Thermodynamics Models

Simulis
Thermodynamics
_____________________________________________________________________________

_____________________________________________________________________________
Thermodynamic properties and phase equilibria
calculation server

Thermodynamics models
Version 1.3

_____________________________________________________________________________

How to contact ProSim Technical Support:

@ support@prosim.net e-mail

+33 (0)5 62 88 24 46 Phone

+33 (0)5 62 88 24 39 Fax

ProSim SA Mail
Stratge Btiment A
BP 27210
F-31672 LABEGE Cedex
France

www.prosim.net Web

To get general information, please contact info@prosim.net

For contact information about representatives and worldwide offices, see www.prosim.net

Copyright notice

The copyright in this manual and its associated software is the property of ProSim SA. All rights
reserved. Both this manual and the software described in this document have been furnished under
a license agreement containing restrictions on use.

This documentation contains ProSim proprietary and confidential information and may not be
disclosed, used, photocopied, reproduced, transmitted, transcribed or translated into any other
language, in any form or by any means without the prior written consent from ProSim SA.

ProSim reserves the right to make changes to this manual or its associated software without
obligation to notify any person or organization.

Users are solely responsible for the proper use of the software and the application of the results
obtained. Although ProSim has tested the software and reviewed the documentation, ProSim
makes no warranty or representation, either expressed or implied, with respect to this
documentation, its quality, performance, merchantability or fitness for a particular purpose.

ProSim, ProSimPlus, ProPhyPlus, RegSol and Simulis are trademarks or registered trademarks of
ProSim SA. All other brand or product names are trademarks or registered trademarks of their
respective holders.

Simulis Thermodynamics
Version 1.3
Copyright 2004-2008 by ProSim SA

Simulis
Thermodynamics Table of content - 1

______________________________________________________________________________________

TABLE OF CONTENT

1. Introduction------------------------------------------------------------------------------------------------------------------------------ 1
1.1. Homogeneous approach (equation of state) .................................................................................. 2
1.2. Heterogeneous approach ( formulation)............................................................................... 3
1.3. Combined approach (equation of state with complex mixing rules)............................................... 5
1.4. Specific models............................................................................................................................... 7
2. Equation of state---------------------------------------------------------------------------------------------------------------------- 8
2.1. Redlich Kwong (RK) .................................................................................................................... 8
2.2. Soave Redlich Kwong (SRK).................................................................................................. 10
2.3. Soave Redlich Kwong Boston Mathias (SRKBM) .................................................................. 12
2.4. Soave Redlich Kwong Kabadi and Danner (SRK KD85) ....................................................... 13
2.5. Soave Redlich Kwong Kabadi and Danner modified by Twu and Bluck(SRK KD88) ............ 16
2.6. Peng Robinson (PR).................................................................................................................. 18
2.7. Peng Robinson Boston Mathias (PRBM) .................................................................................. 20
2.8. Peng Robinson 78 (PR78)......................................................................................................... 21
2.9. Peng Robinson 78 Boston Mathias (PR78BM) ......................................................................... 22
2.10. Predictive Peng Robinson 78 (PPR78) ................................................................................... 23
2.11. Lee Kesler................................................................................................................................ 24
2.12. Lee Kesler Plcker (LKP) ..................................................................................................... 28
2.13. Benedict Webb Rubbin modified Starling Nishiumi (BWRS)............................................ 32
2.14. Nakamura ................................................................................................................................... 38
3. Activity coefficients models calculation------------------------------------------------------------------------------------- 40
3.1. Margules ....................................................................................................................................... 40
3.2. Regular solutions: Scatchard - Hildebrand................................................................................... 40
3.3. Wilson and Wilson Dechema compliant ....................................................................................... 41
3.4. NRTL ............................................................................................................................................ 42
3.5. Modified UNIQUAC ...................................................................................................................... 43
3.6. Original UNIFAC........................................................................................................................... 44
3.7. UNIFAC modified Dortmund......................................................................................................... 47
3.8. UNIFAC modied Lyngby (UNIFAC Larsen) .................................................................................. 49
3.9. UNIFAC PSRK.............................................................................................................................. 51
3.10. Three-phase vapor-liquid-liquid model ....................................................................................... 53
4. Standard state pure liquid fugacity--------------------------------------------------------------------------------------------55
4.1. Standard ....................................................................................................................................... 55
4.2. Standard with Poynting correction................................................................................................ 55
4.3. Vapor pressure ............................................................................................................................. 55
Simulis

______________________________________________________________________________________

4.4. Chao Seader.............................................................................................................................. 56
4.5. Grayson Streed.......................................................................................................................... 57
5. Complex mixing rules ---------------------------------------------------------------------------------------------------------------58
5.1. MHV1............................................................................................................................................ 60
5.2. MHV2............................................................................................................................................ 60
5.3. PSRK............................................................................................................................................ 60
6. Specific thermodynamic models------------------------------------------------------------------------------------------------- 61
6.1. NBS/NRC Steam Tables (pure water).......................................................................................... 61
6.2. Water-hydrocarbon mixtures ........................................................................................................ 62
6.3. Association in vapor phase........................................................................................................... 63
6.4. Formaldehyde-methanol-water systems ...................................................................................... 65
6.5. Engels........................................................................................................................................... 67
6.6. Souers .......................................................................................................................................... 69
6.7. Chao-Seader ................................................................................................................................ 70
6.8. Grayson-Streed ............................................................................................................................ 70
6.9. MHV2............................................................................................................................................ 70
6.10. PSRK.......................................................................................................................................... 71
6.11. Thermodynamic models applied to electrolyte solutions............................................................ 72
6.11.1. Introduction......................................................................................................................... 72
6.11.2. Some definitions................................................................................................................. 72
6.11.3. Mixed solvents UNIQUAC electrolytes (UQMS) ................................................................ 74
6.11.4. Sour Water UNIQUAC electrolytes (UQSW)...................................................................... 76
6.11.5. Sour Water (Edwards) ........................................................................................................ 78
6.11.6. ULPDHS............................................................................................................................. 80
6.11.6.1. Modified UNIFAC Larsen with solvation - ULS ....................................................... 80
6.11.6.1.1. Combinatorial term............................................................................................. 80
6.11.6.1.2. Residual term..................................................................................................... 82
6.11.6.2. Pitzer Debye Hckel contribution PDH - ................................................................. 84
6.11.7. Amines and acid gases ...................................................................................................... 86
7. Enthalpies - Entropies---------------------------------------------------------------------------------------------------------------88
7.1. Enthalpies..................................................................................................................................... 88
7.1.1. Enthalpy basis ...................................................................................................................... 88
7.1.2. Ideal gas state fluid enthalpy (H*) ........................................................................................ 88
7.1.3. Homogeneous approach (equation of state) ........................................................................ 89
7.1.4. Heterogeneous approach ( ) ....................................................................................... 90
7.1.4.1. Vapor phase................................................................................................................. 90
7.1.4.2. Liquid phase................................................................................................................. 90
7.1.4.2.1. General case........................................................................................................90
Simulis

______________________________________________________________________________________

7.1.4.2.2. Special case of Chao-Seader and Grayson-Streed methods.............................. 95
7.2. Entropies....................................................................................................................................... 96
7.2.1. Ideal gas state fluid entropy ................................................................................................. 96
7.2.2. Homogeneous approach (equation of state) ........................................................................ 96
7.2.3. Heterogeneous approach ( ) ....................................................................................... 97
7.2.3.1. Vapor phase................................................................................................................. 97
7.2.3.2. Liquid phase................................................................................................................. 97
7.2.3.2.1. General case........................................................................................................97
7.2.3.2.2. Special case of Chao-Seader and Grayson-Streed methods.............................. 99
8. Molar volume and liquid density ------------------------------------------------------------------------------------------------100
8.1. With equation of state................................................................................................................. 100
8.2. Ideal Mixture ............................................................................................................................... 100
8.3. Helgeson..................................................................................................................................... 100
8.4. API 6A2.22.................................................................................................................................. 101
8.5. COSTALD................................................................................................................................... 103
8.6. Rackett modified for pure components and ideal mixtures ........................................................ 105
8.7. Rackett modified for mixtures..................................................................................................... 106
8.8. Novotny and Sohnel ................................................................................................................... 107
9. Transport properties--------------------------------------------------------------------------------------------------------------108
9.1. liquid viscosity............................................................................................................................. 108
9.1.1. Pure mixing rules ............................................................................................................. 108
9.1.2. CLASSICAL mixing rules ................................................................................................. 108
9.1.3. ELY-HANLEY method (TRAPP method) ......................................................................... 108
9.1.4. PETRO method................................................................................................................ 110
9.1.4.1. Hydrocarbon mixture: Twu [TWU85].......................................................................... 110
9.1.4.2. Particular case: Water-Hydrocarbon model ............................................................... 111
9.2. Vapor viscosity............................................................................................................................ 112
9.2.1. Pure mixing rules ............................................................................................................. 112
9.2.2. Classic mixing rules ......................................................................................................... 112
9.2.2.1. Calculation of viscosity of a gazeous mixture at low pressure................................... 112
9.2.2.2. Calculation of viscosity of a gaseous mixture at high pressure ................................. 113
9.2.3. ELY-HANLEY method (TRAPP method) ........................................................................ 114
9.2.4. PETRO method................................................................................................................ 117
9.2.4.1. Hydrocarbon mixture at low pressure: Yoon and Thodos [YOO70]........................... 117
9.2.4.2. Influence of the pressure: Dean and Stiel (API 11B1.4) [DEA65], [API82]................ 117
9.2.4.3. Particular case : Water-hydrocarbon model............................................................... 117
9.3. Liquid thermal conductivity ......................................................................................................... 118
9.3.1. PURE mixing rules........................................................................................................... 118
Simulis

