gibbs energy as follows:

 GE
ln  i  .
 ni
pisat is the saturated vapour pressure of component i ,  isat is the
fugacity coefficient of the pure saturated vapour of component i
(calculated from the gas phase model associated with the activity
coefficient equation) and p is the total pressure.

The Poynting 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 zero excess volume of mixing, and that the
liquid is incompressible:

( p  pisat )visat
i 
RT
where visat is the saturated liquid volume of component i .

7
Thermodynamic properties
from an Equation of State

Introduction
Any thermodynamic property can be calculated with an equation
of state. This section present the general expressions used in
Multiflash to calculate thermodynamic properties, like enthalpy
and fugacity coefficients from equations of state. Some properties,
like enthalpy and entropy are calculate directly from the equation
of state, while others like the Gibbs energy are calculated as
combinations of other properties.

Enthalpy
In Multiflash the enthalpy is calculated as
H =H ref + H pg + H res ,
where:
H ref is the (arbitrary) enthalpy value in a reference state to be
defined.
H pg is the perfect gas contribution to the enthalpy, given by:
T
H pg =∫T C P , pg dT ,
ref

where C P , pg is the perfect gas heat capacity;

H res is the residual enthalpy, which is calculated from the
thermodynamic model specified for thermal properties, using the
standard thermodynamic relation:

[( ) ]
V
∂P
H res=PV −RT + ∫ −P dV
∞ ∂T V
.

The absolute value of enthalpy has no physical meaning but

enthalpy differences are measurable quantities, therefore H ref can
be chosen at will. Multiflash has two possible reference states that
are user selectable:

8
 1. ‘Compound’ datum (default): The enthalpy of each pure
component in the perfect gas state at 298.15 K and 1 atm is set to
zero. This is done by setting:

H ref =−H 298

pg ,
298
where H pg is the value of H pg at T = 298.15 K.
2. ‘Elements’ datum: The enthalpy of each element is set to zero in
the perfect gas state at 298.15K and 1 atm., which is done by
setting:

H ref =Δ H of − H 298
pg ,
o
where Δ H f is the standard enthalpy of formation of the
compounds in the perfect gas state at 298.15 K and 1 atm.
This datum produces enthalpy values that are much larger
numerically than the ‘compound’ datum but enthalpy differences
between two states are the same. When calculating chemical
reaction equilibrium the ‘elements’ datum must be used because it
is the elemental entities that are conserved rather than the
molecular entities.
The overall enthalpy is obtained by multiplying the mole numbers
of each phase with the enthalpy of each phase, and summing over
all phases:
NP
H =∑ n j H j .
j

Entropy
The entropy is in Multiflash calculated as:
S=S ref + S pg + S res ,
where:
S ref is the (arbitrary) entropy value in a reference state to be
defined.
S pg is the perfect gas contribution to the entropy, given by:
T
C P , pg
S pg= ∫ dT ,
T ref
T
where C P , pg is the perfect gas heat capacity;
S res is the residual entropy at specified T and P, which is
calculated from the thermodynamic model specified for thermal
properties, using the standard thermodynamic relation:

[( ) ]
P
∂P R
S res=∫ − dV + R ln Z ,
0
∂T V V
where Z is the compressibility factor:

9
 PV
Z= .
n RT
Although the absolute entropy can be argued to have a physical
interpretation, in practise, it is entropy differences that are
experimentally accessible and S ref can be chosen at will. Multiflash
has three possible reference states that are user selectable:
1. ‘Compound’ datum (default): The entropy of each pure
component in the perfect gas state at 298.15 K and 1 atm is set to
zero. This is done by setting:

S ref =−S 298

pg ,

where S 298
pg is the value of
S pg at 298.15 K.
2. ‘Elements’ datum: The entropy of each element is set to zero in
the perfect gas state at 298.15K and 1 atm, by setting:

S ref =Δ S of −S 298
pg ,
o
where Δ S f is the entropy of formation at 298.15 K and 1 atm.

This datum produces values that are much larger numerically than
the ‘compound’ datum but entropy differences between two states
are the same. When calculating chemical reaction equilibrium the
‘elements’ datum must be used.
3. ‘Standard’ datum (sometimes called the ‘third-law or ‘absolute’
entropy): The reference entropy is chosen so that the entropy of
each component in the perfect gas state at 298.15K and 1 atm is
equal to the standard entropy of that component. This is done by
setting:

S ref =S o−S 298

pg

The standard entropy, S o is relative to a zero value at absolute

zero. The ‘standard’ datum may also be used in chemical reaction
analysis since the results are equivalent to the ‘elements’ datum.
The overall entropy is obtained by multiplying the mole numbers
of each phase with the entropy of each phase, and summing over
all phases.

Fugacity coefficients
The fugacity coefficient, ϕ̂ i is the ratio between the fugacity and
the partial pressure of a given component:

f̂ i
ϕ̂ i=
P xi
It is calculated as:

[( ) ]
V
−1 ∂P RT
ln ϕ̂ i= ∫
RT ∞ ∂ ni
−
V
dV −ln Z
T ,V , n j

10
Gibbs Energy and Internal Energy
The internal energy, U is calculated from the enthalpy:
U =H −PV
and the Gibbs free energy, G is calculated from the enthalpy and
entropy
G=H −TS

Heat Capacity, constant pressure

The heat capacity at constant pressure, C P is equal 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

contribution:

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.
A number of correlations for the perfect gas heat capacity are
stored in the Infodata databank, but user-defined correlations may
be entered . Which correlation from the databank is used depends
on the component.
As for enthalpy the overall heat capacity is obtained by multiplying
the heat capacity of each phase with the corresponding mole
numbers.

Heat Capacity, constant volume

C V is the heat capacity at constant volume, given by the
temperature derivative of the internal energy at constant volume:

CV = ( )
∂U
∂T V
.

More conveniently it can be calculated from the constant pressure

heat capacity and the temperature and pressure derivatives of V:
2 −1
C V =C P+ T
∂V
∂T( )( ) P
∂V
∂P T
.

As for enthalpy the overall heat capacity is obtained by multiplying

the enthalpy of each phase with the corresponding mole numbers.

11
Isothermal compressibility
The quantity isothermal compressibility, β , is the response of a
material in terms of volume change when pressure is applied at
constant temperature.
It is determined using the following expression:

β=
−1 ∂ V
V ∂p ∣ T =const

Where V is the volume, p is the pressure and T is the temperature.

The inverse of the compressibility is called the bulk modulus.

Isobaric expansivity or thermal expansion

The quantity isobaric expansivity, α , is the response of a material
in terms of volume change when temperature changes at constant
pressure.
It is determined using the following expression:

α=
1 ∂V
V ∂T ∣
p=const

Where V is the volume, p is the pressure and T is the temperature.

Joule Thompson coefficient

The Joule-Thompson effect describes the behaviour of the
temperature of a mixture when it is subjected to pressure changes
without energy transfer to the surroundings.
This is quantified by the Joule-Thompson coefficient ( μ JT ) given
by:

μ JT =
∂T
∂P ∣
H=const
=
V
CP
(α T −1)

The quantity α is the isobaric expansivity described above. The

values V, P and CP are volume, pressure and heat capacity at
constant pressure, respectively.

Activity Coefficient
The activity coefficient of a component is defined as the activity of
that component divided by the mole fraction:
ai (T , P , n)
γi ≡ ,
xi
and it is in Multiflash calculated as the fugacity of the component
in the mixture divided by the pure component fugacity at the same
temperature and pressure:

12
 ̂ i (T , P , n)
ϕ
γi = .
ϕi (T , P )

Speed of Sound
The Speed of Sound of each phase is calculated as:

√
CPV 2
c=
∂V ,
−C V M w
∂P
where M w is the molecular weight of the phase
For multiple phases the overall speed of sound is estimated using
the equation of Wallis. Reference: G. B. Wallis: 'One dimensional
two-phase flow', McGraw-Hill, 1969.
V mix
c=

√
∂V
NP CV NP
∂P
−∑ ni ×∑ n i Mni
i CP i

13
Equations of state provided in
Multiflash

When to use equation of state models

Equations of state (EOS) can be used over wide ranges of
temperature and pressure, including the sub-critical and
supercritical regions. They are frequently used for ideal or slightly
non-ideal systems such as those related to the oil and gas industry
where modelling of hydrocarbon systems, perhaps containing light
gases such as H2S, CO2 and N2, is the norm. Equation of state
methods do not necessarily represent highly non-ideal chemical
systems, such as alcohol-water, well. For this type of system, at low
pressure, an activity coefficient approach is preferable but at
higher pressure you may need to use an equation of state with
excess Gibbs energy mixing rules, see “Mixing Rules” on page 18.
All equations of state will describe any system more accurately
when binary interaction parameters (BIPs) have been derived from
the regression of experimental phase equilibrium data. BIPs are
adjustable factors, which are used to alter the predictions from a
model until these reproduce as closely as possible the
experimental data.
As mentioned earlier the thermal properties of any fluid phase can
be derived from an equation of state. However, one property,
which is often poorly represented by the simpler equations of
state, is the liquid density. Multiflash offers enhanced versions of
both the Redlich-Kwong-Soave (RKS) and Peng-Robinson (PR) cubic
equations of state where the equation of state parameters can be
fitted to reproduce both the saturated vapour pressure using a
databank correlation and the saturated liquid density at 298K or
Tr=0.7 (Peneloux method). These are referred to in Multiflash as the
advanced version of the particular equation of state.
Further guidance on the use of specialised equations of state is
given in the following sections.

Perfect gas equation of state

The perfect gas equation of state is defined as

14
 N RT
p= .
V
This model is normally used in conjunction with an activity
coefficient method when the latter is used to model the liquid
phase. It could also be used to describe the behaviour of gases at
low pressure.

Peng-Robinson equation of state

The Peng-Robinson (PR) equation (D.-Y. Peng and D. B. Robinson,
Ind. Eng. Chem. Fundam., 15, 1, (1976)).is a cubic equation of state.
It is described by
NRT a
p  2
V  b V  2bV  b 2
where a and b are derived from functions of pure component
critical temperatures and pressures and acentric factor.

  
2
a i  a ci 1   i 1  T Tci

R 2 Tci2
a ci  0.45724
pci
and

 i  0.37464  154226
.  i  0.26992 i2
except for water when T Tci < 0.85 where the following
alternative relation is used:

  
2
ai  a ci 10085677
.  0.82154 1  T Tci

The standard (Van der Waals 1-fluid) mixing rules are:

N   ni
i

a   ai a j (1  k ij )ni n j
ij

b   bi ni
i

RTci
bi  0.07780
pci
k ij is usually referred to as a binary interaction parameter, the use
of such parameters is discussed in a later section.

15
Peng-Robinson 1978 (PR78) equation of state
The 1978 revised version of the Peng-Robinson EOS (D. B. Robinson
and D.-Y. Peng, GPA Research Report 28, Gas Processors
Association, Tulsa, (1978)) has a different treatment for the
parameter  . If the acentric factor   0.49 the same expression
is used as before:

 i  0.37464  154226
.  i  0.26992 i2
but, if   0.49 the following relationship is used:

 i  0.379642  1.48503 i  0.164423 i2  0.01666 i3

The new expression removes a defect in the original equation
where heavy components with higher acentric factors become
more volatile than components with somewhat lower acentric
factors. However, for any mixture containing components with
acentric factors greater than 0.49 the PR78 equation will give
different results and must therefore be treated as a different
model.

Redlich-Kwong (RK) equation

The Redlich-Kwong EOS (O. Redlich and J. N. S.. Kwong, Chem. Rev.,
44, 233, (1949)) and its variants are further examples of simple
cubic equations of state.
It has the form:
NRT a
p 
V  b V (V  b)
where

a i  a ci Tci T

R 2 Tci2
a ci  0.42748
pci
The standard (Van der Waals 1-fluid) mixing rules are:

N   ni
i

a   ai a j (1  k ij )ni n j
ij

b   bi ni
i

RTci
bi  0.08664
pci

16
Redlich-Kwong-Soave (RKS) equation
The RKS EOS (G. Soave, Chem. Eng. Sci., 27, 1197, (1972)) .has the
same form and mixing rules as the RK equation but the a
parameter is a function of temperature.

  
2
a i  a ci 1   i 1  T Tci

where:

 i  0.48  1574
.  i  0176
.  i2
and for API variant (M. S. Graboski and T. E. Daubert, Ind. Eng.
Proc. Des. Dev., 17, 443, (1978)):

  
2
a i  a ci 1   i 1  T Tci

where:

 i  0.48508  15517
.  i  015613
.  i2
except for hydrogen, which in the API variant is given by:

 T
a i  1202
. a ci exp 0.30228 
 Tci 

Zudkevitch-Joffe (ZJ)
The ZJ EOS is based on the original version of Redlick-Kwong (RK)
eos (D. Zudkevitch and J. Joffe, AIChEJ, 16, 112 (1970).
For the original version of RK, the “a” and “b” parameters are
expressed explicitly in terms of the critical temperature and
pressure
NRT a
p 
V  b V (V  b)
where the ai and bi for each component are defined as:
RT c
bi =0.08664
pc
2 2
R T ci
a i=0.42748
p ci
√T ci /T

For the ZJ eos, the ai and bi parameters are defined by

simultaneously solving the equations of fugacity coefficients along
the saturation line and the RKS equation for both vapour and
saturated liquid phase, where the required saturation vapour
pressure and saturated liquid density are obtained from the
correlation of the pure components.

17
Advanced Equation of state options
The advanced implementation of both the Peng-Robinson and the
Redlich-Kwong-Soave equations of state (PRA, PR78A and RKSA
models) contain additional non-standard features. These include
the ability to match stored values for the liquid density and the
saturated vapour pressure and a choice of mixing rule.

The Peneloux density correction

This correlation is used to match the density calculated from the
equation of state to that stored in the chosen physical property
data system. For light gases, the density is matched at a reduced
temperature of 0.7 and the volume correction is assumed constant.
For liquid components the volume shift is a function of
temperature.
ci  ci 0  ci1T  ci 2 / T

V  V '   ci xi
The three coefficients may be stored as part of the pure
component data record.
Multiflash usually treats the volume shift as a linear function of
temperature; the density is matched at 290.7K and 315.7K so as to
reproduce the density and thermal expansivity of liquids over a
range of temperatures centred on ambient. However, users may
also use the third term and enter the coefficient values directly.