______________________________________________________________________________________

9.3.2. CLASSIC mixing rules ..................................................................................................... 118
9.3.3. ELY-HANLEY method (TRAPP method) ......................................................................... 118
9.3.4. EZRA K. T. KAM method.................................................................................................121
9.3.5. PETRO method............................................................................................................... 122
9.3.5.1. Hydrocarbons mixture at low pressure: Sato Riedel [REI87].................................. 122
9.3.5.2. Influence of the pressure: API 12A4.1 [API82] .......................................................... 122
9.3.5.3. Particular case: Water-hydrocarbon model................................................................ 123
9.3.6. API 12A3.2 method.......................................................................................................... 124
9.3.6.1. Hydrocarbons mixture at low pressure: API 12A3.2 [API06] ..................................... 124
9.3.6.2. Influence de la pression : API 12A4.1 [API82] ........................................................... 124
9.3.6.3. Cas particulier modle eau hydrocarbures ............................................................. 124
9.4. Vapor thermal conductivity ......................................................................................................... 125
9.4.1. PURE mixing rules.......................................................................................................... 125
9.4.2. CLASSIC mixing rules .................................................................................................... 125
9.4.2.1. Gaseous mixture at low pressure............................................................................... 125
9.4.2.2. Gaseous mixture at high pressure ............................................................................. 126
9.4.3. ELY-HANLEY method (TRAPP method) ........................................................................ 127
9.4.4. PETRO method................................................................................................................ 129
9.4.4.1. Hydrocarbon mixture at low pressure: Roy and Thodos [ROY70] ............................. 129
9.4.4.2. Influence of the pressure: Stiel and Thodos [STI64].................................................. 130
9.4.4.3. Particular case: Water-Hydrocarbons model ............................................................. 130
9.5. Surface tension........................................................................................................................... 131
9.5.1. PURE mixing rules.......................................................................................................... 131
9.5.2. CLASSIC mixing rules ..................................................................................................... 131
9.5.3. Winterfeld-Scriven-Davis mixing rule.............................................................................. 131
9.5.4. PETRO mixing rule ......................................................................................................... 132
9.5.4.1. Hydrocarbon mixture: API 10A3.1 [API82]................................................................. 132
9.5.4.2. Particular case: Water-Hydrocarbons model ............................................................. 132
10. Nomenclature-----------------------------------------------------------------------------------------------------------------------133
11. Bibliography--------------------------------------------------------------------------------------------------------------------------135

Simulis
Thermodynamics Introduction - 1
______________________________________________________________________________________

1. INTRODUCTION
Using a computer to simulate and design chemical processes requires analytical expressions to
access the main thermodynamic state variables (temperature, pressure...) and the transport
properties (viscosity, thermal conductivity, diffusion coefficient). Moreover, a major problem
encountered in chemical engineering lies in fluid phase equilibria and thermodynamics properties
(enthalpies, entropies) for multi components systems. An efficient computation system is only
able to provide reliable results when suitable models are available. Thus, an advanced system
must be able to propose a lot of estimation methods and to integrate new methods easily. These
methods are based on thermodynamic models which must be mainly selected in a concern of rigor,
reliability and validity for a maximum number of pure components and mixtures.
Equilibrium conditions in a multiphase system are formulated by equating the fugacities for
component i in each phase, which gives the following equation for a 2-phase vapor-liquid system:
( ) ( ) x P T f y P T f
L
i
V
i
, , , , = (1)
Fugacities are functions of temperature T, pressure P and composition (y is the vapor mole fraction
vector and x the liquid mole fraction vector). Phase equilibrium could be calculated using two
different methods. A first way of approaching the problem consists in applying to both phases
different models: the liquid phase fugacities are calculated from a reference state, which is
characterized by the pure component in the same conditions of physical state, temperature and
pressure, the laws of the ideal solutions being corrected by using a model of free excess enthalpy,
so called activity coefficient model (NRTL, UNIQUAC, UNIFAC). The gas phase fugacities are
calculated using an equation of state (ideal gas, SRK, PR). These methods are used to
represent the heterogeneousness of the considered system and are classically called
"heterogeneous" methods. Their application covers rather the domain of low pressures and it is
important to note that they do not satisfy the continuity existing in the critical zone between the
state vapor and the liquid state.
The second way groups the said "homogeneous" methods, which apply the same model to both
phases in presence, generally an equation of state, so insuring continuity at the critical point. The
equations of state with their classic mixing rules (SRK, PR, LKP) belong to this second category
However, the domain of application of these models is limited to non polar or few polar systems.
By integrating into the mixing rules of the equations of state the excess enthalpy models, authors
managed to combine these two approaches. This type of model is usually called combined
models, which is in fact a homogeneous approach with complex mixing rules.
It is to note that specific models were also developed for certain domains of application:
electrolytic mixtures, aqueous solutions of strong acid

Thermodynamic representation

Heterogeneous Models
(Activity coefficients)
UNIQUAC
NRTL
WILSON
MARGULES
UNIFAC

Combined Models
(Equations of state
with complex mixing
rules)
MHV1
MHV2
PSRK

Specific Models
Electrolytes
Strong Acid
Amines and acid gases
Pure water

SRK
LKP
PR
BWRS

Homogeneous Models
(Equations of state)
Simulis
______________________________________________________________________________________

1.1. Homogeneous approach (equation of state)

The expression of the fugacity for component i" is the same for each phase:

( )P z P T z f
i i i
, , = with z = x or y (2)

For a vapor-liquid equilibrium, the equilibrium constant K
i
is equal to the ratio of the liquid fugacity
coefficient divided by the vapor fugacity coefficient, as expressed below:

( )
( ) y P T
x P T
x
y
K
V
i
L
i
i
i
i
, ,
, ,
= = (3)

Also, the expression of the enthalpy for a liquid or vapor mixture is unique:

( ) ( )
( )
+ =
=
=

P
0
dP
z , T
T
h
0 P , T
*
i
h
i
z
N
1 i
z , P , T H (4)

where h
i
* is the enthalpy of the i component in the ideal gas state and the second term in the
equation (4) is the mixture enthalpy departure noted ( )
P , T
*
H H .

The fugacity coefficients of each component i" in the mixture and the enthalpy departure are then
calculated from the volumetric data of the mixture, obtained for the whole fluid zone, as a single
suitably chosen equation of state (EOS) and the use of appropriate mixing rules.

Domain of application:
OELLRICH and coll. [OEL81] discuss in their article of the use of the equations of state, with their
standard mixing rules, for the calculation of the phases equilibrium: The domain of application is
restricted to mixture of normal fluids, rare gases, nitrogen, oxygen, carbon monoxide,
hydrocarbons and derivatives. The carbon dioxide, the hydrogen sulfide, the hydrogen and
with limitations some slightly polar substances can be included

Simulis
______________________________________________________________________________________

1.2. Heterogeneous approach ( formulation)
For the chemical systems which give place to complex interactions like chemical or polar
associations, it is then advisable to distinguish the expressions in the vapor phase from those in
liquid phase for the fugacity of the component i" and the enthalpy. Considering that the non-
ideality of the mixture is mainly in the liquid phase, the vapor can be treated using one of the
Equation of State (EOS) presented before, as expressed below:

For the vapor phase :

( )P y P T y f
V
i i
V
i
, , = (5)

( )
( )
|
|
.
|
\
|
+
=
= =

P
0
dP
y , T
P
v
h
N
1 i
0 P , T
*
i
h
i
y y , P , T
V
H
(6a)
so :
( )
( )
P , T
*
H H
N
1 i
0 P , T
*
i
h
i
y y , P , T
V
H
|
.
|
\
|
+
=
= =

(6b)

For the liquid phase:

( ) ( ) P T f x P T x f
L
i i i
L
i
, , ,
0
= (7)
( )
( )
( ) x , P , T
E
h
N
1 i
P , T
L 0
i
h
i
x x , P , T
L
H +
=
=

(8)

Where h
E
is the excess enthalpy term and h
i
0L
is the enthalpy of pure liquid component i"
calculated using the following expressions:

( ) ( )
( )
T
Ln
x RT h
T
P T f Ln
RT P T h P T h
i
i
N
i
E
P
L
i
i
L
i
=
=
|
|
.
|
\
|
= =
1
2
0
2 * 0
,
0 , ,
(9)

Then vapor-liquid equilibrium constant expression is:

( ) ( )
( ) y P T
P T f x P T
K
V
i
L
i i
i
, ,
, , ,
0
=
(10)

While the calculation of the enthalpy and the equilibrium constant following the expressions (3) - (4)
require only the knowledge of the enthalpy of the ideal gas and the volumetric behavior of the
mixture in the whole fluid zone under the form of a single equation of state, the calculation of the
same property following the expressions (6) and (8) - (10) requires:
The enthalpy for each component at the ideal gas state h
i
*
(T, P=0) ;
Simulis
______________________________________________________________________________________

An EOS representing the volumetric behavior of the vapor phase;
An empirical or predictive expression for the excess free enthalpy as g
E
(T,P,x) to be
used for the calculation of the activity coefficient
i
of component i" in the mixture and
the excess enthalpy h
E
(T,P,x);
An expression for the calculation of the fugacity in the standard state f
i
0L
(the fugacity
reference is the fugacity of the component i" at the temperature of the system and at
the pressure and the composition arbitrarily chosen. As an example, the activity
coefficients for the most of the not electrolytic solutions are based on a standard state
where for every component i", f
i
0L
is the fugacity of the pure liquid at the temperature
and pressure of the system).
Among the activity coefficients models, we can quote pure analytical expressions, for example the
model of Margules (1895) and the model of Van Laar (1970), of which one of the modified forms is
interesting for the azeotropics calculations (extractive or heteroazeotropic distillation) and said near
significant representations based on physically plausible models: Scatchard and Hildebrand
[HIL70], Wilson equations [WIL64], N.R.T.L. [REN68] and UNIQUAC [ABR75], [AND78] are based
on the concept of local composition. The last three equations are considered as the most
successful with regard to a certain number of fundamental qualities:
a good validity between the experience and the calculation;
the consistency with respect to the thermodynamics laws;
a good efficiency of use which give a set of parameters so reduced as possible
a good predictive capability, especially with respect to the generalization for complex
mixtures, as well as the possibility of representing the excess functions and the mixture
molar enthalpy.

Furthermore, to mitigate the sometimes tricky handicap of the lack of indispensable experimental
data to determine the binary interaction parameters, models based on the notion of groups
contribution, derived of the model UNIFAC [FRE75], [WEI87], [GME93], [LAR87], [HOL91] are also
available.

The application field of the models based on a heterogeneous approach concerns mixtures of
components which can lead to interactions of chemical and/or polar association type in a range of
temperatures of 0 to 200C and for pressures lower than about fifteen bars.

Simulis
______________________________________________________________________________________

1.3. Combined approach (equation of state with complex mixing rules)

Both approaches previously presented allow handling successfully numerous systems both in
composition and in temperature and pressure. However, in a case as in the other one, certain
numbers of limitations do not allow to apply systematically these two approaches: treatment of the
polar component for the equations of state, low pressure levels for the - approach (classical
treatment). Therefore, certain number of researchers tried to reconcile both approaches to propose
on one hand model so "universal" as possible, while trying on the other hand to keep the
experience of several ten years in applied thermodynamics research. HURON and VIDAL [HUR79]
were the first ones to propose a formalism in which the behavior of the whole fluid zone was
treated by an equation of state for which the mixing rules were based on the use of activity
coefficient models calculation. Unfortunately this model cannot reuse as there are the existing
binaries interaction parameters used in the classical activities coefficients models. Michelsen
[MIC90a], [MIC90b] then proposed a formalism (called MHV for Modified Huron-Vidal) slightly
different from the previous one in the sense that the chosen reference state for the calculation of
the free excess enthalpy (for the mixing rules of the equation of state) is the zero pressure and not
the infinite pressure. Finally, the formulation adopted by Michelsen can be described as follows:

The thermodynamic calculation is as for a normal equation of state, what is indicated by the
following equations:

( ) ( )P z P T z z P T f
i i i
, , , , =
(11)

( ) ( ) ( )
P , T
*
o
*
i i
i
H H P , T H z z , P , T H + =

(12)

This type of mixing rules can apply only to cubic equations of state, a generalized formulation of
which is:

( )
2 2
wb ubv v
T a
b v
RT
P
+ +
= (13)

with :

u w
Van der Waals 0 0
Soave Redlich Kwong 1 0
Peng Robinson 2 -1

The b parameter of the equation of state is calculated with the classic mixing rule:

=
=
Nc
i
i i
b x b
1

Simulis
______________________________________________________________________________________

The calculation of the parameter a of the equation of state is made in the way described below.
Stating that:

( )
i i
ex
Ln x Ln RT G =

(14)

Michelsen proposed as reference state a zero pressure what leads in:

0 P
e ex
0
G mod G

Therefore:

MHV1, PSRK, NRTLPR

( )
(
(
+
=
+ =

i
i
i
e
i
i i
b
b
Ln x
RT
x P T G
q
x
, 0 ,
1

(15)

or
MHV2

( ) ( )
( )
i
i
i
e
i i i i
b
b
Ln x
RT
x P T G
x q x q

+
=
= +
, 0 ,
2 2
2 1

(16)

with
bRT
a
= and
RT b
a
i
i
i
=

As it was mentioned above, this treatment allows widening the domain of application of the two
approaches previously described. It is to note however that even if this approach is treated in a
different paragraph, it is to be classified as an approach by equation of state: only the mixing rules
for the attractive term of the equation of state are different by bringing in a model of free excess
energy. On the other hand, the fact of having chosen a zero pressure as reference pressure, allows
reusing as there are all the already existing binary interaction parameter published in the literature
for the calculation of the activity coefficients. In other words, for a given binary system, the
calculation by this formalism of a vapor-liquid equilibrium (bubble and/or dew curves for example)
has to lead to the same results as by a classic treatment. An important point to note is that a cubic
equation of state which can use a complex mixing rule with any free excess enthalpy model,
when this model is a predictive model (one of the UNIFAC version for example) the equation
of state becomes then totally predictive and is not limited any more either by the nature of
the components or by the temperature and pressure ranges.
Simulis
______________________________________________________________________________________

1.4. Specific models

Some fluids or mixture of fluids present deviations with the ideality which cannot be represented by
the classical models belonging to the approaches presented above. Specific models were thus
developed to model the thermodynamic behavior of these fluids, each of these models belonging
naturally to one of both thermodynamic approach presented previously, namely the homogeneous
approach (specific equation of state for the water for example) or the heterogeneous approach
(electrolytic models).

Simulis
Thermodynamics Equations of state - 8

______________________________________________________________________________________

2. EQUATION OF STATE

2.1. Redlich Kwong (RK)
Redlich and Kwong [RED49] proposed an improvement of the attraction term of the van der Waals
equation and they introduced a temperature dependance of the term a. Density calculations have
been improved with respect to van der Waals equation but vapor pressures remain badly
represented by this model. This equation was used a lot, in particular by Chao and Seader
[CHA61] and Grayson and Streed [GRA63] for their vapor-liquid equilibrium calculation methods.
The form of this equation is the following one:

) b V ( V
a
b V
RT
+
=

with:

=
1
T

C
C a
P
T R
a
5 . 2 2
=
C
C
P
T R
5 . 2 2
42748023 . 0 =
a
=
1
9 2
1/3
- 1

b =

b
RT
c
P
c

= 0. 08664035
RT
c
P
c

b
=
2
1/3
- 1
3

A=
a P
R
2
T
2. 5

= 0. 42748023
P
r
T
r
2. 5

B =
b P
RT

= 0. 08664035
P
r
T
r

Polynomial form

( ) 0 AB Z B B A Z Z
2 2 3
= +

with T
r
=
T
T
c
P
r
=
P
P
c

Simulis

______________________________________________________________________________________

Mixing rules

ij
a
j
y
i
y
j i
a

=
i
b
i
y
i
b

=
ij
A
j
y
i
y
j i
A

=
i
B
i
y
i
B

=
j i
a a
ij
a =

Pure component or mixture enthalpy departure ( )
P T
H H
,
*

( ) ( ) ( ) Z / B 1 Ln a
T
a
T
b
1
1 Z RT H H
P , T
*
+ |
.
|
\
|

+ =

Pure component or mixture entropy departure ( )
P T
S S
,
*

( ) ( ) ( ) Z / B 1 Ln
T
a
b
1
B Z Ln R S S
P , T
*
+

+ =

Pure component or mixture fugacity coefficient

( ) ( ) ( ) Z / B 1 Ln
B
A
B Z Ln 1 Z Ln + =

Fugacity coefficient of the component i in the mixture ( ) y P T
i
, ,

( ) ( ) ( ) Z / B 1 Ln
b
b
a
a
B
A
B Z Ln 1 Z
b
b
Ln
i i i
i
+
|
|
.
|
\
|
=

Data required (for each component)
T
c
Critical temperature
P
c
Critical pressure

Simulis

______________________________________________________________________________________

2.2. Soave Redlich Kwong (SRK)
In 1989, Abbott wrote [ABB89] The cubic equations of state using two parameters cannot
represent with a sufficient precision at the same time the volumetric behavior and the vapor
pressures. The necessity of choosing a priority is consequently imperative. Soave [SOA72] had
already understood it in 1972 and had applied the equation of state of Redlich-Kwong to the
calculation of the vapor pressures of hydrocarbons. In particular, he proposed a new formulation of
the attraction parameter a that brought in a new parameter in the cubic EOS, the Pitzer acentric
factor .
( ) b V V
a
b V
RT
P
+
=

c
2
c 2
P
T
R 42748 . 0 a =

c
c
P
T
R 08664 . 0 b =

( )( ) [ ]
2
5 . 0
r
2
T 1 176 . 0 574 . 1 480 . 0 1 + + =

2
r
r
2 2
T
P
42748 . 0
T R
P a
A =
=

r
r
T
P
08664 . 0
RT
P b
B = =

with:
c
r
c
r
P
P
P et
T
T
T = =

Polynomial form

( ) 0 AB Z B B A Z Z
2 2 3
= +

Mixing rules and binary interaction parameters k
ij

( )
=
i j
ij j i
a z z a

( ) ( ) ( ) ( )
j i ij ij
a a k a = 1

=
i
i i
b z b
Simulis

______________________________________________________________________________________

=
i j
ij j i
A z z A

( )
j i ij ij
A A k 1 A

=
i
i i
B z B

ji ij
k k = 0 k
ii
=

P T
H H
,
*

( ) ( ) ( ) Z / B 1 Ln a
T
a
T
b
1
1 Z RT H H
TP
*
+ |
.
|
\
|

+ =

P T
S S
,
*

( ) ( ) ( ) Z / B 1 Ln
T
a
b
1
B Z Ln R S S
P , T
*
+

+ =


( ) ( ) ( ) Z / B 1 Ln
B
A
B Z Ln 1 Z Ln + =

Fugacity coefficient of the component i in the mixture ( ) z P T
i
, ,

( ) ( ) ( ) ( ) Z / B 1 Ln
b
b
z a
a
2
B
A
B Z Ln 1 Z
b
b
Ln
i
j ij
i
i
i
+
)
`
=

or:
( )
( )
( )
( ) Z / B 1 Ln
b
i
b
j
z
ij
a
a
2
RT b
a
RT
b V P
Ln
RT b V b
i
ab
b V
i
b
i
Ln
j
+
=

T
c
P
c
Critical pressure
Acentric factor
Data wished for each binary i,j
k
ij
Binary interaction parameters

For good results, the binary interaction parameters (k
ij
) must be regressed using experimental
values, such as vapor-liquid equilibrium data.
Simulis

______________________________________________________________________________________

2.3. Soave Redlich Kwong Boston Mathias (SRKBM)
This EOS is based on the Soave-Redlich-Kwong [SOA72] equation formulation:

( ) b V V
a
b V
RT
P
+
=

c
2
c 2
P
T
R 42748 . 0 a =

c
c
P
T
R 08664 . 0 b =

The modification concerns the use of the alpha function proposed by Boston and Mathias for
supercritical components:

if T < T
ci
[SOA72] :
( )( ) [ ]
2
5 . 0
ri
2
i i i
T 1 176 . 0 574 . 1 480 . 0 1 + + =

if T > T
ci
[BOS80] :