Fitting the vapour pressure curve

The function for a i is generalised to the following form:

 
2
a  a ci 1   i1t i   i 2 t i2   i 3 t i3   i 4 t i4   i 5 t i5
where

t i  1  T Tci
.
For each component the constants,  i1 to  i5 are fitted by linear
regression to the vapour pressure over a range of reduced
temperatures corresponding to the stored data. Fewer than 5
coefficients will be fitted if there is insufficient data or if the
extrapolation to low temperatures is unrealistic. If the vapour
pressure is undefined, the correlation for ai reverts to the
standard equation for that component.

Mixing Rules
For highly non-ideal systems it is often useful to be able to use any
Gibbs energy excess model (e.g. UNIQUAC or NRTL) as part of the
mixing rule for the equation of state. There are several different
ways in which this can be done; Multiflash currently provides
options for the MHV2 type mixing rule, the Huron-Vidal type
mixing rule, the PSRK mixing rule and the Infochem modification
18
based on the NRTL equation. The latter is used for modelling the
fluid phases in hydrate calculations.

MHV2-type mixing rules:

N   ni
i

b   bi ni
i

RTb  s2 N 2 
a  Q( )  
s1  Q( ) 

GE   b 
Q( )    ni  Qi ( i )  ln 
RT i   Nbi  

 i s1  ( i s1 ) 2  4 s2
Qi ( i ) 
2

For the RKS equation s1  ln 2 and s2  17.25

1 2  2
s1  ln   0.623225
For the PR equation
2 2 2  2 and
s2  20.129 .

Huron-Vidal type mixing rules:

N   ni
i

b   bi ni
i

 GE  a 
a  b    ni  i  
 s1 i  bi  

For the RKS equation s1  ln 2

1 2  2
s1  ln   0.623225
For the PR equation
2 2 2  2

PSRK type mixing rules:

N   ni
i

b   bi ni
i

19
 a=b
[ G E RT
+
s1 s1
∑ ni ln
i ( ) ( )]
b
bi i
a
+∑ n i i
bi

s 1=−0.64663

Infochem mixing rules:

These mixing rules are similar to the original Huron-Vidal mixing
rules apart from the form of the interaction parameters k ij , k ji
and  ij which gives a different form of temperature dependence.
These rules reduce to the conventional van der Waals mixing rules
when k ij  k ji and  ij  0 .

N   ni
i

b   bi ni
i

 j n j b j  ji G ji
a  b ni
i  j n j b j G ji
where:

2 ai a j (1  k ji )
 ji 
bi  b j
and:

  ji ( ji   ii ) 
G ji  exp 
 RT 

Huron-Vidal-Pedersen (HVP) mixing rules:

The HVP mixing rule was first described in JN Kristensen, PL
Christensen, KS Pedersen and P. Skovborg “A combined Soave-
Redlich-Kwong and NRTL equation for calculating the distribution
of methanol between water and hydrocarbon phases”. Fluid Phase
Equilibria. 82, 199-206, 1993. It was designed to extend the validity
of cubic equations of state to systems containing methanol. It
requires three binary interaction parameters (i.e., Dgij/R, Dgji/R,
and ij=ji).
The mixing rule can be written as:

N   ni
i

b   bi ni
i

ai g ex
a=b [( ∑ n i )− ],
i=1 bi ln 2
with

20
 −α ji Δ g ji
∑ Δ g ji b j n j exp(
RT
)
ex
g =∑ n i j=1
−α Δ g
i=1
∑ b j n j exp( Rji T ji )
j =1

The parameters ij are dimensionless. On the other hand, it is

common in literature to encounter the asymmetric parameters
expressed in the form Dgij/R with the units of K. Indeed,
Multiflash accepts the asymmetrical parameters in this form (i.e.,
Dgij/R) and with units of K.
If for a given pair of components i-j, the phase behaviour can be
accurately described with “classical” WDW kij, we can obtain the
corresponding HVP parameters by setting ij = 0 and using:

Δ g ji =ln 2 [
ai
−2
√(a i a j ) (1−k ) ]
ij
bi bi + b j
Therefore, the Multiflash GUI is also able to deal with “VDW-like”
parameters for the HVP mixing rule.
Finally, if all the pairs of component can be described by classical
and symmetric kij, the HVP mixing rule reduces to the
conventional VDW mixing rule.

When to use cubic equations of state

The simple cubic equations of state, PR and RKS, are widely used
in engineering calculations. They require limited pure component
data and are robust and efficient. Both PR and RKS are used in gas-
processing, refinery and petrochemical applications. They will
usually give broadly similar results, although if one model has
been fitted to experimental data and there are no interaction
parameters for the other then the optimised model is always
preferable. There is some evidence that RKS gives better fugacities
and PR better volumes (densities) but both can be improved if the
Peneloux correction is used.
For most applications we would recommend the use of the RKSA
(or PRA, PR78A) model sets which use the Peneloux correction, fit
a to the vapour pressure and use the Van der Waals 1-fluid mixing
rules.
RKSA with the Infochem mixing rules is used as part of the hydrate
model and provides extra flexibility to represent the highly non-
ideal polar systems. It does, however, require suitable BIPs for such
systems.
The API variant of RKS is applicable to petroleum systems and
mixtures containing hydrogen, while RK may be used instead of
perfect gas model for the vapour phase of systems where the
liquid phase is being modelled with an activity coefficient model.

21
Cubic plus association (CPA) model
The CPA model consists of the Redlich-Kwong-Soave equation plus
an additional term based on Wertheim’s theory that represents the
effect of chemical association.
The form of the model is:

∑ n i F i (1− X i )
i NRT a
p= + +
V −0. 45b V −b V ( V + b )
The parameters a ci and bi are set for each component to satisfy
p  2 p
the critical conditions   0 at the known critical point
V V 2
of that component. The parameter a is a function of temperature
given by:


ai T   a ci 1   1i t i   2i t i2   3i t i3   4i t i4   5i t i5 
2

where:

t i  1  T Tci .

For each component the constants,  0 i to  i5 are fitted by linear

regression to the vapour pressure over a range of reduced
temperatures corresponding to the stored data. Fewer than 5
coefficients will be fitted if there are insufficient data or if the
extrapolation to low temperatures is unrealistic.
The model uses the standard (Van der Waals 1-fluid) mixing rules
which are:

N   ni
i

a   ai a j (1  k ij )ni n j
ij

b   bi ni
i

RTci
bi  0.08664
pci
The Wertheim association term is complex and, for a complete
discussion, the user should refer to the scientific literature. In
summary, the terms X i are found by simultaneously solving the
Wertheim equations, which in the CPA model have the form:

1
j K ij F j X j
 1
Xi V  0.45b
where Fi are the number of (donor) bonding sites on component i
and K ij is the association constant for components i and j .

22
 The CPA model also uses the Peneloux density correction to match
the liquid density calculated from the equation 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 liquid density at two different temperatures. For light
gases, a constant volume shift is used that is fitted to the gas’s
liquid density at a reduced temperature of 0.7.

When to use CPA

The CPA model may be used for hydrate calculations with
methanol, ethanol, MEG, DEG, TEG and salt inhibition, as these are
the only cases for which parameters are currently provided.
Parameters for additional substances may be added in future
versions of Multiflash.

PC-SAFT equation of state

The PC-SAFT equation is a development of the SAFT model that
has been shown to give good results for a wide range of polar and
non-polar substances including polymers. Polymers are one of the
most important areas of application of PC-SAFT. The model
appears to be one of the most accurate and realistic equations of
state currently available for modelling polymer systems.
PC-SAFT stands for the Perturbed Chain Statistical Associating
Fluid Theory and it incorporates current ideas of how to model
accurately the detailed thermodynamics of fluids within the
framework of an equation of state. The mathematical structure is
very complex and cannot be conveniently described in a manual.
Users are referred to Appendix A of the reference given below.
Reference: Perturbed-Chain SAFT: An Equation of State Based on a
Perturbation Theory for Chain Molecules by Gross and Sadowski in
Industrial and Engineering Chemistry Research, 40, 1244, (2001).
The Multiflash version includes an implementation of the
association term of PC-SAFT which is discussed in the paper,
Application of the Perturbed-Chain SAFT Equation of State to
Associating Systems by Gross and Sadowski in Industrial and
Engineering Chemistry Research, 41, 5510, (2002). This paper
however does not discuss the mathematical formulation of the
association term; this can be found in the following reference.
Reference: New Reference Equation of State for Associating Liquids
by Chapman, Gubbins, Jackson and Rodosz in Industrial and
Engineering Chemistry Research, 29, 1709, (1990).
The Multiflash implementation follows the same general structure
as the association term in the CPA model.
Multiflash also has a version of PC-SAFT with simplified mixing
rules as proposed by researchers at the Danish Technical
University.
Reference: Computational and Physical Performance of a Modified
PC-SAFT Equation of State for Highly Asymmetric and Associating
Mixtures by von Solms, Michelsen and Kontogeorgis in Industrial
and Engineering Chemistry Research, 42, 1098, (2003).

23
Polymer Components
Polymers are not well-defined chemical compounds but rather a
distribution of chain molecules of varying molecular weight. In
Multiflash, polymers must be represented by one or more pseudo
components, which must be set up as user-defined components.
Using PC-SAFT, every pseudo component for a given polymer must
be assigned the same values of the pure-compound parameters
SAFTSIGMA (in metres, not Ångstrom units) and SAFTEK. In
addition, the SAFTM parameter must be specified. This is normally
quoted as a ratio to the molecular weight, so it has to be calculated
for each polymer pseudo component knowing the molecular
weight. For polystyrene, for example, Gross and Sadowski give the
ratio as 0.019, so for a polystyrene pseudo component of
molecular weight 100000, the SAFTM parameter should be set to
1000000.019=1900, etc.
Additionally, the user can define association parameters if the
polymer forms hydrogen bonds. These parameters are SAFTBETA
which defines the volumetric or entropic parameter, and
SAFTEPSILON the energy or enthalpy parameter. Multiflash also
provides an extension to the PC-SAFT definition: the user can also
supply a heat capacity parameter SAFTGAMMA for the association
term. For the association term to be non-zero, the user must also
define the parameter SAFTFF which denotes the number of donor
bonding sites per segment of polymer.
Values of PC-SAFT parameters for polymers can be found in
Modeling Polymer Systems Using the Perturbed-Chain Statistical
Associating Fluid Theory Equation of State by Gross and Sadowski
in Industrial and Engineering Chemistry Research, 41, 1084, (2002)
and in Modeling of polymer phase equilibria using Perturbed-Chain
SAFT by Tumakaka, Gross and Sadowski in Fluid Phase Equilibria,
194-197, 541, (2002).

Defining Polymers and Copolymers from their

Segments
Multiflash also allows the user to define up to four polymer
segments which can be used to define any number of
homopolymers or copolymers following the method of Tumakaka,
Gross and Sadowski described in the reference above.
For each segment the user must define the molecular weight MW
and the SAFT parameters SAFTEK and SAFTSIGMA. Optionally, the
association parameters SAFTBETA, SAFTEPSILON, optionally
SAFTGAMMA and SAFTFF can be defined.
Once a number 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 SAFT component. To define polymer
components in this manner, all the user has to do is define the
molecular weight MW of the polymer and specify the bond
fractions between 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 segment; if it is formed of
two or more types of segment, it is a copolymer. The definition of
the bond fractions is given by Tumakaka, Gross and Sadowski,

24
 (although their examples of actual values of bond fractions are not
realistic).
All other parameters of the polymer, including the segments
fractions, are then internally calculated by Multiflash from the
supplied molecular weight and bond fractions. The user can define
the BIPs between normal components and/or segments. Note that
in the fluid composition, the amounts of the segments must all be
set to zero, as the segments are not real components of the
mixture.

PSRK equation of state

This model consists of the RKSA equation of state with vapour
pressures fitted using Mathias-Copeman parameters (if available),
the Peneloux volume correction and the PSRK type mixing rules.
The excess Gibbs energy is provided by the PSRK variant of the
UNIFAC method. This is the same as the normal VLE UNIFAC
model except that the group table has been extended to include a
large number of common light gases.

When to use PSRK

The PSRK model is an extension of the UNIFAC method. It is
intended to predict the phase behaviour of a wide range of polar
mixtures using the solution of groups concept as embodied in
UNIFAC. The main benefit of PSRK is that it is able to handle
mixtures containing gases much better than UNIFAC and unlike a
normal equation of state it can handle polar liquids. This is
because (a) it uses an equation of state with an excess Gibbs
energy mixing rule thereby avoiding problems of how to handle
supercritical components in an activity coefficient equation; (b) the
UNIFAC group parameter table has been extended in PSRK to
include 32 common light gases.

PSRK-NRTL equation of state

This model is the same as the PSRK model except that the excess
Gibbs energy is provided by the NRTL equation. So unlike the PSRK
equation, the PSRK-NRTL variant requires that BIPs are provided
for the NRTL equation in order to give accurate results. Its
advantage is that, provided the BIPs are fitted to relevant phase-
equilibrium data, the model can give more accurate predictions
than the PSRK equation.

Lee-Kesler (LK) and Lee-Kesler-Plöcker (LKP)

equations of state
The LK and LKP methods are 3 parameter corresponding states
methods based on interpolating the reduced properties of a
mixture between those of two reference substances. The equation
for each property is of the form:

25
  (1)
z mix  z ( 0) 
 (1)

z  z ( 0) 
where z ( 0 ) and z (1) are the compressibility factors of the two
reference fluids expressed as functions of reduced temperature,
pressure and volume. To apply the method to a mixture, therefore,
it is necessary to obtain averaged critical properties by the use of
mixing rules. The only difference between the LK and LKP methods
lies in the value of the parameter  in the mixing rules which are
defined as follows. First the critical compressibility factor for each
component i is defined from the acentric factor by:
Z ci  0.2905  0.085 i
and hence the critical molar volumes:
v ci  Z ci RTci / p ci
The main mixing rules have the form:
Z c , mix  x Z
i
i i

3
 v ci
1/ 3
 v 1cj/ 3 
v c , mix   xi x j  
 2 
ij  
3
1  v 1ci/ 3  v 1cj/ 3 
Tc , mix  
vc
 x x 
i j
2


Tci Tcj k ij
ij  
p c , mix  RTc , mix Z c , mix / v c , mix

where Tc and p c denote the critical pressure and temperature,

k ij denotes the BIP the default value of which is 1, and R
denotes the gas constant. Subscript i denotes component i . For
the LK method   1 , whereas for the LKP method   0.25 .
In Multiflash, all the BIPs for the LK method are set to the default
value of 1. For the LKP method, it is quite important to adjust the
BIPs in order to get reasonable phase equilibrium predictions.
Multiflash uses correlations for the BIPs proposed by Knapp et al.
In these correlations the BIPs are all set to constant values,
although Multiflash allows the user to use temperature dependent
BIPs if required. A complete description of the method can be
found in Vapor-Liquid Equilibria for Mixtures of Low Boiling Point
Substances by Knapp, Döring, Oellrich, Plöcker and Prausnitz,
Chemistry Data Series Volume VI, Dechema 1982.