( ) ( ) [ ] [ ]
2
d
ri i i
i
T 1 c exp T =

with
2
m
1 d
i
i
+ =

i
i
d
1
1 c =

2
176 . 0 574 . 1 480 . 0
i i i
m + =

T
c
P
c
Critical pressure
Acentric factor
k
ij

ij

Simulis

______________________________________________________________________________________

2.4. Soave Redlich Kwong Kabadi and Danner (SRK KD85)
The SRK equation of state [SOA72] has been modified by Kabadi and Danner [KAB85] to be
applicable to water-hydrocarbons systems for the whole phase equilibrium diagram. The difficulties
to predict the data in the liquid regions rich in hydrocarbons and those rich in water were overcome
by using an asymmetric mixing rule. A term dependent on the concentration was introduced into
the water-hydrocarbon interactions to represent the structural effects of the hydrophobic
interactions. The correlation so obtained is applicable in a wide domain of temperatures.
Its polynomial expression is as follow:

0 . ). (
2 2 3
= + B A Z B B A Z Z
with :

= =
= =
2 2
2 2
.
.
) , , (
.
). (
) , , (
T R
P b
P T x f B
T R
P a
P T x f A
i
i

( ) [ ]
+ =
= + =
2
, ,
2
. 15613 . 0 . 55171 . 1 48508 . 0
1 . 1
1 : ) (
i i i
i hyd C
ri ri i i
m
T
T
T T m
NC i n Hydrocarbo

( ) [ ]
= + =
water C
rw rw w
T
T
T T
Water
,
2
8 . 0
1 . 662 . 0 1

|
|
.
|
\
|
=
ci
2
ci
2
i
P
T . R
. 42747 . 0 a , attractive term

|
|
.
|
\
|
=
ci
ci
i
P
T . R
. 08664 . 0 b , covolume

i
ci
2
ci
2
i i i
.
P
T . R
. 42747 . 0 . a ) a (
|
|
.
|
\
|
= = , for Hydrocarbons

w
cw
2
cw
2
w w w
.
P
T . R
. 42747 . 0 . a ) a (
|
|
.
|
\
|
= = , for water

Simulis

______________________________________________________________________________________

Mixing rules and interaction parameters

=
i
i i
b x b .

) 1 ( ) .( ) ( . . ) (
ij
i j
j i j i
k a a x x a =

In order to calculate the binary interaction parameters k
ij
for water-hydrocarbons systems, Kabadi
and Danner [KAB85] proposed the following mean k
ij
corresponding to each chemical familly.

Chemical family k
ij

Alkanes 0.500
Alkenes 0.393
Dialkenes 0.311
Acetylenes 0.348
Naphthenes 0.445
Cycloalkenes 0.355
Aromatics 0.315

On the other hand, the authors assume that the total strengths related to the molecular attraction
are established on one part by the molecular attraction between the water and the hydrocarbon
and on the second part by the structural effect of the hydrocarbon on the water, or:

w wi wi iw wi
x a a a a . ' ' ) ( ) ( + = =

And therefore:

+ =
k
k w wk
i j
ij j i
x x a a x x a . . " ) .( . ) (
2

with:
) k 1 .( ) a .( ) a ( ) a (
wi i w wi
= , i : hydrocarbon and w : water

j i ij
a a a ) .( ) ( ) ( = , i, j : hydrocarbon or i, j : water

|
|
.
|
\
|
(
=
1 C
cw
k
n Hydrocarbo : k
wk
T
T
1 . G ' ' a

=
j
j i
g G

Simulis

______________________________________________________________________________________

In the expression of the secondary water-hydrocarbon energy interaction parameter:

|
|
.
|
\
|
(
=
1
1 . ' '
C
cw
i wi
T
T
G a

C
1
= 0,8

= =
= =
cw wi
i wi
a
G a
T T : 0 ' '
0 T : ' '

g
j
values for different groups are indicated in the following table :

Group j
5 6
10 . , m atm g
j

4
CH 1.3580
3
CH 0.9822

2
CH 1.0780
> CH 0.9728
Quaternary carbon 0.8687

2
CH (cyclic) 0.7488
> CH (cyclic) 0.7352
= CH CH (cyclic) 0.6180
2
2
CH CH = 1.7940
= CH CH
2
1.3450
< = C CH
2
0.9066
CH CH
2
1.6870
C CH
2
1.1811
= CH (aromatic) 0.5117
= > C (aromatic) 0.3902

T
c
Critical pressure
P
c
Critical pressure
Acentric factor
UNIFAC 93 decomposition
Chemical family

Simulis

______________________________________________________________________________________

2.5. Soave Redlich Kwong Kabadi and Danner modified by Twu and Bluck(SRK KD88)
Twu and Bluck [TWU88] proposed some improvements for the cubic equation of state SRK
[SOA72] done by Kabadi and Danner [KAB85]. The modifications concern the water-hydrocarbons
binary interaction parameters (k
iw
). The Watson factor was introduced instead of chemical familly
as well as the calculation of secondary energy interaction parameters for the interaction between
water and hydrocarbon (G
i
) with a formulation not depending on UNIFAC decomposition. This
version is more convenient than the one presented by Kabadi and Danner.

The new formulation for the water-hydrocarbon binary interaction parameters is:

>
+
<
=
13.5 Kw 0.5
13.5 Kw 10.5 Kw 0.061667 0.3325 -
10.5 Kw 315 . 0
k
iw

With:
SG
T
Kw
3
b
= Watson characterization factor

The secondary energy parameter for water-hydrocarbon interaction is:

2
0
2 1
2 1
. ln
|
|
.
|
\
|
+
=
f
f
G LnG

+ =
+ =
+ =
(R) T ) ( /
(R) T ) ( /
. .
4 3 2
2 1 1
2
2 1
b
b
T Ln C C f
T Ln C C f
SG f SG f f

1
) .( 5
0
=
SG SG
e SG

|
|
.
|
\
|
+
=
|
|
.
|
\
|
0
gv
0
6 gv
4
a
0
F N
F . a N
Ln
a
1
358 . 1 426
358 . 1 G
5

4
4
6
1
. 1
a
a
gv
e
e a
N

+
=

. 1
. 3
. 1
1
1
3 0
1
1
.
1
. 1
a
a
a
a
e a
e
e
e a
F

+
=

2 a
b
988 . 200 2000
988 . 200 T
|
.
|
\
|
=

Simulis

______________________________________________________________________________________

12 3 0
5 . 13749 . 36159 . 3 . 128624 . 0 843593 . 0 = SG

c
b
T
T
=1

13
3 10
2 7 3
0
100
9468 . 95 . 10 284376 . 0
. 10 779681 . 0 . 10 191017 . 0 533272 . 0

|
.
|
\
|
+
+ + =
b
b
b b
c
b
T
T
T T
T
T

a
1
= 0.405040 a
6
= -0.958481
a
2
= 1.99638 c
1
= -0.178530
a
3
= 34.9349 c
2
= 1.41110
a
4
= 0.507059 c
3
= 0.237806
a
5
= 1.2589 c
4
= -1.97726

Required data (for each component)
T
b
Normal boiling point
T
c
P
c
Critical pressure
Acentric factor

Simulis

______________________________________________________________________________________

2.6. Peng Robinson (PR)
Peng and Robinson [PEN76] proposed cubic equation of state formulation is as follow:

2 2
b bV 2 V
a
b V
RT
P
+
=

C
2
C
2
P
T R
45724 . 0 a =

C
C
P
RT
07780 . 0 b =

( )( ) [ ]
2
5 . 0
r
2
T 1 26992 . 0 54226 . 1 37464 . 0 1 + + =

2
r
r
2 2
T
P
45724 . 0
T R
P a
A

=
=

r
r
T
P
07780 . 0
RT
bP
B = =

with :
c
r
c
r
P
P
P et
T
T
T = =

Polynomial form

( ) ( ) ( ) 0 B B AB Z B 2 B 3 A Z B 1 Z
3 2 2 2 3
= +

ij

( )
=
i j
ij j i
a z z a
=
i
i i
b z b

=
i j
ij j i
A z z A
=
i
i i
B z B

Simulis

______________________________________________________________________________________

( ) ( ) ( ) ( )
j i ij ij
a a k 1 a =

( )
j i ij ij
A A k 1 A =

ji ij
k k = 0 k
ii
=

P T
H H
,
*

( ) ( )
( )
( )B 1 2 Z
B 1 2 Z
Ln a
T
a
T
b 2 2
1
1 Z RT H H
P , T
*

+ +
|
.
|
\
|

+ =

P T
S S
,
*

( ) ( )
B / 1 2 Z
B / 1 2 Z
Ln
T
a
b
2
B Z Ln R S S
P , T
*

+ +

+ =


( ) ( )
B / 1 2 Z
B / 1 2 Z
Ln
B 2 2
A
B Z Ln 1 Z Ln

+ +
=

Fugacity coefficient of the component i in the mixture ( ) z P T
i
, ,

( ) ( )
( )
( )B 1 2
B 1 2 Z
Ln
b
b
a z
a
2
B 2 2
A
B Z Ln 1 Z
b
b
Ln
i
j
ij i
i
i
+ +
=

T
c
P
c
Critical pressure
Acentric factor
Data wished for each binaries i,j
k
ij

ij
Simulis

______________________________________________________________________________________

2.7. Peng Robinson Boston Mathias (PRBM)
This equation is based on Peng Robinson equation formulation:

) ( ) (
) (
i i i
i
i
b v b b v v
T a
b v
RT
P
+ +
=

2
,
2
,
2
. . 457235529 . 0
i
i c
i c
i
P
T R
a =

i c
i c
i
P
RT
b
,
,
. 0777960739 . 0 =

The modification is for the alpha function proposed by Boston et Mathias [BOS80] for supercritical
components:

If T < T
ci
[PEN76]:
( )( ) [ ]
2
5 . 0
ri
2
i i i
T 1 26992 . 0 54226 . 1 37464 . 0 1 + + =

If T > T
ci
[BOS80]:
( ) ( ) [ ] [ ]
2
d
ri i i
i
T 1 c exp T =

with
2
m
1 d
i
i
+ =

i
i
d
1
1 c =

2
26992 . 0 54226 . 1 37464 . 0
i i i
m + =

ij
T
c
P
c
Critical pressure
Acentric factor
k
ij
Simulis

______________________________________________________________________________________

2.8. Peng Robinson 78 (PR78)
In 1978, Peng and Robinson [PEN78] proposed an improvement for heavy component. EOS
formulation is still identical to the original one:
) b v ( b ) b v ( v
) T ( a
b v
RT
P
i i i
i
i
+ +
=

2
i , c
i
i , c
2
i , c
2
i
T
T
1 . m 1 .
P
T R
. 457235529 . 0 a
(
(
|
|
.
|
\
|
+ =

i , c
i , c
i
P
RT
. 0777960739 . 0 b =

Improvement concerns the expression of the function m
i
for components having an Acentric factor
greater than the n-Decane Acentric factor, as expressed:

+ + = >
+ =
3
i
2
i i i i
2
i i i i
016666 . 0 164423 . 0 48503 . 1 379642 . 0 m 491 . 0
26992 . 0 54226 . 1 37464 . 0 m 491 . 0

T
c
P
c
Critical pressure
Acentric factor
k
ij

ij

Simulis

______________________________________________________________________________________

2.9. Peng Robinson 78 Boston Mathias (PR78BM)
This equation is based on the Peng-Robinson equation of state presented in the 1978s version
[PEN78]:

) ( ) (
) (
i i i
i
i
b v b b v v
T a
b v
RT
P
+ +
=

2
,
2
,
2
. . 457235529 . 0
i
i c
i c
i
P
T R
a =

i c
i c
i
P
RT
b
,
,
. 0777960739 . 0 =
The modification concerns the alpha function proposed by Boston and Mathias [BOS80] for
supercritical components:

if T < T
ci
[PEN76] :
Si
i
< 0,491
( )( ) [ ]
2
5 . 0 2
1 26992 . 0 54226 . 1 37464 . 0 1
ri i i i
T + + =
Si
i
< 0,491
( )( ) [ ]
2
5 . 0 3 2
1 016666 . 0 164423 . 0 48503 . 1 379642 . 0 1
ri i i i i
T + + + =
if T > T
ci
[BOS80] :
( ) ( ) [ ] [ ]
2
d
ri i i
i
T 1 c exp T =
with
2
m
1 d
i
i
+ =

i
i
d
1
1 c =

+ + = >
+ =
3
i
2
i i i i
2
i i i i
016666 . 0 164423 . 0 48503 . 1 379642 . 0 m 491 . 0
26992 . 0 54226 . 1 37464 . 0 m 491 . 0

T
c
P
c
Critical pressure
Acentric factor
k
ij

ij
Simulis

______________________________________________________________________________________

2.10. Predictive Peng Robinson 78 (PPR78)
This model developed by Jaubert and al. [JAU04], [JAU05], [JAU06] is a group contribution method
allowing the prediction of the binary interaction parameters (BIP, (k
ij
(T))) used in the 1978s PENG-
ROBINSON equation of state [PEN78]. Therefore this model is called PPR78 (Predictive Peng
Robinsion 1978). The important point is that the BIP k
ij
between two components i and j depends
only on the temperature (T) and on the pure components data (critical temperature (T
Ci
, T
Cj
),
critical pressure (P
Ci
, P
Cj
) and acentric factor (
i
,
j
)). That means no other parameters than those
necessary for the resolution of classical cubic equation of state (T
C
, P
C
, ) need to be provided.
Fourteen groups are available in the actual version, allowing the description of alcanes, aromatics
components, naphtenics and gases. The table of the binary interaction parameters between groups
is presented hereafter:
1 CH3
1
2 CH2
2
3 CH
3
4 C
4
5 CH4
5
6 C2H6
6
7 ACH
7
8 AC
8
9 AC POLYC
9
10 CY-CH2
10
11 CY-C
11
12 CO2
12
13 N2
13
14 H2S
No parameter
1 parameter
2 parameters
3 parameters
1.0

The formulation presented by Jaubert et al. for the BIP estimate is as follow:
j i
j i
2
j
j
i
i
Ng
k
Ng
l
1
A
B
kl jl il jk ik
ij
b . b
) T ( a ). T ( a
. 2
b
) T ( a
b
) T ( a
T
15 . 298
A ). ).( (
2
1
k
kl
kl
(
(
|
.
|
\
|
|
.
|
\
|
=
|
|
.
|
\
|

g
N Number of groups used
ik
, Fraction of molecule (i) occupied by the group (k)
ij ij
B A , Interaction parameters between groups

T
c
P
c
Critical pressure
Acentric factor
PPR78 molecules decomposition

Advice
Before making a calculation with the model PPR78, it is advisable to verify that
the decompositions of the molecules are correctly informed and that the
interactions between the groups involved in the mixture were well identified by
using the UnifacModelEditor software

Simulis

______________________________________________________________________________________

2.11. Lee Kesler
Pitzer et al. [PIT55] proposed a method based on the hypothesis that residual properties are, at a
given reduced pressure and temperature, linear function of the acentric factor. Lee and Kesler
[LEE75] have taken into account this hypothesis and published a linear interpolation of the residual
properties based on:
The simple fluid (=0), estimated with data for argon, krypton and methane
The fluid called heavy reference (=0,3978), volume and enthalpic data from n-octane
have been used

( )
( )
( ) ( )
( )
( ) ( ) 1 0 0 r
r
0
Z Z Z Z Z Z + =
+ =

Benedict Webb Rubin modified EOS [BEN40] is used for representing both fluids volumetric
properties:

|
|
.
|
\
|
|
|
.
|
\
|
+ + + + + = =
2
r
2
r
2
r
3
r
4
5
r
2
r r r
r r
V
exp
V V T
c
V
D
V
C
V
B
1
T
V P
Z

r
2
1
3
r
3
r
2
1
3
r
4
2
r
3
r
2
1
T
d
d D
T
c
T
c
c C
T
b
T
b
T
b
b B et et + = + = =

Constants Simple fluid (0) Reference fluid (r)
b
1
0.1181193 0.2026579
b
2
0.265728 0.331511
b
3
0.154790 0.027655
b
4
0.030323 0.203488
c
1
0.0236744 0.0313385
c
2
0.0186984 0.0503618
c
3
0 0.016901
c
4
0.042724 0.041577
d
1
x10
4
0.155488 0.48736
d
2
x10
4
0.623689 0.0740336
0.65392 1.226
0.060167 0.03754

(r)
= 0.3978

Simulis

______________________________________________________________________________________

Mixing rules

ci ci ci ci
P / RT Z V =

with
i ci
085 . 0 2905 . 0 Z =

=
i
cij
T
cij
V
j
z
i
z
cM
V
1
cM
T
j

=
i j
cij
V
j
z
i
z
cM
V

M cM
085 . 0 2905 . 0 Z =

cM cM cM cM
V / Z RT P =

with ( )
5 . 0
cj ci cij
T T T =

( )
3
3 / 1
cj
3 / 1
ci cij
V V
8
1
V + =

=
i
i i
z
M

Pure component fugacity coefficient

E
V 5
D
V 2
C
V
B
LnZ 1 Z Ln
5
r
2
r r
+ + + + =

(
(
|
|
.
|
\
|

|
|
.
|
\
|

+ + +
=
2
r
2
r
3
r
4
V
exp
V
1 1
T 2
c

Simulis

______________________________________________________________________________________

Pure component enthalpy departure

(
(
+ +
+ +
=
E 3
V T 5
d
V T 2
T / c 3 c
V T
T / b 3 T / b 2 b
1 T
T R
H H
5
r r
2
2
r r
2
r 3 2
r r
2
r 4 r 3 2
r
c
*

Pure component entropy departure

atm 1 P E 2
V 5
d
V 2
T / c 2 c
V
T b 2 T / b b
Z Ln
P
P
Ln
R
S S
*
5
r
1
2
r
3
r 3 1
r
3
r 4
2
r 3 1
*
= +
+ +
= |
.
|
\
|
+

Fugacity coefficient of component i" in the mixture

|
|
.
|
\
|

=
|
|
.
|
\
|
=
i j
j
z
M
Ln
j
z Ln
P z
F
Ln Ln
zk
M
i
i
i
( ) j , i k

|
|
.
|
\
|
=
M
cM cM
M
,
P
P
,
T
T
f Ln

( ) 1 Z LnZ dV
V
RT P
RT
1
Ln
M M
V
T
M
+
(

zl
j
z d
M
d
i j
Pr , Tr
M
M
Ln
k
z
j
z d
cM
P d
j
z
i j
cM
P
1
M
Z
k
z
j
z d
cM
T d
j
z
i j
cM
T R
M
H
M
Ln
i
Ln
|
|
|
.
|
\
|
|
|
.
|
\
|
|
|
|
.
|
\
|
|
|
|
.
|
\
|

=

with:
( )
( ) ( )
[ ]
o
M
r
M
r
Tr
M
M
Ln Ln
Ln

=
|
|
.
|
\
|
1
Pr ,

Using the mixing rules defined by Plcker, Knapp and Prausnitz [PLO78]:
cM
V /
cM
T
k
z
j
z d
cM
V d
cli
T
cli
V
clj
T
clj
V
l
z
l
2
k
z
j
z d
cM
T d
(
(
(
(
|
|
|
.
|
\
|
|
.
|
\
|
|
|
|
.
|
\
|
=

Simulis

______________________________________________________________________________________

( )

|
|
.
|
\
|
=
l
2
k
z
j
z d
cM
V d
cli
V
clj
V
l
z

(
(
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
+ =
cM
V /
k
z
j
z d
cM
V d
cM
T /
k
z
j
z d
cM
T d
cM
Z /
k
z
j
z d
cM
Z d
cM
P
k
z
j
z d
cM
P d

k
z
j
z d
M
d
85 . 0
k
z
j
z d
cM
Z d
|
|
.
|
\
|
|
|
.
|
\
|

=

i j
k
z
j
z d
M
d
=
|
|
.
|
\
|

Application Range

0,3 < T
r
< 4
0 < P
r
< 10

T
c
P
c
Critical pressure
Acentric factor

For good results, the binary interaction parameter (k
ij
Simulis

______________________________________________________________________________________

2.12. Lee Kesler Plcker (LKP)
Pitzer et al. [PIT55] proposed a method based on the hypothesis that residual properties are, at a
given reduced pressure and temperature, linear function of the Acentric factor. Lee and Kesler
[LEE75] have taken into account this hypothesis and published a linear interpolation of the residual
properties based on:
The simple fluid (=0), estimated with data for argon, krypton and methane
The fluid called heavy reference (=0,3978), volume and enthalpic data from n-octane
have been used