When to use LK or LKP

The methods predict fugacity coefficients, thermal properties and
volumetric properties of a mixture. However, they are rather slow
and complex compared to the cubic equations of state and are not
particularly recommended for phase equilibrium calculations,
although they can yield accurate predictions for density and
enthalpy. They would normally be applied to non-polar or mildly
polar mixtures such as hydrocarbons and light gases.

26
Benedict-Webb-Rubin-Starling (BWRS) equation of
state
The BWRS equation method is an 11 parameter non-cubic equation
of state. It is described by

RT  B C D C'   2   2 
p  N   2  5  2 1  2  exp  2  
V 
 V V V V  V   V 


where:

1  C D E 
B  B0   A0  02  30  04 
RT  T T T 

1  3 d3 
C b  3
 a  
RT  T 
3  3 d3 
D  a  
RT  T 
c3
C' 
RT 3
Mixing rules are used to calculate the parameters from pure
component properties as follows:

N   ni
i

B0   B0 i n i
i

A0   A0i A0 j 1  k ij ni n j
ij

C 0   C 0i C 0 j 1  k ij  ni n j
3

ij

D0   D0i D0 j 1  k ij  ni n j
4

ij

E 0   E 0i E 0 j 1  k ij  ni n j
5

ij

b   bi ni
i

a   a i ni
i

c   c i ni
i

27
 d   d i ni
i

    i ni
i

    i ni
i

where k ij is a binary interaction parameter. For methane, ethane,

ethylene, propane, propylene, isobutane, n-butane, isopentane, n-
pentane, hexane, heptane, octane, carbon dioxide, hydrogen
sulphide and carbon dioxide, the pure component parameters B0 i ,
A0i , C 0i , D 0i , E 0i , bi ai , ci , d i ,  i and  i are set to values
recommended by Starling in his book ‘Fluid Thermodynamic
Properties for Light Petroleum Systems’, Gulf Publishing Co.,
Houston, 1973. For other substances the pure component
parameters are estimated using correlations developed by Starling
and Han which are given in the same book.

When to use the BWRS equation

The BWRS equation gives much more accurate volumetric and
thermal property predictions for light gases and hydrocarbons.
Given suitable interaction parameters it should give reasonable
vapour-liquid phase equilibrium predictions but owing to its
complexity, it requires more computing time than the cubic
equations of state. The BWRS model has been superseded by the
GERG-2008 model (see below) and is not recommended unless
there is a specific requirement.

Multi-reference fluid corresponding states (CSMA)

model
The Multiflash CSMA model is based on a collection of very
accurate equations of state for a number of reference fluids. It
provide accurate values of properties for any of the reference
fluids (see below for a list) and uses a 1-fluid corresponding states
approach to estimate mixture properties. It are formulated so that
mixture properties will reduce to the (accurate) pure component
values as the mixture composition approaches each of the pure
component limits.
The CSMA model definition can be considered in two distinct
parts: the definition of pseudo-critical properties for a mixture
(mixing rules), and the prescription for combining the properties of
the reference substances to give the total mixture properties
(combining rules).

Mixing rules for critical properties

For the CSMA model, the mixture (pseudo) critical volume is
defined as

28
 1
2 ∑ ∑ i j c , ij ij
V c , mix = nn V l
N i =1 j=1

where N  n i
i is the total mole number of the mixture, ni is

the mole number of component i. l ij is a temperature-dependent

binary interaction parameter for the critical volume, normally close
to 1 and

Vc ,ij 
8
Vc ,i  Vc1, /j 3 
1 1/ 3 3

The mixture (pseudo) critical temperature is defined as

∑ ∑ ni n j T c , ij V c , ij k ij
1 i=1 j=1
T c , mix = 2
N V c , mix
where T c , ij=√ T c , i T c , j and k ij is a temperature-dependent
binary interaction parameter (BIP), normally close to 1.0. This BIP
has a significant effect on phase equilibrium calculations and must
be fitted to match experimental data.
The mixture (pseudo) critical compressibility factor is defined as

Z c ,mix   xi Z c ,i
i

Pc ,iVc ,i
Z c, j 
RTc ,i
The mixture (pseudo) critical pressure is then defined as
Z c ,mix RTc ,mix
Pc ,mix 
Vc ,mix
BIPs for some pairs of components are stored in the INFOBIPS BIP
databank. In order to improve phase equilibrium predictions, BIPs
that are not available in the databank should be obtained by fitting
experimental data.
The GERG-2008 mixing rules (see below) may also be used with the
CSMA model combining rules and reference equations.

Combining rule for mixture thermodynamic

properties
The total mixture reduced Gibbs energy is obtained by combining
the pure component reduced properties as follows:

Gmix Tr , Pr    xi Gi0 Tr , Pr 

i

where the reduced properties are defined as

Tr  T Tc , mix

29
 Pr  P Pc , mix
All other thermodynamic properties are obtained from the Gibbs
energy by differentiation.

Reference fluids
The current model implementation includes reference equations of
state for the following substances:
acetone fluorine n-pentane R13
ammonia helium propane R134A
argon heptane propylene R14
benzene cyclohexane sulphur dioxide R141B
iso-butane iso-hexane SF6 R142B
n-butane n-hexane toluene R143A
1-butene hydrogen water R152A
iso-butene hydrogen sulphide xenon R161
cis-2-butene krypton R11 R218
trans-2-butene methane R113 R22
carbon dioxide methanol R114 R227EA
carbon monoxide neon R115 R23
carbonyl sulphide nitrogen R116 R236EA
decane nitrogen trifluoride R12 R236FA
DME nonane R123 R245FA
dodecane octane R1234YF R32
ethane oxygen R1234ZE R365MFC
ethanol iso-pentane R124 R41
ethylene neo-pentane R125 RC318

The reference equations of state are taken from various sources

and do not all have the same quality or range of applicability.
Any hydrocarbons that do not have reference eos are modelled by
the corresponding state model published by L. Sun and J.F. Ely,
International Journal of Thermoplastics, vol. 26, no. 2, p705 (2005).
This model is a three-parameter model that involves two reference
fluids, propane and octane, and the acentric factor of the
hydrocarbons.

Applicability
The models are very accurate for pure substances that are
included in the above list of reference substances. For mixtures it
is necessary to fit values of the binary interaction parameters to
match experimental data. in order to get the best results.

Water
A high-accuracy model for water is available as a separate model
option and is also included as part of the CSMA mixture model.
The reference equation of state is the IAPWS-95 formulation: ‘The
IAPWS Formulation 1995 for the Thermodynamic Properties of
30
 Ordinary Water Substance for General and Scientific Use’, W.
Wagner and A. Pruss, J. Phys. Chem. Ref. Data., Vol. 31, 387 (2002).
The IAPWS recommended equations for transport properties have
also been implemented.

Water-Ammonia
The high accuracy corresponding state model for water-ammonia
binary system is based on the work developed by Beiner Tillner-
Roth and Daniel G . Friend. The model not only has the high
accuracy models for pure water and ammonia but also has terms
for correcting the mixing behaviour. The model covers the
thermodynamic space between the solid-liquid-vapour boundary
and the critical locus, and is also valid in the vapour and liquid
phases for pressures up to 40 MPa. It represents vapour-liquid
equilibrium properties with an uncertainty of  0.01 in liquid
and vapour mole fractions. Typical uncertainties in the single-
phase regions are  0.3% for the density and  200 J / mol for
enthalpies.

Reference: Beiner Tillner-Roth and Daniel G . Friend, J. Phys. Chem.

Ref. Data,Vol, 27, No. 1, 1998.

Carbon Dioxide
A high-accuracy model for carbon dioxide is available as a separate
model option and is also included as part of the CSMA mixture
model The equation of state is defined in: ‘A New Equation of State
for Carbon Dioxide Covering the Fluid Region from the Triple-Point
Temperature to 1100 K at pressures up to 800 MPa’, R. Span and W.
Wagner, J. Phys. Chem. Ref. Data., Vol. 25, 1509 (1996). The
viscosity obtained from the correlation: ‘The Viscosity of Carbon
Dioxide’, A. Fenghour, W.A. Wakeham and V. Vesovic, J. Phys.
Chem. Ref. Data., Vol. 27, 31 (1998). The thermal conductivity
formulation is: ‘A Reference Multiparameter Thermal Conductivity
Equation for Carbon Dioxide with an Optimized Functional Form’,
G. Scalabrin, P. Marchi, F. Finezzo and R. Span, J. Phys. Chem. Ref.
Data., Vol. 35, 1549 (2006).

GERG 2008 Model

The GERG-2008 EOS is an industry standard (ISO 20765-2/3)
model for natural gases. It is described in the publication: O. Kunz
and W. Wagner, The GERG-2008 Wide-Range Equation of State for
Natural Gases and Other Mixtures: An Expansion of GERG-2004, J
Chem. Eng. Data., 57, 3032 (2012).
It is similar in some respects to the CSMA model described above.
GERG-2008 includes accurate reference EOS for 21 natural gas
components:

31
methane n-pentane argon
nitrogen iso-pentane oxygen
CO2 hexane hydrogen
ethane heptane CO2
propane octane water
n-butane nonane helium
iso-butane decane H2S

The model uses different mixing rules from CSMA and additional
binary departure functions that further improve the accuracy of
the multi-component mixture model in the description of
thermodynamic properties.

GERG-2008 Mixing rules for critical

properties
The mixture (pseudo) critical volume is defined as

1 ni n j ni  n j  ijVc Vc ,ij

Vc ,mix  2
N

i 1 j 1  ijVc ni   Vjic n j
where ni is the mole number of component i,  ijV
c
is a linear
temperature-dependent binary interaction parameter for the
critical volume, normally close to 1 and

Vc ,ij 
8
Vc ,i  Vc1, /j 3 
1 1/ 3 3

V
The  ijV c
and β jic are constant BIPs with values usually close to 1
V V
and β ij c=1/ β jic
The mixture (pseudo) critical temperature is defined as

1 ni n j ni  n j  ijTc Tc ,ij

Tc ,mix  2
N

i 1 j 1  ijTc ni   Tjic n j
and  ij c is a linear temperature-
T
where Tc ,ij  Tc ,iTc , j
T T
dependent BIP. The β ij c and β jic are constant BIPs with values
T T
usually close to 1 and β ij c=1 / β jic
The BIPs for the special selected 21 natural gas components are
stored in the INFOBIPS databank. If the BIPs are not available in the
databank, the values are set to 1 by default.
In order to improve the phase equilibrium prediction, the BIPs that
are not available in the databank for both CSM and GERG models
should be obtained by fitting the experimental data.

32
Departure function for mixtures in GERG-
2008
The Helmholtz energy reduced departure function for multi-
component mixtures includes individual terms for each pure
substance and binary correction terms:

α r ( T r , V r , X )=∑ x i α ri + Δα r
i=1

where

Δαijr (T r , V r , X )= xi x j F ij αijr ( T r , V r )
The parameter Fij , the weighting factor of the component, i and j
in the mixture, is obtained from fitting the specific binary mixtures.
The values of Fij for the natural gases in the GERG-2008 model
are stored in the INFOBIPS databank. If there is no departure
function for a binary components, the value of Fij is set to zero
by default. The binary departure function,  ij Tr , Pr  is similar to
r

the structure of a pure substance equation of state but with different

equation coefficients for a typical pair of binary mixture.

Applicability
The GERG-2008 model is the recommended model for natural
gases.

33
Activity coefficient equations
in Multiflash

A number of activity coefficient equations are available in

Multiflash and are described below. The nomenclature is to denote
binary interaction parameters between components i and j by Aij .
The NRTL equation has an additional parameter  ij .

When to use activity coefficient models

Activity coefficient models are usually used to model any
combination of polar and non-polar compounds including those
exhibiting very strong non-ideality. If the gas phase model is the
perfect gas ,the pressures should be limited to 3-5 bar. If Redlich-
Kwong or another equation of state is used to model the gas phase
then the pressure limit is higher, maybe of the order of 10-20 bar.
However, the mixture should be subcritical. If the mixture contains
some components which are above their critical point, such as
dissolved gases, then you should be aware that the properties of
components, e.g. vapour pressure, will be extrapolated.
NRTL, UNIQUAC and UNIFAC may be used to model VLE, LLE and
VLLE but both Wilson models are limited to VLE only.
To obtain accurate predictions from any of the activity coefficient
models, except UNIFAC, it is necessary to use interaction
parameters. If these are not available in INFOBIPS for your system
the you need to supply interaction parameters for the missing
values which match the model specification given above and which
are in the correct units. Parameters in INFOBIPS are in standard SI
units, Jmol-1, except for Wilson A where the BIPs are dimensionless.
The user can introduce BIPs in other units provided these units are
set correctly.

Ideal solution model

This is described by:

GE
0
RT

34
 The ideal solution model may be used when the mixture is ideal,
i.e. when there are no mixing effects. It an also be used for single
components to calculate some pure component properties from
the physical property databank.

Wilson equation
Wilson E equation
This is defined by:

GE   j Gij n j 
  ni ln 
RT i   j nj 
where:

V j*  Aij 
Gij  exp  
Vi *  RT 

Vi * is the saturated liquid molar volume of component i

(extrapolated in the case of supercritical gases) evaluated at a fixed
reference temperature of 298.15K.
This model may be used for vapour-liquid equilibrium calculations
but it is not capable of predicting liquid-liquid immiscibility. Binary
interaction parameters are provided in our INFOBIPS bank for
some component pairs. If no BIPs are included for your particular
mixture then to obtain accurate predictions you must supply
binary interaction parameter values in the correct units.