( )
( )
( ) ( )
( )
( ) ( ) 1 0 0 r
r
0
Z Z Z Z Z Z + =
+ =

Benedict Webb Rubin modified EOS [BEN40] is used for representing both fluids volumetric
properties:

|
|
.
|
\
|
|
|
.
|
\
|
+ + + + + = =
2
r
2
r
2
r
3
r
4
5
r
2
r r r
r r
V
exp
V V T
c
V
D
V
C
V
B
1
T
V P
Z

r
2
1
3
r
3
r
2
1
3
r
4
2
r
3
r
2
1
T
d
d D
T
c
T
c
c C
T
b
T
b
T
b
b B et et + = + = =

Constants Simple fluid (0) Reference fluid (r)
b
1
0.1181193 0.2026579
b
2
0.265728 0.331511
b
3
0.154790 0.027655
b
4
0.030323 0.203488
c
1
0.0236744 0.0313385
c
2
0.0186984 0.0503618
c
3
0 0.016901
c
4
0.042724 0.041577
d
1
x10
4
0.155488 0.48736
d
2
x10
4
0.623689 0.0740336
0.65392 1.226
0.060167 0.03754

(r)
= 0.3978

Simulis

______________________________________________________________________________________

The modifications made by Plcker, Knapp and Prausnitz [PLO78] on the original Lee-Kesler
equation was to introduce different mixing rules that take into account binary interaction parameters
between species.

ij

ci ci ci ci
P / RT Z V =

with
i ci
085 . 0 2905 . 0 Z =

= =
i
25 . 0
cij
T
cij
V
j
z
i
z
cM
V
1
cM
T
j

=
i j
cij
V
j
z
i
z
cM
V

M cM
085 . 0 2905 . 0 Z =

cM cM cM cM
V / Z RT P =

with ( )
ij
5 . 0
cj ci cij
k T T T = 1 k and k k
ii ji ij
= =

( )
3
3 / 1
cj
3 / 1
ci cij
V V
8
1
V + =

=
i
i i
z
M

Pure component fugacity coefficient

E
V 5
D
V 2
C
V
B
LnZ 1 Z Ln
5
r
2
r r
+ + + + =

(
(
|
|
.
|
\
|

|
|
.
|
\
|

+ + +
=
2
r
2
r
3
r
4
V
exp
V
1 1
T 2
c

Simulis

______________________________________________________________________________________


(
(
+ +
+ +
=
E 3
V T 5
d
V T 2
T / c 3 c
V T
T / b 3 T / b 2 b
1 T
T R
H H
5
r r
2
2
r r
2
r 3 2
r r
2
r 4 r 3 2
r
c
*


atm 1 P E 2
V 5
d
V 2
T / c 2 c
V
T b 2 T / b b
Z Ln
P
P
Ln
R
S S
*
5
r
1
2
r
3
r 3 1
r
3
r 4
2
r 3 1
*
= +
+ +
= |
.
|
\
|
+

Fugacity coefficient of component i" in the mixture

|
|
.
|
\
|

=
|
|
.
|
\
|
=
i j
j
z
M
Ln
j
z Ln
P z
F
Ln Ln
zk
M
i
i
i
( ) j , i k

|
|
.
|
\
|
=
M
cM cM
M
,
P
P
,
T
T
f Ln

( ) 1 Z LnZ dV
V
RT P
RT
1
Ln
M M
V
T
M
+
(

zl
j
z d
M
d
i j
Pr , Tr
M
M
Ln
k
z
j
z d
cM
P d
j
z
i j
cM
P
1
M
Z
k
z
j
z d
cM
T d
j
z
i j
cM
T R
M
H
M
Ln
i
Ln
|
|
|
.
|
\
|
|
|
.
|
\
|
|
|
|
.
|
\
|
|
|
|
.
|
\
|

=

with:
( )
( ) ( )
[ ]
o
M
r
M
r
Tr
M
M
Ln Ln
Ln

=
|
|
.
|
\
|
1
Pr ,

Using the mixing rules defined by Plcker, Knapp and Prausnitz [PLO78]:

=
(
(
(
(
|
|
|
.
|
\
|
|
.
|
\
|
|
|
|
.
|
\
|
cM
V /
cM
T
k
z
j
z d
cM
V d
1
cM
V
cli
T
cli
V
clj
T
clj
V
l
z
l
2
k
z
j
z d
cM
T d

Simulis

______________________________________________________________________________________

( )

|
|
.
|
\
|
=
l
2
k
z
j
z d
cM
V d
cli
V
clj
V
l
z

(
(
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
+ =
cM
V /
k
z
j
z d
cM
V d
cM
T /
k
z
j
z d
cM
T d
cM
Z /
k
z
j
z d
cM
Z d
cM
P
k
z
j
z d
cM
P d

k
z
j
z d
M
d
85 . 0
k
z
j
z d
cM
Z d
|
|
.
|
\
|
|
|
.
|
\
|

=

i j
k
z
j
z d
M
d
=
|
|
.
|
\
|

Application Range

0,3 < T
r
< 4
0 < P
r
< 10

T
c
P
c
Critical pressure
Acentric factor
k
ij
Binaries interaction parameters

For good results, the binary interaction parameter (k
ij
Simulis

______________________________________________________________________________________

2.13. Benedict Webb Rubbin modified Starling Nishiumi (BWRS)
The Benedict Webb Rubbin equation of state has been generally used to allow the interpolation
or the smoothing of experimental results related to the volumetric behavior of light hydrocarbons.
Starling [STA71], [STA72] proposed a reduced coordinates equation with parameters depending
only on critical coordinates and Acentric factor. The extension proposed by Nishiumi [NIS75],
[NIS77], [NIS80], [NIS83] allows extending the application field to heavier hydrocarbons and to
mixtures containing hydrogen.

( )
( )
2
e 1 T
T
h
T
g
T
c
T
f
T
e
T
d
a
T
f
T
e
T
d
a bRT
T
E
T
D
T
C
A RT B RT P
2 3
S
17 8 2
6
23 4
3
23 4
2
4
E 0
3
0
2
0
A 0 0

+ |
.
|
\
|
+ + + + |
.
|
\
|
+ + + +
|
.
|
\
|
+ |
.
|
\
| +
+ + + =

with: A
0
, B
0
, C
0
, D
0
, E
0
,
A
,
E
, a, b, c, d, e, f, g, h, , coefficients calculated from mixing
rules and pure components coefficients

1 1 1 0
B A B
i ci
+ =
i i ci
B A
7 7
3
+ =
3
2 2
0
095 . 0
i i
ci
i ci
B A
RT
A

+ + =
i 8 8
3
ci
i
2
ci
B A
RT
c
+ =

i 3 3
3
ci
i 0 ci
B A
RT
C
+ =

i 9 9
4
ci
i 0 ci
B A
RT
D
+ =

i 4 4 i
2
ci
B A + =
i 10 10
2
ci
i ci
B A
RT
d
+ =

i i ci
B A b
5 5
2
+ =
i 8 . 3
i 11 11
5
ci
i 0 ci
e B A
RT
E

+ =

i 6 6
ci
i
2
ci
B A
RT
a
+ =

2
i
12 i 12
F E
12
2
i 12 i 12 12
5
ci
i
2
ci
e D C B A
RT
e +
+ + + =

2
i
13 i 13
F E
13
2
i 13 i 13 13
24
ci
i
2
ci
e D C B A
RT
f +
+ + + =

i 14
i
i E
14 i 14 14
9
c
i
2
c
e D B A
RT
g

+ + =

Simulis

______________________________________________________________________________________

i 14
i
i E
14 i 14 14
9
c
i
2
c
e D B A
RT
g

+ + =

i 15
i
i E
15 i 15 15
18
c
i
2
c
e D B A
RT
h

+ + =

*
A
c
A c
i
i
i i
RT
=

*
E
5
c
E c
i
i
i i
RT
=

*
3
3
2
c
S
R
S
i i
=

*
1
S
c
3
2
c
S
RT
S
i
2
i
i i
=

i
2
i
i i S
1
3 S
T
S
S + =

i A
i
B
i
C
i
D
i
E
i
F
i
1 0.443690 0.115449
2 1.29438 -0.920731
3 0.356306 1.70871
4 0.544979 -0.270896
5 0.528629 0.349261
6 0.484011 0.754130
7 0.0705233 -0.044448
8 0.504087 1.32245
9 0.0307452 0.179433
10 0.0732828 0.463492
11 0.006450 -0.022143
12 0.00465593 -0.030793 0.0558125 -0.00340721 -7.72753 -45.3152
13 0.697.10
-13
8.08.10
-13
-16.10
-13
0.363078.10
-13
30.9009 -283.680
14 0.000022 -0.0001065 0.0000109 -26.024
15 -2.4.10
-11
11.8.10
-11
-2.05.10
-11
-21.52