Wilson A equation
GE   j Aij n j 
  ni ln 
RT i   j nj 
This model which is a simplified form of the Wilson E model, may
be used for vapour-liquid equilibrium calculations but it is not
capable of predicting liquid-liquid immiscibility. To obtain accurate
predictions you must supply binary interaction parameters (BIP)
values, which are dimensionless.

NRTL equation
∑ n j A ji G ji
G =∑ n i
E j

i ∑ n j G ji
j

where:

 aij Aij 
Gij  exp  
 RT 
35
 The NRTL model may be used for vapour-liquid, liquid-liquid and
vapour-liquid-liquid calculations (the VLE option should be used
for VLLE). Again if BIP values are not provided in INFOBIPS they
must be supplied for accurate predictions. In cases where the user
does not specify any value for the non-randomness factor,  ij , it is
automatically set to 0.3 if the VLE version of NRTL is specified or
to 0.2 if the LLE version is specified. Note that  ij   ji so only
 ij need be supplied.

UNIQUAC equation
 ri  n j   qi  r j n j    G ji q j n j 
GE  j  z    j 
  ni ln    qi ni ln     qi ni ln 
j

RT i   rj n j  2 i  ri  q j n j  i  q jnj 
 j   j   j 
where:
z  10
and:

 Aij 
Gij  exp  
 RT 
The UNIQUAC model may be used for vapour-liquid, liquid-liquid
and vapour-liquid-liquid calculations. In Multiflash we provide
UNIQUAC VLE and LLE variants as for the NRTL equation. Again
BIP values must be supplied for accurate predictions if they are not
included in INFOBIPS. For VLLE the variant chosen should be
guided by the BIPs available.

UNIFAC group-contribution methods

Original UNIFAC method
The UNIFAC method is similar to UNIQUAC but the interaction
parameters are predicted based on the molecular group structure
of the components in the mixture. The is completely predictive and
does not require the user to supply BIPs.

( ) ( )
ri ∑ n j qi ∑ r j n j
GE j z j G G(i)
=∑ ni ln + ∑ qi ni ln + −∑ ni
RT i ∑ r jn j 2 i ri ∑ q j n j RT i RT
j j

where q i and ri are the UNIQUAC/UNIFAC surface and volume

parameters for component i and z  10 . For UNIFAC they are
found by summing the contributions from the groups from which
each component is formed. G is the residual excess Gibbs energy
of the solution and G (i ) is the residual excess Gibbs energy of

36
 pure component i according to the principle of solution of
groups. The UNIFAC residual term is given by:

  lk Ql N l 
G  
  N k Qk ln l 
RT k   Ql N l 
 l 
The summation is over all groups in the mixture (or pure
component). N k is the total number of moles of group k , Qk
is the surface area parameter for group k and lk is the
interaction parameter:

 A 
lk  exp  lk 
 RT 
In original UNIFAC, the two binary parameters Alk between
components l and k are normally taken as constants.

Dortmund modified UNIFAC method

 ri3 / 4  n j   qi  r j n j 
G E   z   G G (i)
  ni ln     qi ni ln    ni
j j

  rj n j  ri  q j n j
3/ 4
RT i  2 i  RT i RT
 j   j 
where q i and ri are the UNIQUAC/UNIFAC surface and volume
parameters for component i and z  10 . For UNIFAC they are
found by summing the contributions from the groups from which
each component is formed. G is the residual excess Gibbs energy
of the solution and G (i ) is the residual excess Gibbs energy of
pure component i according to the principle of solution of
groups. The UNIFAC residual term is given by:

  lk Ql N l 
G  
  N k Qk ln l 
RT k   Ql N l 
 l 
The summation is over all groups in the mixture (or pure
component). N k is the total number of moles of group k , Qk
is the surface area parameter for group k and lk is the
interaction parameter:

 A 
lk  exp  lk 
 RT 
For Dortmund modified UNIFAC, the two binary parameters Alk
between components l and k are treated as quadratic functions
of temperature.
Dortmund modified UNIFAC is better able to represent the
simultaneous vapour-liquid equilibria, liquid-liquid equilibria and
excess enthalpies of polar mixtures than the original UNIFAC
37
 method. Like original UNIFAC, however, it does not allow for the
presence of light gases in the mixture.
References: Gmehling and co-workers, A Modified UNIFAC Model. 1.
Prediction of VLE, hE, and , Industrial and Engineering Chemistry
Research, 26, 1372, (1987); A Modified UNIFAC Model. 2. Present
Parameter Matrix and Results for Different Thermodynamic
Properties, ibid., 32, 178, (1993); A Modified UNIFAC (Dortmund)
Model. 3. Revision and Extension, ibid., 37, 4876, (1998); A Modified
UNIFAC (Dortmund) Model. 4. Revision and Extension, ibid., 41,
1678, (2002).

Regular solution theory

G En n VV A ij
i j i j ij


RT RT  n V i i
i

where:

 i  j 
2

Aij    i  j k ij
2
 i and Vi are the solubility parameters and molar volumes at
25°C of component i.
Regular solution theory can be used for vapour-liquid calculations
for mixtures of non-polar or slightly polar components. The theory
is applicable to systems which exhibit negligible entropies and
volumes of mixing. However, it has been largely superseded by
equations of state.

Flory-Huggins theory
The Multiflash implementation of Flory-Huggins theory includes a
correction term. It is defined by:

 Vi  n j   ni n jViV j Aij
GE  
  ni ln
j ij

RT i   n jV j  2 RT  niVi
 j  i

The Multiflash expression reduces to the standard Flory-Huggins

theory if all interaction parameters Aij are set to zero. However,
to obtain reasonable results it is usually necessary to adjust the
values of the interaction parameters to fit the data.
Flory-Huggins theory is able to describe systems which include
some long chain molecules. It has consequently applied to model
polymer systems but it has been to some extent superseded by
other models such as PC-SAFT. However, Flory-Huggins theory still
offers the advantages of simplicity, and hence speed.

38
Gas phase models for activity coefficient methods
The quantity ln i can be calculated from any of the gas phase
sat

models in Multiflash. The normal choices would be the perfect gas

equation, the RK equation of state or a virial equation of state.
The first two are described in the section on equations of state and
the HOC second virial model is described below.

The Hayden-O’Connell (HOC) model

The Multiflash implementation of the HOC model treats each
component in the gas phase as forming a monomer-dimer
equilibrium. For most components that deviate only slightly from
ideal behaviour, the model reduces to the volume-explicit virial
equation:
RT
V  B
p
The second virial coefficient B is estimated for each component
from a generalised correlation (J.G. Hayden and J.P. O’Connell, Ind.
Eng. Chem. Proc. Des. Dev, 14, 209 (1975)). This correlation
accounts for non-polar, polar and chemical association effects. The
pure component properties required by the model are: critical
temperature, critical pressure, radius of gyration, dipole moment
and an empirical association parameter. Values for these quantities
are stored in the Infodata databank.
A second virial coefficient model such as HOC can account for gas
phase non-idealities up to pressures of about 5 to 10 bar. The
implementation of the HOC model in Multiflash allows the vapour
phase association of substances such as acetic acid to be
represented.

39
Models for solid phases

Introduction
Multiflash may also be used to calculate the phase equilibrium of
systems containing solid phases, either mixed or pure. These may
occur either when a normal fluid freezes or may be a particular
type of solid phase such as a hydrate.

Solid freeze-out model

This model is used to calculate the thermodynamic properties of
solid phases formed by freezing one or more of the components in
the fluid mixture. It may be applied to any component where this
may be a consideration. The freeze-out model in general is defined
by:

(
ln ϕ i=α ln ϕ liq
i −
ΔH −T ref Δ
R
C p
)( 1
−
1
T T ref )
+
S corr Δ
R
+
C p
R
ln
( )
T
T ref
−
( p− p atm ) V
RT
Δ

For the freeze-out of pure solids, the parameters are as follows:

 i is the fugacity coefficient of pure solid component i ,  iliq is
the fugacity coefficient of the same component as a pure liquid at
the same pressure p and temperature T (calculated from the
liquid phase model associated with the freeze-out model),   1 ,
DH , DC p and DV are the changes in molar enthalpy, molar
heat capacity and molar volume respectively on fusion at the
melting point, Tref is a reference temperature which corresponds
to the normal melting point when S corr  0 which is assumed in
this case. patm is atmospheric pressure. DH , DC p and DV
are constants, which are normally obtained from the chosen data
source.
Solid freeze-out can be used to model the solidification of
compounds such as water, carbon dioxide or methane, for example
in natural gases. It can also be used to model eutectics.

Scaling and general freeze-out model

In its general form, the freeze-out model can be applied to any
solid phase of fixed composition, which must be defined. The

40
 model can for example be applied to hydrated salts such as
monoethylene glycol (MEG) monohydrate or to crystalline mineral
salts, i.e. scales. If   1 , the solid fugacity coefficient is defined
relative to the liquid phase of the same composition whereas, if
  0 , the solid fugacity coefficient is an absolute value. S corr is
a molar enthalpy correction factor that allows the reference
temperature Tref to be different from the normal melting point.
For solid phases that are not pure substances, the parameters
DH , DC p DV , S corr and Tref must be defined specifically
for the phase in question.

Modelling hydrate formation and inhibition

Natural gas hydrates are solid ice-like compounds of water and the
light components of natural gas. They form at temperatures above
the ice point and are therefore a serious concern in oil and gas
processing operations. The phase behaviour of systems involving
hydrates can be very complex because up to seven phases must
normally be considered. The behaviour is particularly complex if
there is significant mutual solubility between phases, e.g. when
inhibitors or CO2 are present. Multiflash offers a powerful set of
thermodynamic models and calculation techniques for modelling
gas hydrates.

Hydrate model
The original Infochem model uses a modification of the RKS
equation of state for the fluid phases plus the van der Waals and
Platteeuw model for the hydrate phases. An alternative model uses
the CPA model for the fluid phases. The hydrate models have also
been extended to include hydrate structure H in addition to
structures I and II. The model can explicitly represent all the
effects of the presence of inhibitors, although parameters for the
CPA model are only provided for methanol, ethanol, MEG, DEG,
TEG and salt.
The main features of the models are:
 Our description of hydrate phase behaviour uses a
thermodynamically consistent set of models for all
phases present including hydrate structures I, II and H,
ice, water, liquid and gas. The vapour pressures of pure
water and sublimation pressures of ice are very
accurately reproduced.
 The following natural gas hydrate formers are included:
methane, ethane, propane, isobutane, butane, nitrogen,
CO2 and H2S.
 Other hydrate formers that are not usually present in
natural gas but which form structure I or II are also
included. These compounds are: SF6 , ethylene,
propylene, cyclopropane, oxygen, argon, krypton and
xenon.
 Parameters are provided for the following compounds
that form hydrate structure II in the presence of small
‘help-gases’ such as methane or nitrogen: cyclopentane,

41
 benzene and neopentane. These compounds and the
structure H formers listed below may be present in
condensate and oil systems.
 Structure H hydrates form in the presence of small
‘help-gases’ such as methane or nitrogen but the
formation temperatures are significantly higher (about
10 K) than pure methane or nitrogen hydrate. In
practice it seems that structure II hydrates form before
structure H but, if there is enough water, structure H
may be formed too. The structure H model includes
parameters for:

isopentane
neohexane
2,3-dimethylbutane
2,2,3-trimethylbutane
2,2-dimethylpentane
3,3-dimethylpentane
methylcyclopentane
methylcyclohexane
cis-1,2-dimethylcyclohexane
2,3-dimethyl-1-butene
3,3-dimethyl-1-butene
cycloheptene
cis-cyclooctene
adamantane
ethylcyclopentane
1,1-dimethylcyclohexane
ethylcyclohexane
cyclohexane
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 be made for any possible combination
of phases including cases without free water. No
modification of the phase models is required to do this.
 The properties of the hydrates have been fixed by
investigating data for natural gas components in both
simple and mixed hydrates to obtain reliable
predictions of structure I, structure II and structure H
hydrates.
 The properties of the empty hydrate lattices have been
investigated and the most reliable values have been
adopted.
 Proper allowance has been made for the solubilities of
the gases in water so that the model parameters are not
distorted by this effect. This is particularly important
for carbon dioxide and hydrogen sulphide which are
relatively soluble in water.
 Correct thermodynamic calculations of the most stable
hydrate structure have been made.
The model is used to calculate the hydrate equilibrium formation
temperature at a given pressure or pressure at a given temperature
where the first very small quantity of hydrate appears after a
sufficiently long time. This point corresponds to the
42
thermodynamic formation point, also known as the hydrate
dissociation point. Before the thermodynamic formation point is
reached hydrate cannot form - this point is also called the stability
limit. Beyond the stability limit hydrate can form but may not do
so for a long time.
The model has been tested on a wide selection of open literature
and proprietary experimental data. In most cases the hydrate
dissociation temperature is predicted to within ±1K.

Hydrates in water sub-saturated systems

Hydrates can form even in systems where there is no free water
present. Our hydrate model, with both RKSAINFO and CPA used to
model the fluid phase, is capable of modelling this, although the
data available for validating the results are very limited. What we
have noticed is that for systems with very little water and at high
pressures the predicted hydrate dissociation temperatures using
RKSAINFO and CPA tend to diverge with increasing pressure, with
CPA predicting lower hydrate dissociation temperatures than
RKSAINFO. There are no data presently available to confirm which
is correct. If this causes any difficulty it is possible to reproduce
the CPA predictions with RKSAINFO by using parameters which
reduce the Infochem mixing rule to van der Waals. These
parameters, for methane, ethane and propane with water, are
stored in the file vdwbip.mfc. They can be used to overwrite the
existing BIPs for these binaries by loading this file after you have
defined the hydrate model based on RKSAINFO as the fluid model.
When compared to the available data all three possible variants
(CPA, RKSAINFO with standard and vdw BIP) give hydrate
dissociation results within experimental error.

Nucleation model
The nucleation model was developed in collaboration with BP as
part of the EUCHARIS joint venture. This model is an extension of
the existing thermodynamic model for hydrates described above.
In order to extend the nucleation model into the Multiflash
program, the following enhancements to the nucleation model
were made:
 The model was extended to cover the homogeneous
nucleation of ice and fitted to available ice nucleation
data.
 The model was generalised to cover in principle
nucleation from any liquid or gas phase.
 A correction for heterogeneous nucleation was included
that was matched to available hydrate nucleation data.
 An improved expression was adopted for fluid
diffusion rates.
 More robust numerical methods were introduced into
the program.
The nucleation model provides an estimate of the temperature or
pressure at which hydrates can be realistically expected to form.
The model is based on the statistical theory of nucleation in
multicomponent systems. Although there are limitations and
approximations involved in this approach it has the major benefit
43
that a practical nucleation model can be incorporated within the
framework of a traditional thermodynamic hydrate modelling
package.
Many of the comparisons of model predictions with experimental
data have been made. In general measurements of hydrate
nucleation result in an experimental error of  2ºC and predictions
are usually within this error band.
With the existing Infochem hydrate model and the nucleation
model, the hydrate formation and dissociation boundaries can be
predicted between which is the hydrate formation risk area.

Inhibitor modelling
Thermodynamic hydrate inhibitors decrease the temperature or
increase the pressure at which hydrates will form from a given gas
mixture. The original Infochem hydrate model includes parameters
for the commonly used inhibitors: methanol, salts, and the glycols
MEG, DEG and TEG and for the less well-tested inhibitors ethanol,
iso-propanol, propylene glycol and glycerol. A new mixing rule was
developed for the SRK equation of state to model the effects of the
inhibitors on the fluid phases.
The hydrate model using CPA to model the fluid phases is limited
in the current version of Multiflash to hydrate calculations with
pure water or with methanol, ethanol, MEG, DEG, TEG and salt.
Additional parameters to extend the CPA model to cover the full
range of thermodynamic inhibitors listed above may be included in
future versions.
The treatment of hydrate inhibition has the following features:
 The model can explicitly represent all the effects of
inhibitors including the depression of the hydrate
formation temperature, the depression of the freezing
point of water, the reduction in the vapour pressure of
water (i.e. the dehydrating effect) and the partitioning
of water and inhibitor between the oil, gas and aqueous
phases.
 The model has been developed using all available data
for mixtures of water with methanol, ethanol, MEG, DEG
and TEG. This involves representing simultaneously
hydrate dissociation temperatures, depression of
freezing point data and vapour-liquid equilibrium data.
 Two salt inhibition models are available. The older
model is based on a salt component. The new model is
a (restricted) electrolyte model. A salinity calculator tool
is provided, see User Guide for Multiflash for Windows,
which allows the salt composition to be entered in a
variety of ways. The salt component model expresses
the salt composition in terms of an equivalent “salt
component” present in INFODATA with the properties
of sodium chloride. The Electrolyte model in versions of
Multiflash to 3.4 calculated the equivalent amount of
Na+ and Cl- in the mixture. In MF3.5 the Electrolyte
model has been extended to include K+ and Ca++ ions.
This does not affect the equivalence calculations if the
salt composition is entered as TDS (Total Dissolved
Solid). If an Ion Analysis or Salt Analysis is supplied
44
 then any values entered for K+ or Ca++ will be allocated
to those ions in the Composition table and the
equivalence for any ions other than Na+, K+, Ca++ or Cl-
will be expressed in terms of all these four ions. The
equivalent composition is based on experimental data
for the freezing point depression and hydrate inhibition
effect of salts.
 The solubilities of hydrocarbons and light gases in
water/inhibitor mixtures have also been represented.
The original binary interaction parameters for the RKSA fluid
model stored for alkanes with MEG correctly reproduce all the
reported data for alkane solubility in MEG, for MEG solubility in
heptane and the inhibition effect of MEG on hydrate dissociation
temperatures. However, the measured data for MEG solubility in
alkanes is limited to a single data set for the solubility of MEG in
heptane. For mixtures containing hydrocarbons greater than C7
the parameters in versions prior to 2.9 predicted an increasing
MEG solubility with increasing carbon number. This may have led
to over prediction of the amount of MEG required to inhibit
hydrates for heavy crude oils.
Later versions of Multiflash include new parameters for alkanes
with MEG which stabilise the solubility of MEG in higher alkanes
and correctly reproduce the MEG inhibition effect on hydrates.
However, they fail to predict the correct solubility of alkanes in
MEG. The new parameters were included in the BIP databank,
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 BIP databank, oilandgas3.

Salinity Model
The original salt model operates only on a sodium chloride
equivalent basis. The model represents the effect of sodium
chloride in aqueous solution by a special equation of state
component called “salt component” or “saltcomp”. The salt
component works for all versions of RKS and PR/PR78, but it is
only recommended to use it with PR, PRA, PRA-Infochem, PR78,
PR78A, PR78A-Infochem, RKSA, and RKSA-Infochem. The salt
component model cannot be used with the CPA model or any other
equation of state.
The electrolyte salt model is designed to be added on to any
equation of state. The models selection form allows it to be
selected for use with the Advanced RKS equation and the CPA
model. From Multiflash version 3.8 it represents the salt as a
combination of sodium, potassium, calcium, chloride and bromide
ions. Future versions of Multiflash may extend this to other ions

Modelling wax precipitation

Waxes are complex mixtures of solid hydrocarbons that freeze out
of crude oils if the temperature is low enough. Under conditions of
interest to the oil industry, waxes consist mainly of normal
paraffins. Waxes are thought to consist of many crystals each of

45
 which is a solid solution of n-paraffins of a fairly narrow range in
molecular weight.
The available wax model in Multiflash is the Coutinho model. The
features of the model are:
 The Coutinho model represents wax as a solid solution.
There are two versions of the model, the Wilson and
UNIQUAC variants. The version normally selected in
Multiflash is the Wilson model which approximates the wax
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
complex UNIQUAC variant models the tendency of waxes to
split into several separate solid solution phases. The
UNIQUAC variant can be activated by configuration files that
can be supplied by Infochem for users who wish to simulate
the detailed physical chemistry of wax precipitation.
 The model gives good predictions of waxing behaviour, both
wax appearance temperature and the amount of wax
precipitated at different temperatures. The method is
applicable to both live and dead oils.
 The model requires that the normal paraffins are explicitly
present in the fluid model, as these are the wax forming
components. The user must therefore use the PVT Analysis
either to enter the measured n-paraffin concentrations or
else to estimate the n-paraffin distribution. The composition
of the wax phase is determined by the known thermal
properties (normal melting point, enthalpy of fusion, etc.) of
the n-paraffins combined with their solution behaviour in
both oil and wax phases.
 In principle the wax model can be used in conjunction with
any conventional cubic equations of state. The default
options in the Multiflash implementation is RKSA.

Modelling asphaltene flocculation

Asphaltenes are polar compounds that are stabilised in crude oil
by the presence of resins. If the oil is diluted by light
hydrocarbons, the concentration of resins goes down and a point
may be reached where the asphaltene is no longer stabilised and it
flocculates to form a solid deposit. Because the stabilising action
of the resins works through the mechanism of polar interactions,
their effect becomes weaker as the temperature rises, i.e.
flocculation may occur as the temperature increases. However, as
the temperature increases further the asphaltene becomes more
soluble in the oil. Thus, depending on the temperature and the
composition of the oil, it is possible to find cases where
flocculation both increases and decreases with increasing
temperature.
The asphaltene model is based on the RKS cubic equation of state
with additional terms to describe the association of asphaltene
molecules and their solvation by resin molecules. The interactions
between asphaltenes and asphaltenes-resins are characterised by
two temperature-dependent association constants: K AA and K AR .
46
 The remaining components are described by the van der Waals 1-
fluid mixing rule with the usual binary interaction parameters k ij
so the asphaltene model is completely compatible with existing
engineering approaches that are adequate for describing vapour-
liquid equilibria. The model is a computationally efficient way of
incorporating complex chemical effects into a cubic equation of
state.

Other thermodynamic models

Multiflash also incorporates a corresponding states method for
estimating the density of liquid mixtures, the COSTALD model.

COSTALD liquid density model

The volume of a liquid on the saturation line is defined by:

V sat
V * 
 V R( 0) 1  V R(1) 
whereV sat is the saturated liquid volume, V * is a characteristic
volume for each substance,  is the acentric factor and V R and
( 0)

V R(1) are generalised functions of reduced temperature. In the

Infochem implementation V * is obtained by matching the
saturated liquid volume stored in the databank at 298 K or a
reduced temperature of 0.7, whichever is the lower.
The volume of a compressed liquid is given by:

V   B  p  
sat  1  C ln 
V   B   p sat  
where B  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 COSTALD method can provide very accurate volumes for pure
substances and simple mixtures, such as LNG. It is valid for liquids
on the saturation line and compressed liquids up to a reduced
temperature of 0.9. It is not necessarily accurate for heavy
hydrocarbon mixtures with dissolved gases.

47
Transport property models

Introduction
For each of the transport properties, viscosity, thermal
conductivity and surface tension, Multiflash offers two approaches
to obtaining values for mixtures. One route is to calculate the
property for a mixture by combining the property values for the
pure components of which it is composed; the mixing rule
approach. The other is to use a predictive method suitable for the
property in question.

Viscosity
SuperTRAPP viscosity model
The SuperTRAPP method is a predictive extended corresponding
states model that uses propane as a reference fluid. It can predict
the viscosity of petroleum fluids and well-defined components
over a wide range of thermodynamic states from the dilute gas to
the dense fluid. The basic idea behind this model is that the
viscosity of a mixture can be equated to the viscosity of a
hypothetical pure fluid which is then related to the viscosity of a
reference fluid at a corresponding-state point (ρ0 ,T0). In order to
improve the viscosity prediction for cycloalkanes and highly
branched alkanes, the concept of mass shape factor in introduced
in this method. In order to apply the method, the following are
required:
 An equation 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 mixture of the interest.
The original method is not applicable to aqueous mixtures of
alcohols, glycols or salts. The Infochem implementation of Super
TRAPP model includes modification to ensure that the viscosity of
aqueous solutions of methanol, ethanol MEG, DEG and TEG or salts
and ions are predicted reasonably well.
Two variants of the SuperTRAPP model are implemented:
 Standard Super TRAPP model as described above.
48
  Liquid viscosity fitting. An internal model parameter is
adjusted to match the experimental measurements.
Overall the SuperTRAPP method is the most versatile method for
viscosity predictions and its performance is generally better than
the other methods available in Multiflash. We would recommend
this method for oil and gas application. It is the default viscosity
model for use with equations of state.
Reference: Huber, M. L. & Hanley, H.J.M. (1996) The corresponding-
states principle: Dense Fluids. In J. Millat, J. H. Dymond & C. A.
Nieto (Eds.), Transport properties of Fluids: Their correlation,
Prediction and Estimation. Cambridge University Press.

Pedersen Model
This is a predictive corresponding states model originally
developed for oil and gas systems. It is based on accurate
correlations for the viscosity and density of the reference
substance which is methane. The model is applicable to both gas
and liquid phases. The Infochem implementation of the Pedersen
model includes modifications to ensure that the viscosity of liquid
water, methanol, ethanol, MEG, DEG and TEG and aqueous
solutions of these components or salt are predicted reasonably
well.
Reference: Pedersen, Fredenslund and Thomassen, Properties of
Oils and Natural Gases, Gulf Publishing Co., (1989).

Pedersen Heavy Oil Model

Even though the performance of the Pedersen model in the
classical form, with methane as reference component, can be
stretched somewhat into the region where methane is in solid
form, the classical Pedersen model is generally not suited for heavy
oil mixtures with viscosities above ~10 cp.
The Pedersen heavy oil viscosity model extends the applicability
area of the model for heavy oils. In this approach instead of using
methane as reference component, the viscosity of the stabilised
crude is used as starting point. The Ronningsen semiempirical
correlation for stabilised crude viscosities is used in this model:
371.8 6.215M
log 10 η0=−0.07995−0.1101M− +
T T
The correlation is valid at temperatures at which the fluids behave
in a Newtonian manner and are not influenced by precipitated wax.
For methane reference temperature > 75 K the classical Pedersen
model is used. For reference temperatures < 50 K the heavy oil
model is used and for the temperature range of 50K < T < 75K the
viscosity is calculated as:
η=F 1 ηClassic + F 2 ηheavy
where F1 and F2 are defined as below:
HTAN + 1
F1=
2

49
 1−HTAN
F 2=
2
exp (Δ T )−exp (−Δ T )
HTAN =
exp (Δ T )+exp(−ΔT )
T −70
With ΔT =
5
For the temperature T in K.
By implementing the heavy oil viscosity correlation in this manner,
the classical Pedersen model is still used for higher temperatures
and lighter oil mixtures. Averaging the classical Pedersen model
and the heavy oil correlation viscosities for methane reference
temperatures in the range 50 K to 75 K ensures a smooth
transition to the heavy oil viscosity correlation.
Reference: Pedersen, Fredenslund and Thomassen, Properties of
Oils and Natural Gases, Gulf Publishing Co., (1989).

Twu Model
This is a predictive model suitable for oils. It is based on a
correlation of the API nomograph for kinematic viscosity plus a
mixing rule for blending oils. It is only applicable to liquids.
Reference: Twu, Generalised method for predicting viscosities of
petroleum fractions, AIChE Journal, 32, 2091, (1986).

Lohrenz-Bray-Clark method
This model is a predictive model which relates gas and liquid
densities to a fourth degree polynomial in reduced density
r   c :

     10 
1/ 4
* 4
 a1  a 2  r  a 3  2r  a 4  3r  a5  4r

where a1 , a 2 , a 3 , a 4 and a5 are constants. For pure components

the viscosity reducing parameter  is defined by
  Tc1/ 6 MW 1/ 2 pc2 / 3
where Tc and pc are respectively the critical temperature and
critical pressure and MW is the component molecular weight. For
a mixture these properties are calculated using mole fraction
averages.
In Multiflash the fluid densities are derived from any chosen
equation of state, rather than the correlations proposed by
Lohrentz et al. This has the advantage that there is no
discontinuity in the dense phase region when moving between
liquid-like and gas-like regions.
Multiflash also allows two variants of the LBC model. The first uses
the original LBC method to estimate the critical volume of
petroleum fractions and takes the critical volume of other

50
 components from the chosen data source. The second variant fits
the critical volume of each component to reproduce the liquid
viscosity at the boiling point.
The method is mainly applicable to the types of components found
in oil and gas processing but we would recommend that the
SuperTRAPP method is normally used in these cases.
Reference: Lorentz, Bray and Clark, Calculating viscosities of
Reservoir Fluids from their Compositions, Trans. Soc. Pet. Engs. Of
the AMMPE 231 1171 (1964)

Liquid viscosity mixing rule

This method obtains the liquid mixture viscosity by applying a
simple mixing rule to the pure component saturated liquid
viscosities generated from a databank. Each component in the
mixture must have a liquid viscosity correlation stored in the
databank.
 i ni ln  i
ln  
 i ni

Vapour viscosity mixing rule

The viscosity of a gas mixture at low density is calculated from the
databank correlations for the zero pressure gas viscosities of the
pure components. Each component in the mixture must have a
vapour viscosity correlation stored in the databank.

 i ni M i  i

 i ni M i

where M i and  i are the molecular weight and pure gas viscosity
for component i.