For hydrogen:
A
*
= - 0. 39

E
*
= - 0. 0265

S
3
*
= - 0. 39

S
1
*
= - 0. 0711

S
2
= 4.247

Simulis

______________________________________________________________________________________

ij

=
i j
ij 0 0
A
j
z
i
z A
=
i j
ij 0 0
B
j
z
i
z B
=
i j
ij 0 0
C
j
z
i
z C
=
i j
ij 0 0
D
j
z
i
z D
=
i j
ij 0 0
E
j
z
i
z E
=
i j
Aij A
j
z
i
z
=
i j
Eij E
j
z
i
z
ij 1 1 0 c
B A B
ij ij
+ =
3
ij ij 2 2
c
0 c
095 . 0 B A
RT
A
ij
ij ij
+ + =

ij 3 3
3
c
0 c
B A
RT
C
ij
ij ij
+ =

ij 9 9
4
c
0 c
B A
RT
D
ij
ij ij
+ =

ij
ij
ij ij 8 . 3
ij 11 11
5
c
0 c
e B A
RT
E

+ =

*
A
c
A c
ij
ij
ij ij
RT
=

*
E
5
c
E c
ij
ij
ij ij
RT
=

With :
( )( )
2 / 1
c c ij c
i i ij
T T k 1 T =
3
3 / 1
c
3 / 1
c
c
2
i i
ij

|
|
.
|
\
|
+
=
2
j i
ij
+
=

2
*
A
*
A
*
A
j i
ij
+
=
2
*
E
*
E
*
E
j i
ij
+
=

3
3 / 1
i
i
a
i
z a
(
(
=

3
3 / 1
i
i
b
i
z b
(
(
=

3
3 / 1
i
i
c
i
z c
(
(
=

3
3 / 1
i
i
d
i
z d
(
(
=

Simulis

______________________________________________________________________________________

3
3 / 1
i
i
e
i
z e
(
(
=

3
3 / 1
i
i
f
i
z f
(
(
=
i
i
g
i
z g
=
i
i
h
i
z h
=
i
i
s i
z
s

3
3 / 1
i
i i
z
(
(
=

2
2 / 1
i
i i
z
(
(
=

kij = kji kii = kjj = 0

( ) ( )
( )
( )
|
.
|
\
|
+
+
|
|
.
|
\
|
|
.
|
\
|
+
+
|
|
.
|
\
|
|
|
.
|
\
|

+
|
.
|
\
|
+ + + + |
.
|
\
|
+
|
.
|
\
| +
+ + =

2
2 2
e 8 18 18
T
h
e
2
7
9 9
T
g
e
2
3 3
T
c
T 5
f 29
T
e 2
T 5
d 7
a
5
6
T
f 13
T 2
e 7
T
d 2
a
2
3
bRT
T
E 6
T
D 5
T
C 4
A 2 RT B H H
4 2 2
17
4 2 2
8
4 2
2
2
5
23 4
2
23 4
4
E 0
3
0
2
0
A 0 0 P , T
*

( ) ( )
( )
|
|
.
|
\
|
|
|
.
|
\
|

+ |
.
|
\
|
+ +
|
.
|
\
|
+ +
|
.
|
\
|
+ + + |
.
|
\
| +
+ + =

2
e
2
1 1
T
h 17
T
g 8
T
c 2 1
T
f 23
T
e 4
T
d
5
T
f 23
T
e 4
T
d
bR
2
1
T
E 4
T
D 3
T
C 2
R B RT Ln R S S
2
S
18 9 3
5
24 5 2
2
24 5 2 5
E 0
4
0
3
0
0 P , T
*

( ) ( )
|
|
.
|
\
|
|
|
.
|
\
|

|
.
|
\
|
+ + +
+
|
.
|
\
|
+ + +
+ |
.
|
\
|
+
|
.
|
\
| +
+ + + =

2
e
2
1 1 T
T
h
T
9
T
c 1
T
f
T
e
T
d
a
5
6
T
f
T
e
T
d
a bRT
2
3
T
E
T
D
T
C
A RT B 2 RT ln RT f ln RT
4 2
2
S
17 8 2
5
23 4
2
23 4
4
E 0
3
0
2
0
A 0 0

Simulis

______________________________________________________________________________________

Fugacity coefficient of the component i in the mixture

( ) ( )
( ) ( )
( ) ( ) ( )
( )
|
|
.
|
\
|

|
.
|
\
|
+ +
|
|
.
|
\
|
+ + +
|
|
.
|
\
|

|
|
.
|
\
|
+
|
|
|
|
.
|
\
|
+ +
+
+
+
+
|
.
|
\
|
+
|
|
|
|
|
.
|
\
|
|
|
.
|
\
|
+ + + |
.
|
\
|
+
|
|
|
|
.
|
\
|
|
.
|
\
|
+
|
.
|
\
|
+
|
.
|
\
|
+ |
.
|
\
|
+
|
|
.
|
\
|
+
|
|
.
|
\
| +
+ + + =

2
e
4
2
1
2
1 1
2 / 3
2 / 1
i
S
T
17
T
h
8
T
g
2
T
c
2
2
e
2
1
2
1
2
1
S
2
Si
T
17
T
h 2
i
h
8
T
g 2
i
g
2
T
3 / 1
i
c
2
c 3
2
23
T
f
4
T
E
T
d
a
3 / 1
i
2
23
T
3 / 1
i
f
2
f
4
T
3 / 1
i
e
2
e
T
3 / 1
i
d
2
d
3 / 1
i
a
2
a
5
5
3
T
f f
T
e e
T
d d
a a
3 / 1
b b RT
2
3
T
E
T
D
T
C
A RT B
j
z
j
2
i
RTz ln RT
i
f ln RT
23
3 / 1
i
2
4
3 / 1
i
2
3 / 1
i
2
3 / 1
i
2
i
2 2
4
Eij ij 0
3
ij 0
2
ij 0
Aij ij 0 ij 0

Isobar calorific capacity

T
T
P
T
P
T
T
*
H H
T
*
H H
*
p
C
p
C
|
|
.
|
\
|
|
|
.
|
\
|
|
|
|
|
.
|
\
|
|
.
|
\
|

|
|
|
|
.
|
\
|
|
.
|
\
|

=
with :

( ) ( )
( )
|
.
|
\
|
+
|
|
.
|
\
|
|
|
.
|
\
|

|
|
.
|
\
|
|
|
.
|
\
|

|
.
|
\
|
+
|
.
|
\
|
+ + + + |
.
|
\
| +
+ + =
|
|
.
|
\
|
2 2
2
e 8 18 18
T
h 17
e
2
7
9 9
T
g 8
e
2
3 3
T
C 2
T
f
5
667
T
e 8
T
d
5
7
T
f 299
T
e 14
T
d 2
bR
T
E 24
T
D 15
T
C 8
R B
T
H H
4 2 2
18
4 2
2
9
4 2
2
3
5
24 5 2
2
24 5 2 5
E 0
4
0
3
0
0
*

( )
( )
( )
( )
2
2 2
e 10 10
T
h 2
e
2
11
2
11
T
g 2
e
2
5
2
5
T
C 2
T 5
f 29
T
e 2
T 5
d 7
a
5
6
5
T
f 13
T 2
e 7
T
d 2
a
2
3
bRT 2
T
E 6
T
D 5
T
C 4
A 2 R B
H H
4 2 2
17
4 2 2
8
4 2 2
2
4
23 4 23 4
4
E 0
3
0
2
0
A 0 0
T
*

+ +
|
.
|
\
|
+ + |
.
|
\
|
+ +
|
.
|
\
|
+ + + +
|
.
|
\
|
+
|
.
|
\
| +
+ + =
|
|
.
|
\
|

Simulis

______________________________________________________________________________________

( )
( )
2
e 1
T
h 17
T
g 8
T
C 2
T
f 23
T
e 4
T
d
T
f 23
T
e 4
T
d
bR
T
E 4
T
D 3
T
C 2
R B R
T
P
2 3
S
18 9 3
6
24 5 2
3
24 5 2
2
5
E 0
4
0
3
0
0

+
|
.
|
\
|
+ +
|
.
|
\
|
+
|
.
|
\
|
+ + + + |
.
|
\
| +
+ + + =
|
.
|
\
|

( )
( )
2
e 2 3 3 T
T
h
T
g
T
c
T
f
T
e
T
d
a 6
T
f
T
e
T
d
a bRT 3
T
E
T
D
T
C
A RT B 2 RT
P
2 4 2 2
S
17 8 2
5
23 4
2
23 4 4
0
3
0
2
0
A 0 0
T

+ |
.
|
\
|
+ + + + |
.
|
\
|
+ + +
|
.
|
\
|
+ |
.
|
\
|
+ + + =
|
|
.
|
\
|

T
c
P
c
Critical pressure
Z
c
Critical compressibility factor
c
Critical molar density
Acentric factor
k
ij

ij

Simulis

______________________________________________________________________________________

2.14. Nakamura
This equation of state [NAK76] is based on the "hard sphere" approximation (Perturbed-hard-
sphere) and is based on the equation of Carnahan and Starling [CAR72]. The formulation proposed
by Nakamura is as follow:

( )
( ) c
a
1
1 RT
P
3
3 2
+
(
(

+ +
=
with:
: Reduced density, defined as
=
b
4

c : Adjustment parameter

The parameter b represents the size of the hard sphere and the parameter a describes the
attraction strength between molecules. These parameters have the same meaning than
parameters a and b of the Van der Waals equation, the Nakamura equation being a modern
version of the Van der Waals theory of fluids. These two parameters characterize the equation of
state and depends on the temperature. The formulations used are as follow:

T
a

+ =

( ) T b log =

The parameters , , and are the characteristic parameters of the equation of state and
correspond to empirical constants.

Mixing rules

With the aim of spreading the equation to gas mixtures, the formulation of the equation of state
presented above is preserved but the constants depend then on the composition in phase gas. The
mixing rules used for the various terms of the equation are presented below.

=
=
Nc
1 i
i i m
b y b

=
=
Nc
1 i
i i m
c y c

Simulis

______________________________________________________________________________________

= =
=
Nc
1 i
Nc
1 j
ij j i m
a y y a

T
a
ij
ij ij

+ =

Constants
ij
and
ij
represent the intermolecular attraction forces between molecules i and j.
These terms are calculated from constants relatives to each pure component with following rules:

j i ij
=

j i ij
=

Fugacity coefficient calculation

( ) ( )
( ) z ln
2
1
c
ln
RT
c a
+
c
1
a y
RT
2
1
2 4
b
b
1
3 4
ln
m
2
i m
m
Nc
1 j
ij j
3
2
m
i
2
2
i

+
|
|
.
|
\
|
+
)
`

|
|
.
|
\
|
+

=

=

Enthalpy departure calculation

( )
( )
( )
( ) 1 z
c
1
T
y y
a
RT
1
1
2 4
b y 10 ln
b
T
RT
H H
m
Nc
1 i
Nc
1 j
ij j i
m
3
2 Nc
1 i
i i i
m
*

)
`

)
`
= =
=


Characteristic parameters of the equation of state

Simulis
Thermodynamics Activity coefficients models calculation- 40

______________________________________________________________________________________

3. ACTIVITY COEFFICIENTS MODELS CALCULATION
3.1. Margules
Margules [MAR95] proposed an empirical correlation for the calculation of the binary mixture
activity coefficients, which is difficult to extend to a multi-components mixture.

|
.
|
\
|
|
.
|
\
|
=
RT
G
RT
G
Ln
i
x
i
2

with ( )
klm
A
m
x
l
x
k
x
n
l m
n
k l
n
k
lk
A
l
x
k
x
k l
n l
n
k
RT
G

+ =
+ =
=
+
= =
=
1
1
1
2
1
2
, 1 1

( )
ml mk lm lk km kl klm
A A A A A A A + + + + + = 5 . 0

( )
ilm
A
m
x
l
x
i m
n l m
i l
n l
li
A
l
x
i l
n l
i
x
il
A
l
x
i l
n l
RT
G
i
x

+ =
=
+
=
+
=
=
|
.
|
\
|
, 1 1 , 1 , 1
2
2
, 1

Required data for each binary i,j
A
ij
Binary interaction parameter

The binary interaction parameter (A
ij
) must be regressed using experimental values, such as vapor-
liquid equilibrium data.