Thermal conductivity
Chung-Lee-Starling thermal conductivity
method
This is a predictive method for both gas and liquid mixture
thermal conductivities. It requires the critical properties, Tci , Vci
and ci for non-polar components. For polar and associating fluids
the dipole moment and an association parameter are also required.
Association parameters for water, acetic acid and the lower
alcohols are provided. The fluid density is required as part of the
calculation and this quantity may be obtained from any of the
thermodynamic models in Multiflash.
     p

51
  1 
   0   Bi Y 
 H2 
where  0 is a generalised function of reduced temperature, Bi is a
generalised function of  , H 2 is a generalised function of  r
and Y is a function of volume.
This method can be used for oil and gas processing and also for
polar mixtures.
Reference: Reid, Prausnitz and Poling, The Properties of Gases and
Liquids, McGraw-Hill., (1987).

SuperTRAPP thermal conductivity method

The SuperTRAPP (STRAPP) method is an extended corresponding
states model that can be used for petroleum fluids, well-defined
components and pure substances.
In general the thermal conductivity is defined as the sum of the
internal contribution and the translational contribution. The
translational contribution can be defined as three parts: the dilute gas
contribution, the residual and critical enhancement contribution. In
the current version of STRAPP in Multiflash 3.9, the critical
enhancement term, Crit
x is omitted since the critical enhancement
for mixtures is usually very small.

 x (T ,  , {x})  int
x (T , {x})   x
dilute gas
(T , {x})  res
x (T ,  , {x})   x
Crit
(T ,  , {x})
For a mixture, the internal contribution x
int
can be estimated from
the empirical mixing and combining rules using the modified Eucken
correlation for the individual components.
For the dilute gas term, the expression for the translational
contribution is formulated as

15R xo (T )
 dilute  gas
x (T ,{x}) 
4M x
in units of mW/m/K. R is the molar gas constant in units of
J / mol / K and M x is the molecular weight for the mixture in
unit of g/mol and the expression of  x (T ) for a mixture is given
o

as follows.
n

x i i
o
(T ) M i1 / 2 n
 xo (T )  i 1
n
and M x   xi M i
x M
i 1
x
1/ 2
i
i 1

Where  i
o
is the dilute gas viscosity given by Lucas correlation in
unit of P .
The expression of the residual contribution term is evaluated using
the extended corresponding state method and is related to the
thermal conductivity of a reference fluid of propane at a
corresponding state, (  o , To ) .
52
res
x (T ,  )   o (To ,  o ) F
res

where the F calculation requires mixing and combining rules for

the mixtures.
References:
James F. Ely and H.J.M. Hanley , “Prediction of transport properties. 2.
Thermal conductivity of pure fluids and fluid mixtures. Ind. Eng.
Chem. Fund., 22, 90-97 (1983).
M.L. Huber and H.J.M. Hanley, “ The
Corresponding-States Principle:
Dense Fluids”, p283, edited by Jϋrgen
Millet, John H. Dymond and C.A. Nieto de Castro, “Transport
Properties of Fluids”, IPUAC, (1996).
M.E. Baltatu, R.A. Chong, M.L. Huber, “Thermal conductivity of defined
and undefined hydrocarbon liquids with an extended corresponding
states model”, The fourth Asian Thermophysical Properties
Conference, Tokyo, Sept. 1995.
M.E. Baltatu, R.A.Chong et al, “Transport Properties of Petroleum
Fractions”, International Journal of Thermophyics, Vol. 20, No. 1, p85-
95 (1999).
Huber(1996), p10.24, “The Properties of Gases and Liquids”, edited by
Bruce E. Poling, John M. Prausnitz and John P. Oconnell, fifth edition,
2001.

Liquid thermal conductivity mixing rule

This method obtains the liquid mixture thermal conductivity by
applying a simple mixing rule to the pure component saturated
liquid thermal conductivities generated from a databank. Each
component in the mixture must have a liquid thermal conductivity
correlation stored in the databank.
1
 i ni M i
1 2i

2  i ni M i
where M i and  i are the molecular weight and pure saturated
liquid thermal conductivity of component i .

Vapour thermal conductivity mixing rule

The thermal conductivity of a gas mixture at low density is
calculated from the correlations for zero density gas thermal
conductivity of the pure components at the same temperature.

 i ni M i  i

 i ni M i

53
Surface Tension
Linear Gradient Theory method
This method predicts the interfacial tension between two phases.
The possible pairs of phases are: Liquid / Gas and Liquid / Liquid.
The prediction of interfacial tension between Liquid / Solid and
Gas / Solid phases is not yet possible.
The model uses the difference in densities between the two phases
and the energy gradient that arrives from the fact that the phases
are immiscible to predict the interfacial tension.
II
ρref
 
=     
2c  ρi μi  ρ   μieq  P  ρ   P eq  dρref
 Iref
 i 

The variable c is characteristic of the mixture and varies with

temperature. The mixing rule used for this parameter is of the
following type:
cij = cii c jj 1  l ij 

The parameter l ij is the binary interaction parameter (BIP).

And the parameter has to be calculated along the interface
gradient:
Nc Nc
Δρi Δρ j
c =  cij
i=1 j=1 Δρ ref Δρ ref
As the Linear Gradient Theory model is defined in this particular
way, an Equation of State that can describe the interface between
the two phases is necessary. The supported Equations of State in
Multiflash are SRK(A), PR(A), CPA, BWRS and SAFT.
This method has more reliable results with components present in
the oil and gas processing, while using the SRK, PR or CPA
Equations of State.
Reference: Zuo, Y. X. and Stenby, E. H., A Linear Gradient Theory
Model for Calculating Interfacial Tensions of Mixtures, Journal of
Colloid & Interface Science, 182 p12, Elsevier (1996)

Macleod-Sugden method
This method predicts the surface tension of a liquid mixture based
on the pure component parachors stored in a databank.

 1/ 4   Pi (  l xi   v yi )
where:
Pi is the parachor for component i
 l is the liquid molar density
 v is the vapour molar density

54
 xi is the liquid mole fraction
yi is the vapour mole fraction.
It is mainly applicable to the types of component found in oil and
gas processing. There are two variants of the method: a) the 1-
phase variant (MCS) where the density of the gas phase is
calculated using the perfect gas equation of state. b) The 2-phase
variant or advanced version (MCSA) where the properties of the gas
phase are estimated using a suitable model.
Reference: Pedersen, Fredenslund and Thomassen, Properties of
Oils and Natural Gases, Gulf Publishing Co., (1989).

Sutton
The Sutton method predicts the interfacial tension between an
aqueous phase and a gas or a liquid hydrocarbon phase. The
method uses the density difference between the phases and the
critical pressure of the hydrocarbon phase.

[( ) ]
c3
c1 (ρw −ρh ) + c 2
σ hw = a 2 + a3 T + a4 T 2
T
Tc
where
σ hw is the surface tension between water and a
hydrocarbon phase
T is the temperature
T c is the critical temperature of the hydrocarbon phase
ρw is the density of the aqueous phase
ρh is the density of the hydrocarbon phase
and

a1 = 0.272727 c1 = 1.53988
a2 = 0.821976 c2 = 2.08339
a3 = −1.83785×10
−3
c 3 = 1/a 1 = 3.66667
a4 = 1.34016×10−6
a5 = 302.881
The model is mainly applicable to the type of components found in
the oil and gas processing including hydrate inhibitors.
Reference: Sutton, RP, An Improved Model for Water-Hydrocarbon
Surface Tension at Reservoir Conditions, SPE 124968 (2009).

Surface tension mixing rule

The surface tension for a liquid mixture may be calculated from
the correlations for the surface tension of the pure saturated
55
 liquids at the same temperature and pressure using a power law
model.
1
 i ni
1 i

  i ni
where  i is the surface tension of the pure saturated liquid for
component i .
Reference: Pedersen, Fredenslund and Thomassen, Properties of
Oils and Natural Gases, Gulf Publishing Co., (1989).

Diffusion coefficients
Fuller method
The Fuller method calculates gas diffusion coefficients. It is an
empirical modification of Chapman-Enskog theory. The Fuller
expression for the diffusion coefficient for components i and j
in SI units is:
1/ 2
1.0112  10 22 T 1.75 k ij  1 1 
Dij   

p 1i / 3  1j/ 3 
2 M
 i Mj


T is the temperature, p is the pressure, M i is the relative

molecular weight of component i (in g mol-1) and  i is a
characteristic volume that is found for each component using
Fuller’s tables. k ij is an empirical adjustment factor for the user
to match the Fuller method to experimental data if available; to
obtain the standard result from Fuller’s method, k ij should be set
to unity.
Reference: Chapter 11 of The Properties of Gases and Liquids, 5th.
Ed. by Poling, Prausnitz and O’Connell, McGraw-Hill, New York,
2001.

Hayduk-Minhas method
The Hayduk-Minhas method calculates liquid diffusion
coefficients. It consists of a number of empirical correlations for
different classes of mixture. For example for normal paraffins the
diffusion coefficient of a trace amount of component i in
component j in SI units is:

7.309  10 16 T 1.47 1000 j 



Dij0 
Vi 0.71
1.02  10 5
   0.791
Vi

56
T is the temperature, Vi is the molar volume of component i
and  j is the liquid viscosity of component j . The viscosity is
calculated from the liquid viscosity model specified by the user.
Details of the other correlations that form the Hayduk-Minhas
method are described in the Reference. Multiflash actually returns
effective diffusion coefficients for a liquid of defined composition.
The expression used is:

  D 
Dij  Dij0
xj 0 xi
ji k ij
 ln  i  ln  j
  1  xi  1 xj
xi x j

where xi and  i are the mole fractions and activity coefficients

of component i in the binary mixture. For the sake of efficiency,
the activity coefficients are calculated from the Margules
expression which in turn is fitted to the activity coefficients for an
equimolar binary mixture calculated with the thermodynamic
model for the liquid phase specified by the user. k ij is an
empirical adjustment factor for the user to match the calculated
result to experimental data if available; to obtain the standard
result, k ij should be set to unity.
Reference: Chapter 11 of The Properties of Gases and Liquids, 5th.
Ed. by Poling, Prausnitz and O’Connell, McGraw-Hill, New York,
2001.

57
Binary interaction parameters

Introduction
Binary interaction parameters (BIPs) are adjustable factors which
are used to alter the predictions from a model until these
reproduce as closely as possible the experimental data. BIPs are
usually generated by fitting experimental VLE or LLE data to the
model in question, with the exception of UNIFAC and PSRK BIPs
which are predicted by group contribution. BIPs apply between
pairs of components. However, the fitting procedure may be based
on both binary and multi-component phase equilibria information,
the former being the most common.

Number of BIPs related to any model

Different models require differing numbers of BIPs and these may
or may not have physical significance. The cubic equations of state
(RK, RKS, PR) require only a single BIP. The closer the binary
system is to ideality the smaller the size of the BIP, which will be
zero for ideal systems. It is unlikely that the value of the BIP will
be greater than 1, although it is possible for it to be negative. For
the LK and LKP models the default value of the interaction
parameter is 1.
When non-standard mixing rules are used, e.g. when using
RKSA(Infochem), then the number of BIPs increases. For the excess
Gibbs energy type mixing rules (MHV2-type and Huron-Vidal-type)
the number of BIPs will be determined by the activity coefficient
model used to describe the liquid phase. For the Infochem mixing
rule 3 BIPs are needed.
PC-SAFT requires two symmetric BIPs, in addition to the pure
component model parameters. The default value for both is zero.
CPA uses the same interaction parameters as RKSA with the
addition of three association parameters to describe cross
association and self association where this occurs.
The Wilson A and UNIQUAC models require two BIPs; Wilson E
needs the same number of BIPs, but these are not interchangeable
with Wilson A. NRTL needs two binary energy interaction
parameters and a non-randomness factor,  . With the exception
of  , these BIPs may take a wide range of numerical values and
more that one set may adequately represent the same
experimental data. The BIPs for the activity models are asymmetric
58
 and it is important to define the binary pair of components i and
j in the correct order to agree with the fitted or reported BIPs.
The NRTL  parameter defaults to 0.3 for VLE calculations and
0.2 for LLE calculations. Values derived from fitting to
experimental data will vary but are unlikely to be much greater
than 0.6.
The Regular Solution and Flory Huggins models both use a BIPs
that are symmetrical, dimensionless and with a default value of
zero.

Units for BIPs

The BIPs for equation of state methods are dimensionless, with the
exception of two of the CPA association parameters. For some of
the activity coefficient models they are dimensioned with the
exception of Wilson A, Regular Solution and Flory Huggins. The
dimensions used in Multiflash are J/mole. If BIPs from external
sources are used in Multiflash it is important that either the BIP
units are changed to match the input values or the numeric values
of the BIPs are changed to J/mole.
The choice of units appears once the Units button is selected in the
BIP display. J/mol is the Multiflash standard for the dimensioned
activity model BIPs. Cal/mol and K are the values used in the
Dechema Data Series for activity VLE and LLE BIPs. The “Aspen”
format allows you to transfer the BIP values for the NRTL equation
produced from Aspen Plus without further change.

Temperature dependence of BIPs

In most of the open literature sources the reported binary
interaction parameters will be temperature independent, i.e.
constants. However, Multiflash allows for any BIP to be
temperature dependent with either a linear or a quadratic
dependence, although we do not recommend this for the NRTL 
parameter. The BIPs can in general be defined as
Aij  a ij  bij T  cij T 2

where T is the absolute temperature in K. The user can enter the

three coefficients aij, bij and cij.

Changing units
For activity coefficient BIPs, it is possible to change units. The
equation above is valid for the default units of J/mol. To convert
to calories the coefficients are divided by 4.18J/cal. To convert to
K, the coefficients are divided by the gas constant, R =
8.31441J/mol K. To convert to the dimensionless form, the
expression for Aij is divided by RT and the first two terms are
reordered to give
Aij / RT =d ij+ eij / T + f ij T
where

59
 d ij=b ij /R
e ij =a ij /R
f ij =c ij / R
The NRTL  parameter is dimensionless so it is given by

α ij =a ij + bij T + c ij T 2
for all units except the Aspen units when it is expressed as
2
α ij =d ij + eij t+ f ij t
where t is the temperature in C. The conversion factors are
2
d ij=aij + b ij ×273 .15+ c ij×273. 15
e ij =bij + 2cij ×273 .15
f ij =c ij

BIPs available in Multiflash

Our main BIP bank is applicable to oil and gas processing
operations and called appropriately, OILANDGAS. This contains
BIPs for the cubic equation of state models PR, PRA, PR78, PR78A,
PR-HVP, RKS, RKSA, RKS-HVP, and RKSA (Infochem) for
hydrocarbons, water, methanol, glycols, H2S, CO2 and N2, and for
the CPA model. The correlations have been extended to include
BIPs for the LKP model for hydrocarbon and light gas mixtures.
Multiflash also provides methods for estimating BIPs for the PR,
RKS and CPA equations for mixtures that include petroleum
fractions.
The INFOBIPS BIP bank includes BIPs for the WilsonE and the VLE
variants of NRTL and UNIQUAC, based on the data reported in the
Dechema Chemistry Data Series. Some BIPs are also available for
equations of state such as BWRS, LKP and the cubics for systems
not covered by the normal correlations, e.g. binaries including
ammonia. The INFOBIPS databank is updated as data are available.
A BIP bank, INFOLLBIPS, stores BIPs for use with the LLE variants
of NRTL and UNIQUAC.
For the UNIFAC model, BIPs are predicted from group
contributions. The data records for pure components in the
INFODATA databank contain information on UNIFAC groups,
where applicable, enabling the BIPs to be generated. Groups for use
with the PSRK and Dortmund Modified UNIFAC models are also
stored as part of the pure component UNIFAC record. Where the
groups vary, Multiflash applies the correct group structure to
match the chosen model. We have created an Infochem version of
DIPPR that includes the same group information. You will see a
warning message if the group contributions are missing for any
chosen component.
It is possible to have two BIP banks in force for any problem. All
the .mfc model descriptions for the equations of state define both
INFOBIPS and OILANDGAS. When the model is defined Multiflash
will first search INFOBIPS for any specific binary BIPS, then define
BIPs from the correlations in OILANDGAS and if any are still

60
missing they will be set to default values. The VLE variants of the
activity methods only access INFOBIPS, but the LLE variants access
INFOLLBIPS, followed by INFOBIPS.
Between releases of Multiflash we may amend, or add to, the BIPs
stored. For the OILANDGAS databank we will supply a copy of the
previous banks in order to maintain backward compatibility. The
current version will still be known as OILANDGAS4, and also the
default, OILANDGAS. Previous versions such as OILANDGAS3 can
be recalled if you wish. For INFOBIPS 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.

61
Model data requirements

Each model requires a certain amount of pure component data.

These are listed in the following table.

Model Minimum input

Thermodynamic
RKS critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
perfect gas Cp (CPIDEAL)
RKSAPI critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
perfect gas Cp (CPIDEAL)
RKSA critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
vapour pressure (PSAT), saturated liquid density
(LDENS), perfect gas Cp (CPIDEAL)
RKSAINFO critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
vapour pressure (PSAT), saturated liquid density
(LDENS), perfect gas Cp (CPIDEAL)
RKS-HVP critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
perfect gas Cp (CPIDEAL)
PR critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
perfect gas Cp (CPIDEAL)
PR78 critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
perfect gas Cp (CPIDEAL)
PRA critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
vapour pressure (PSAT), saturated liquid density
(LDENS), perfect gas Cp (CPIDEAL)
PR78A critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
vapour pressure (PSAT), saturated liquid density
(LDENS), perfect gas Cp (CPIDEAL)
PR-HVP critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
perfect gas Cp (CPIDEAL)

PSRK critical temperature (TCRIT), critical pressure

62
 (PCRIT), acentric factor (ACENTRICFACTOR),
vapour pressure (PSAT), saturated liquid density
(LDENS), perfect gas Cp (CPIDEAL) ), UNIFAC
subgroup structures (UNIFAC)
PSRK-NRTL critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
vapour pressure (PSAT), saturated liquid density
(LDENS), perfect gas Cp (CPIDEAL) ).
LK critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
perfect gas Cp (CPIDEAL)
LKP critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
perfect gas Cp (CPIDEAL)
BWRS critical temperature (TCRIT), critical pressure
(PCRIT), critical volume (VCRIT) and acentric
factor (ACENTRICFACTOR) for components
not in model database, perfect gas Cp
(CPIDEAL)
CSMA critical temperature (TCRIT), critical pressure
(PCRIT), critical volume (VCRIT), perfect gas
Cp (CPIDEAL)
CPA critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
vapour pressure (PSAT), saturated liquid density
(LDENS), association parameters (ASSBE,
ASSEP, ASSGA), perfect gas Cp (CPIDEAL)
ZJ critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
perfect gas Cp (CPIDEAL)
PC-SAFT critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
PC-SAFT parameters (SAFTEK, SAFTSIGMA,
SAFTM, SAFTKAPPA, SAFTEPSILON,
SAFTFF), perfect gas Cp (CPIDEAL).
Note (1) TCRIT, PCRIT and
ACENTRICFACTOR are necessary to generate
starting values for flash calculations but do not
affect the computed results from PC-SAFT. (2)
SAFTKAPPA, SAFTEPSILON and SAFTFF are
only needed for associating components.

Ideal solution vapour pressure (PSAT), saturated liquid density

(LDENS)
NRTL vapour pressure (PSAT), saturated liquid density
(LDENS)
Wilson vapour pressure (PSAT), saturated liquid density
(LDENS)
UNIQUAC vapour pressure (PSAT), saturated liquid density
(LDENS), surface and volume parameters
(UNIQQ, UNIQR)
UNIFAC vapour pressure (PSAT), saturated liquid density
(LDENS), UNIFAC subgroup structures
(UNIFAC)
Dortmund Modified vapour pressure (PSAT), saturated liquid density
63
UNIFAC (LDENS), UNIFAC subgroup structures
(UNIFAC)
Regular Solution vapour pressure (PSAT), saturated liquid density
(LDENS), solubility parameter (SOLUPAR) and
molar volume at 25°C (V25).
Flory-Huggins vapour pressure (PSAT), saturated liquid density
(LDENS), solubility parameter (SOLUPAR) and
molar volume at 25°C (V25).
perfect gas perfect gas Cp (CPIDEAL)
RK critical temperature (TCRIT), critical pressure
(PCRIT), perfect gas Cp (CPIDEAL)
Hayden O’Connell critical temperature (TCRIT), critical pressure
(PCRIT), radius of gyration (RADGYR), dipole
moment (DIPOLEMOMENT), Hayden-
O’Connell association parameter (HOCASS),
perfect gas Cp (CPIDEAL)

Freeze-out melting point (TMELT), enthalpy of fusion

(HMELT), heat capacity change on fusion
(CPMELT), volume of fusion (VMELT)
Hydrate potential parameters (HYD1, HYD2, HYD3),
cavity occupation code (HYDOC)
Wax melting point (TMELT), enthalpy of fusion
(HMELT), heat capacity change on fusion
(CPMELT), volume of fusion (VMELT)
Asphaltene critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
vapour pressure (PSAT), saturated liquid density
(LDENS),

Transport properties

Pedersen critical temperature (TCRIT), critical pressure

(PCRIT), molecular weight
(MOLECULARWEIGHT)
Twu molecular weight (MOLECULARWEIGHT),
boiling point (TBOIL), vapour pressure (PSAT),
saturated liquid density (LDENS)
LBC critical temperature (TCRIT), critical pressure
Lohrenz-Bray-Clark (PCRIT), critical volume (VCRIT), dipole
moment (DIPOLEMOMENT), molecular weight
(MOLECULARWEIGHT)
CLS critical temperature (TCRIT), critical volume
Chung-Lee-Starling (VCRIT), dipole moment (DIPOLEMOMENT),
molecular weight (MOLECULARWEIGHT)
STRAPP critical temperature (TCRIT), critical pressure
SuperTRAPP method (PCRIT), acentric factor (ACENTRICFACTOR),
critical volume (VCRIT), dipole moment
(DIPOLEMOMENT), molecular weight
(MOLECULARWEIGHT)
Linear Gradient Theory surface tension (STENSION), critical
temperature (TCRIT)
Macleod-Sugden parachor (PARACHOR)
Costald critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
saturated liquid density (LDENS)
64
Liquid viscosity mixing liquid viscosity (LVISC)
rule
Vapour viscosity mixing vapour viscosity (VVISC)
rule
Liquid thermal liquid thermal conductivity (LTHCOND)
conductivity mixing rule
Vapour thermal vapour thermal conductivity (VTHCOND)
conductivity mixing rule
Surface tension mixing surface tension (STENSION)
rule
Diffusivity – Fuller's molecular weight (MOLECULARWEIGHT),
method chemical formula (FORMULA), UNIFAC
subgroup structures (UNIFAC).
Diffusivity - Hayduk- critical temperature (TCRIT), critical molar
Minhas method volume (VCRIT), normal boiling point (TBOIL),
parachor (PARACHOR) dipole moment
(DIPOLEMOMENT), saturated liquid density
(LDENS), chemical formula (FORMULA),
UNIFAC subgroup structures (UNIFAC).

65
Components

Introduction
Multiflash recognises three types of component. Normal
components are pure compounds such as hydrocarbons,
petrochemicals and chemicals, which may exist as gas, liquid or
solid depending on conditions of temperature and pressure. A
petroleum fraction is a pseudo component, usually a complex
mixture of hydrocarbons, whose aggregate properties are
characterised by standard tests, the results of which may be found
in PVT laboratory reports.
The physical properties for each type of component are stored or
defined differently.

Normal components
The physical properties of normal components are usually stored
in databanks. Multiflash offers two, INFODATA and DIPPRTM.
INFODATA is the Infochem fluids databank, which contains data
on about 200 compounds and is always supplied as part of
Multiflash. DIPPR, produced under the auspices of AIChE, currently
has data for over 1700 compounds, but is extended annually.

Properties of normal components

Both INFODATA and DIPPR store data for each variable property
(e.g. vapour pressure, liquid density) of a component as a function
of temperature. Properties that are not temperature dependent are
stored as constant values. A list of the properties available in
DIPPR and INFODATA is shown below. Some properties may be
missing for individual components.
Constant properties
Molecular Weight
Critical Temperature
Critical Pressure
Critical Volume
Critical Compressibility Factor
Melting Point
Triple Point Temperature
Triple Point Pressure
Normal Boiling Point (at 1 atm)

66
 Liquid Molar Volume at 298.15K
Standard perfect gas Enthalpy of
Formation at 298.15K
Standard perfect gas Gibbs Energy of
Formation at 298.15K
Standard perfect gas Entropy at 298.15K
Enthalpy of Fusion at Melting Point
Entropy of Fusion at Melting Point
Heat capacity change on fusion
Volume change on fusion
Standard Net Enthalpy of Combustion at 298.15K
Acentric Factor
Radius of Gyration
Parachor
Solubility Parameter at 298.15K
Dipole Moment
van der Waals Volume (UNIQUAC r)
van der Waals Area (UNIQUAC q)
Refractive Index
Flash Point
Lower Flammability Limit
Upper Flammability Limit
Autoignition Temperature

plus some model specific parameters.

Additionally there is a group of properties that allow unique
identification of the name and type of the component. These are

TYPE
CAS number
FORMULA
FAMILY code
Normal databank components will be TYPE 1.

Temperature Dependent Properties

Solid Density
Liquid density
Vapour Pressure
Enthalpy of vaporisation
Solid Heat Capacity
Liquid Heat Capacity
perfect gas Heat Capacity
Second Virial Coefficient
Liquid Viscosity
Vapour Viscosity
Liquid Thermal Conductivity
Vapour Thermal Conductivity
Surface tension
Relative permittivity (dielectric constant)
Both databanks, in addition to the properties above, also contain
the UNIFAC and PSRK group structures, where applicable. For
some components, coefficients will also be stored for the second
virial coefficient and relative permittivity, both used for model
calculations.

67
 INFODATA contains only a limited range of components, about
247, mainly suitable for oil and gas processing. Although every
effort has been made to ensure that the data stored are correct we
do not offer INFODATA as a quality assured databank.
DIPPR is developed under the auspices of the American Institute of
Chemical Engineers. The databank contains a broad range of
components including hydrocarbons, petrochemicals, chemicals
and some metals. The correlations used in Multiflash are the
recommended set for each property and component. Questions
concerning quality codes and sources of data for the DIPPR
databank should be referred to Infochem.
Each temperature dependent property may be stored by a variety
of correlations
The temperature dependent properties are stored as coefficients of
designated correlation equations. For each property there is a
choice of correlation equations; each is assigned an equation
number and it is this plus the property ID code and coefficients
that is displayed through the Tools/Pure Component menu.
The correlation equations for each property are shown in the
following table.

Pure component temperature-dependent

properties
The form of each correlation is defined below. Property units are
given in parentheses. They are fixed and are not affected by the
UNITS or INPUTUNITS command.
The format require for each property correlation is
property_name equation_number coefficients Tmin Tmax;
property_name is one of the keywords from the following table.
equation_number identifies the correlation.
coefficients are the numerical values of the correlation
coefficients. The number of coefficients required depends on the
equation number.
For temperature dependent properties both databanks contain
information on the upper and lower temperature limits for the
correlation used for each component. Extrapolation routines are
included in Multiflash so that pure component properties from
either bank behave sensibly beyond the temperature limits of the
stored correlation.

Keyword Equation Additional information

number
Cpideal perfect gas Cp correlation (J/mol K)
0 data unknown; 0 coefficients
1 Harmens method, 9 coefficients
a3, a4, a5, a6, a7, a8, a9, Tmin, Tmax
C p / R  a3  a4  a3  y 2 1   y  1 F ( y )

68
 T
where F ( y )  a 6  a 7 y  a8 y 2  a9 y 3 , y 
T  a5
2 DIPPR equation 107, 7 coefficients
a3, a4, a5, a6, a7, Tmin, Tmax
2 2
 a5 / T   a7 / T 
C p  a3  a 4    a6  
 sinha5 / T    cosh a 7 / T  
5 DIPPR equation 100, 7 coefficients
a3, a4, a5, a6, a7, Tmin, Tmax
C p  a 3  a 4 T  a 5T 2  a 6 T 3  a 7 T 4
Cpliquid liquid Cp correlation (J/mol K)
0 data unknown, 0 coefficients
1 DIPPR equation 114, 9 coefficients
a1, a2, a3, a4, a5, a6, a7, Tmin, Tmax
C p  a1 /   a2  a3  a4 2  a5 3  a6 4  a7 5
where   1  T / Tc
5 DIPPR equation 100, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
C p  a1  a2T  a3T 2  a4T 3  a5T 4
Cpsolid solid Cp correlation (J/mol K)
0 data unknown, 0 coefficients
5 DIPPR equation 100, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
C p  a1  a2T  a3T 2  a 4T 3  a5T 4
psat saturated vapour pressure (Pa)
0 data unknown, 0 coefficients
1 Wagner (form 1) 5 coefficients
a1, a2, a3, Tmin, Tmax
a1  a 2 2  a3 3
ln p  ln pc 
Tr
where Tr  T / Tc ,   1  Tr
2 Antoine equation, 9 coefficients
a1, a2, a3, a4, a5, a6, a7, Tmin, Tmax
a2 a
ln p  a1   a 4T a6  a5 ln T  72
T  a3 T
Note that if the third term is unused a4 should be set to 0 and
a6 must be set to a positive value such as 1.0.
3 Wagner (form 2), 6 coefficients
a1, a2, a3, a4, Tmin, Tmax
3
a1  a 2  a3 3  a 4 6
2
ln p  ln pc 
Tr
where Tr  T / Tc ,   1  Tr
4 Wagner (form 3), 6 coefficients
a1, a2, a3, a4, Tmin, Tmax

69
 3 5
a   a 2 2  a 3 2  a 4 5
ln p  ln pc  1
Tr
where Tr  T / Tc ,   1  Tr
5 DIPPR equation 100, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
p  a1  a2T  a3T 2  a4T 3  a5T 4
7 IAPWS equation
3 7 15
2 3 2 4 2
ln p=ln pc + (a 1 τ+ a 2 τ + a 3 τ + a 4 τ + a 5 τ + a 6 τ )/T r
where Tr  T / Tc   1  Tr
,
T > T c :ln p=ln p c+ ( a 1 τ )/T r
T < T min :ln p=ln pc + (b 1+ b 2 /T r )
hvap enthalpy of vaporisation correlation (J/mol)
0 data unknown, 0 coefficients
1 Watson/DIPPR 106 equation, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
DH  a1 Y
where Y  a 2  a3Tr  a 4 Tr  a5Tr , Tr  T / Tc ,
2 3

Tr  T / Tc ,   1  Tr
2 Wagner type equation for enthalpy of
vaporisation, 9 coefficients
a1, a2, a3, a4, a5, a6, a7, Tmin, Tmax
Δ /RT c=a 1 τ 1/3+ a 2 τ 2/3 + a 3 τ+ a 4 τ 4/3+ a 5 τ 5/3
H
+ a 6 τ 2+ a 7 τ 6
where   1  T / Tc
5 DIPPR equation 100, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
DH  a1  a2T  a3T 2  a4T 3  a5T 4
ldens saturated liquid density correlation (mol/m3)
0 data unknown, 0 coefficients
1 Infochem equation, 5 coefficients
a1, a2, a3, Tmin, Tmax
a
ρ=a 1 + a 2 τ 3
where   1  T / Tc
2 Hankinson and Thompson equation
(modified), 6 coefficients
a1, a2, a3, a4, Tmin, Tmax
1 2 4
  1 / Vc  a1  a 2  a3  a 4
3 3 3

where   1  T / Tc
Note that in the above equation ρ is the mass density and Vc
is the critical volume per unit mass
3 Rackett equation (modified), 5 coefficients
a1, a2, a3, Tmin, Tmax

70
 1 /   a1 a 2  a3 
Y

2
where
Y  1   7 ,   1  T / Tc
4 DIPPR equation 105, 6 coefficients
a1, a2, a3, a4, Tmin, Tmax
1 /   a 2 Y / a1
Y  1  1  T / a3 
a4
where

5 DIPPR equation 100, 7 coefficients

a1, a2, a3, a4, a5, Tmin, Tmax
  a1  a 2T  a3T 2  a4T 3  a5T 4
7 IAPWS equation
1 2 5 16 43 110
ρ
=1+ a 1 τ 3 + a 2 τ 3 + a3 τ 3 + a 4 τ 3 + a 5 τ 3 + a 6 τ 3
ρc
Where ρc is the critical density and
  1  T / Tc
T > T H : hyperbolic extrapolation
T < T min : Linear/quadratic extrapolation
sdens solid density correlation (mol/m3)
0 data unknown, 0 coefficients
5 DIPPR equation 100, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
  a1  a 2T  a3T 2  a4T 3  a5T 4
lthcond liquid thermal conductivity correlation (W/m K)
0 data unknown, 0 coefficients
1 Jamieson equation, 6 coefficients
a1, a2, a3, a4, Tmin, Tmax
 1 2

  a1 1  a 2 3  a3 3  a 4 
 
where   1  T / Tc
2 DIPPR equation 101, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
ln   a1  a 2 / T  a3 ln T  a 4T a5
5 DIPPR equation 100, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
  a1  a2T  a3T 2  a4T 3  a5T 4
vthcond vapour thermal conductivity correlation (W/m K)
0 data unknown, 0 coefficients
1 DIPPR equation 102, 6 coefficients
a1, a2, a3, a4, Tmin, Tmax
a1 T a2

1  a3 / T  a4 / T 2
2 Reduced correlation, 6 coefficients
a1, a2, a3, a4, Tmin, Tmax

71
 Tr

a1  a 2Tr  a3Tr2  a 4Tr3
where Tr  T / Tc
3 Monatomic ideal gas, 2 coefficients, Tmin, Tmax
  3750 0 R / M
5 DIPPR equation 100, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
  a1  a2T  a3T 2  a4T 3  a5T 4
lvisc liquid viscosity correlation (Pa s)
0 data unknown, 0 coefficients
1 Reid, Prausnitz and Poling equation 1,
4 coefficients a1, a2, Tmin, Tmax
  a1T a2
2 DIPPR equation 101, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
ln   a1  a 2 / T  a3 ln T  a 4T a5
3 Reduced correlation, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
1 4
ln  / a5   a1 X  a 2 X
3 3

a3  a 4
where X  1
T  a4
4 Reid, Prausnitz and Poling equation 2/3, 6
coefficients a1, a2, a3, a4, Tmin, Tmax
ln   a1  a 2 / T  a3T  a 4T 2
5 DIPPR equation 100, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
  a1  a2T  a3T 2  a4T 3  a5T 4
vvisc vapour viscosity correlation (Pa s)
0 data unknown, 0 coefficients
1 DIPPR equation 102, 6 coefficients
a1, a2, a3, a4, Tmin, Tmax
a1T a2

1  a3 / T  a 4 / T 2
2 Reichenberg equation, 5 coefficients
a1, a2, a3, Tmin, Tmax
a1Tr
 1

1  a 2Tra3 Tr  1  6

where Tr  T / Tc
3 Chapman-Enskog equation, 5 coefficients
a1, a2, a3, Tmin, Tmax
1
26.69  10 7  MT  2


a12  2, 2 T * , a3 
72
 where
   
 2, 2  AT * B  C exp  DT *  E exp  FT *  0.2a32 / T *
T *  T / a 2 , A  116145
. , B  014874
. , C  0.52487 ,
D  0.77320 , E  216178
. , F  2.43787
5 DIPPR equation 100, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
  a1  a2T  a3T 2  a4T 3  a5T 4
stension surface tension correlation (N/m)
0 data unknown, 0 coefficients
1 DIPPR equation 106, 7 coefficients
a1, a2, a3, a4, a5 Tmin, Tmax
  a1 1  Tr 
Y

where Y  a2  a3Tr  a4Tr2  a5Tr3 , Tr  T / Tc

2 Extended Sprow and Prausnitz equation, 5
coefficients a1, a2, a3, Tmin, Tmax
  a1 a2 1  a3 
where   1  T / Tc
5 DIPPR equation 100, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
  a1  a 2T  a3T 2  a 4T 3  a5T 4
virialcoeff second virial coefficient correlation (m3/mol)
0 data unknown, 0 coefficients
1 DIPPR equation 104, 7 coefficients
a1, a2, a3, a4, a5 Tmin, Tmax
B  a1  a 2  a3 3  a 4 8  a5 9
where   Tc / T
5 DIPPR equation 100, 7 coefficients
a1, a2, a3, a4, a5, Tmin, Tmax
B  a1  a2T  a3T 2  a4T 3  a5T 4
dielectric relative permittivity/dielectric constant correlation
0 data unknown, 0 coefficients
1 Maryott-Smith equation 1, 6 coefficients
a1, a2, a3, a4, Tmin, Tmax
ε=a 1 + a 2 T + a 3 T 2 + a 4 T 3
2 Maryott-Smith equation 2, 4 coefficients
a1, a2, Tmin, Tmax
ε=exp ( a 1 + a 2 T )
3 Infochem equation, 6 coefficients
a1, a2, a3, a4, Tmin, Tmax
ε=1+ a1 exp (−a 2 T −a 3 T 2 −a 4 T 3 )

73
Petroleum fractions
To define a single petroleum fraction the program requires certain
characteristic properties and Multiflash will then estimate the
other properties needed to support the range of calculations
available in the program.
The list of possible properties to support characterisation of the
fraction are:
Carbon number
Molecular weight (g/mol)
Specific gravity at 60oF relative to water at 60oF
Normal boiling point
Critical temperature
Critical pressure
Pitzer’s acentric factor
However, not all of these are necessary. The minimum input sets
are molecular weight, molecular weight and specific gravity;
molecular weight and boiling point; boiling point and specific
gravity; critical temperature, critical pressure and acentric factor.
Alternatively, the boiling point can be used instead of the acentric
factor.
The properties that are estimated, if they have not been provided,
are:
Carbon number
Molecular weight
Normal boiling point
Critical temperature
Critical pressure
Critical volume
Acentric factor
Parachor
Dipole moment
Enthalpy of formation
Standard entropy
Perfect gas Cp
Saturated liquid density
Saturated vapour pressure
Enthalpy of evaporation
Liquid viscosity
Petroleum fractions will normally be designated as TYPE 12.

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 basis for the calculations:
Molecular weight Riazi, M.R. and Al-Sahhaf, T.A., Fluid Phase
Equilibria 117 217-224 (1996)
Boiling point Edmister, W.C. Pet. Refiner 37 154 (1958)
Brule, M.R. and Whitson, C.H., SPE
Monograph 20 (2000)
Riazi, M.R. and Al-Sahhaf, T.A., Ind. Eng.
Chem. Research, 34 4145 (1995)

74
Specific gravity Riazi, M.R. and Al-Sahhaf, T.A., Ind. Eng.
Chem. Research, 34 4145 (1995)
Tc, Pc,  Kesler, M.G. and Lee, B.I., Hydrocarbon
Processing 55(3) 153 (1976)
Brule, M.R. and Whitson, C.H., SPE
Monograph 20 (2000)
Riazi, M.R. and Al-Sahhaf, T.A., Ind. Eng.
Chem. Research, 34 4145 (1995
Vc Riazi, M.R., Daubert, T.E., Hydrocarbon
Processing, 59, 115 (1980)
Lira-Galeana, C., Firoozabadi, A. and
Prausnitz, J.M., AIChE J., 42(1) 239
(1996)Riazi, M.R. and Al-Sahhaf, T.A., Ind.
Eng. Chem. Research, 34 4145 (1995)
Enthalpy of Formation and Standard Entropy
Reid, R.C., Prausnitz, J.M. and Poling, B.E.;
"The Properties of Gases and Liquids", Gulf,
Houston (1987)
Ideal Cp Kesler, M.G. and Lee, B.I., Hydrocarbon
Processing 55(3) 153 (1976) and
Harmens, A., "Chemical Thermodynamics
Data on Fluids and Fluid Mixtures", IPC
Science and Technology Press (1979)
Melting Point Won, K.W., Fluid Phase Equilibria, 30 265
(1986)
Lira-Galeana, C., Firoozabadi, A. and
Prausnitz, J.M., AIChE J., 42(1) 239 (1996)
Fusion properties Morgan, D.L. and Kobayashi, R., Fluid Phase
Equilibria, 63 317 (1991)
Won, K.W., Fluid Phase Equilibria, 30 265
(1986)
Brown, T.S., Niesen, V.G. and Erikson, D.D.,
SPE 8505 (1994)
Lira-Galeana, C., Firoozabadi, A. and
Prausnitz, J.M., AIChE J., 42(1) 239 (1996)
Solubility Parameter Pedersen, K.S., et al, Energy and Fuels. 5 924
(1991)
Surface Tension Quale, O.R., Chem. Rev., 53 439 (1958)
Liquid Viscosity Orbey, H. and Sandler, S.I., Canadian J. Che.
Eng., 74 437 (1993)

75
Index

A
Activity coefficient models
Activity coefficient equations in Multiflash
34
Flory-Huggins theory 38
Gas phase models for activity coefficient
methods 39
Ideal solution model 34
NRTL equation 35
Regular solution theory 38
UNIFAC group-contribution methods 36
UNIQUAC equation 36
Wilson equation 35
C
Cubic plus association (CPA) model 22
E
Equations of state
Benedict-Webb-Rubin-Starling (BWRS)
equation of state equation of state 27
Cubic plus association (CPA) model 22
Equations of state provided in Multiflash
14
Ideal gas equation of state 14
PC-SAFT equation of state 23
Peng-Robinson 1978 (PR78) equation of
state 16
Peng-Robinson equation of state 15
PSRK equation of state 25
PSRK-NRTL equation of state 25
Lee-Kesler (LK) and Lee-Kesler-Plöcker
(LKP) equation of state 25
Redlich-Kwong (RK) and Redlich-Kwong-
Soave (RKS) equations 16
H
Hydrates
Hydrate inhibitor model 44
M
Models 57
W
Wilson A equation 35