3.2. Regular solutions: Scatchard - Hildebrand
The regular solutions theory has been introduced by Hildebrand [HIL24], [HIL70] and then by
Scatchard [SCA31]. One of the big advantages of this model is to require only the knowledge of
easily accessible data (liquid molar volumes of pure components and the solubility parameters
which can be obtained from heat of vaporization data). This model is notably used in the model
proposed by Chao and Seader [CHA61] as well as the extension of this model proposed by
Grayson and Streed [GRA63].

( )
2
0
=
i
L
i
i
RT
v
Ln
where
L
i
v
0
: molar liquid volume for the pure component i (cm3/mole)

i
: solubility parameter of the component i ((cal/cm3)
1/2
)
: mixture solubility parameter
L
i i
i
L
i i
v x
i
v x
i
0
0

i
Solubility parameter
L
i
v
0
Liquid molar volume
Simulis

______________________________________________________________________________________

3.3. Wilson and Wilson Dechema compliant
The model proposed by Wilson [WIL64] is based on the local composition concept and on Flory
theory.

kj j
x
n
j
ki k
x
n
k
ij j
x
n
j
Ln
i
Ln
=
+
|
|
|
.
|
\
|
=
=

1
1
1
1

with:
|
|
.
|
\
|
=
RT v
v
ii ij
L
i
L
j

exp
0
0

ii
=
jj
= 1

where
L
i
v
0
is the liquid molar volume of the component i

Data required

Wilson formulation:
T
T
ij ij ij
+ =
0

T
ij ij
,
0

Wilson DECHEMA compliant formulation:
( ) ( ) T
T
ii ij ii ij ii ij
+ =
0

( ) ( )
T
ii ij ii ij
,
0
L
i
v
0
Liquid molar volume of each components

Caution
It can be shown that, because of its mathematical formulation, the equation of
Wilson does not allow to represent the liquid- liquid phase splitting.

Simulis

______________________________________________________________________________________

3.4. NRTL
The NRTL equation (Non Random Two Liquids) proposed by Renon and Prausnitz [REN68] is
based on the expression of the mixture internal energy function of local compositions.

|
|
|
|
|
.
|
\
|
=
=
=
=
=
=
n
1 k
n
1 k
n
1 j
n
1 k
n
1 k
n
1 j
k
x
kj
G
kj
G
kj k
x
ij
k
x
kj
G
ij
G
j
x
k
x
ki
G
j
x
ji
G
ji
i
Ln

with:

RT
g g
ij ij
ij

=

( )
ij ij ij
G =exp

0 = =
jj ii

1 = =
jj ii
G G

0 = =
jj ii

( ) 15 . 273
0
+ = T C C g g
T
ij ij jj ij

( ) 15 . 273
0
+ = T
T
ij ij ij

C
0
ij

C
0
ji

0
ij

C
T
ij

C
T
ji

T
ij

Binary interaction parameters (BIP)

The binary interaction parameters must be regressed from experimental data, such as vapor-liquid
data or liquid-liquid data

Simulis

______________________________________________________________________________________

3.5. Modified UNIQUAC
The UNIQUAC model (UNIversal QUAsi Chemical) is based on the concept of local composition
[ABR75], [AND78]. Activities coefficients are the result of the sum of two terms, one called
combinatory, the other called residual.

R
i
C
i i
Ln Ln Ln + =

The combinatory term results from differences in sizes and shape between components. The
residual term take into account interactions between molecules.

|
|
|
|
.
|
\
|
|
.
|
\
|
+
|
|
|
.
|
\
|
+ + =

=
= = =
kj k
ij j
i
q
ji j
Ln
i
q
i
q
j
l
j
x
i
x
i
i
l
i
i
Ln
i
q
Z
i
x
i
Ln
i
Ln
n
k
n
j
n
j
n
j

'
'
' ' '
2
1
1 1 1

( ) ( ) 10 Z 1 - r q - r
2
Z
L
i i i i
= =

1
RT
u u
exp
jj ii
ii ji
ji
= =
|
|
.
|
\
|
=

j j
n
j
i i
i
j j
n
j
i i
i
x r
x r
x q
x q

= =
= =
1 1

( ) ( ) T u u u u u u
T
ii ij ii ij ii ij
+ =
0

Required data for each component
r
i
van der Waals volume
q
i
van der Waals area
( )
0
ii ij
u u
( )
0
jj ji
u uj
( )
T
ii ij
u u
( )
T
jj ji
u uj
Binary interaction parameters (BIP)

The binary interaction parameters must be regressed from experimental data, such as vapor-liquid
data or liquid-liquid data

Simulis

______________________________________________________________________________________

3.6. Original UNIFAC
The UNIFAC method has been proposed by Fredenslund and al. [FRE75] and ensues directly from
the formalism defined by Wilson and from the UNIQUAC method. Activity coefficients calculation by
this method is given by two terms, first called combinatory resulting mainly from differences in
sizes and shape between components, and the second called residual taking into account
interaction between groups.

R
i
C
i i
ln ln ln + =

Combinatory term:
=
NOC
1 j
j j
i
i
i
i
i
i
i
i C
i
l x
x
l ln q
2
z
x
ln ln
with:
) 1 r ( ) q r (
2
z
l
i i i i
= 10 = z
=
=
NOG
k
k
i
k i
R r
1

=
=
NOG
k
k
i
k i
Q q
1

=
=
NOC
j
j j
i i
i
r x
r x
1

=
=
NOC
j
j j
i i
i
q x
q x
1

Residual term:

( )
=
=
NOG
1 k
i
k k
i
k
R
i
ln ln ln
(
(
(
(
|
|
.
|
\
|
=

=
=
=
NOG
1 m
m , n
NOG
1 n
n
m , k m
k , m
NOG
1 m
m k k
ln 1 q ln
(
=
T
a
exp
m , n
m , n

=
=
NOG
1 n
n n
m m
m
X Q
X Q

= =
=
|
|
.
|
\
|

=
NOC
1 j
NOG
1 n
j
n j
NOC
1 j
j
j
m
m
x
x
X

The last third equations are also valid for the calculation of
i
k
ln , with the exception that the group
composition variable
k
is now the k group fraction in the pure fluid i.

Simulis

______________________________________________________________________________________

NOC : number of components
NOG : number of groups
xi : mole fraction of the i component in the mixture
Xi : group i mole fraction in the mixture
Z : lattice coordination number
i
k
: number of functional groups k type in the component i
a
n,m
: binary interaction parameters between groups n and m
Rk : k functional group volume parameter
Qk : k functional group surface parameter

As for other UNIFAC methods, two categories of groups are defined. First of all, the groups called
main , which correspond to a type of interaction, thus to a couple of given interaction
parameters. The group "CH2" is an example. For the majority of these main groups, subgroups
are defined. These last ones differ from some of the others by the values of the Bondi parameters
(Rk, Qk). The subgroups "CH3", "CH2, CH and C are subgroups from the main group
CH2.

The matrix of the binary interaction parameters between the groups defined in the UNIFAC original
method is supplied below. The user can consult it, even modify it, by using the UnifacModelEditor
software installed in the Simulis installation directory.

Advice
Before making a calculation with a predictive model like UNIFAC, it is advisable
to verify that the decompositions of molecules are duly informed and that the
interactions between the groups involved in the mixture were correctly identified
by using the UnifacModelEditor software

Simulis

______________________________________________________________________________________

UNIFAC original model: Available parameters

1 CH2
1
2 C=C
2
3 ACH
3
4 ACCH2
4
5 OH
5
6 CH3OH
6
7 H2O
7
8 ACOH
8
9 CH2CO
9
10 CHO
10
11 CCOO
11
12 HCOO
12
13 CH2O
13
14 CNH2
14
15 CNH
15
16 (C)3N
16
17 ACNH2
17
18 PYRIDINE
18
19 CCN
19
20 COOH
20
21 CCL
21
22 CCL2
22
23 CCL3
23
24 CCL4
24
25 ACCL
25
26 CNO2
26
27 ACNO2
27
28 CS2
28
29 CH3SH
29
30 FURFURAL
30
31 DOH
31
32 I
32
33 BR
33
34 C=-C
34
35 DMSO
35
36 ACRY
36
37 CLCC
37
38 ACF
38
39 DMF
39
40 CF2
40
41 COO
41
42 SIH2
42
43 SIO
43
44 NMP
44
45 CCLF
45
46 CON (AM)
46
47 OCCOH
47
48 CH2S
48
49 MORPH
49
50 THIOPHEN
50
51 NCO
51
55 SULFONES
No parameter
1 parameter
2 parameters
3 parameters

Simulis

______________________________________________________________________________________

3.7. UNIFAC modified Dortmund
This model [WEI87], [GME93] is a modification of the UNIFAC model proposed by Fredenslund
and al. [FRE75]. Two main modifications were brought:

Modification 1: Dependence of the binary interaction parameters with temperature
(
=
T
A
exp
m , n
m , n

2
n , m n , m n , m n , m
T c T b a A + + =

n m
a
,
,
n m
b
,
and
n m
c
,
: binary interaction parameters between groups.

Modification 2: Different evaluation of the combinatory term

(
+ =
i
i
i
i i
i
i
i
i C
i
ln 1
2
zq
x
w
1
x
w
ln ln

=
=
NOC
1 j
4 / 3
j j
4 / 3
i i
i
r x
r x
w

CH2.

The matrix of the binary interaction parameters between the groups defined in the UNIFAC
modified Dortmund is supplied below. The user can consult it, even modify it, by using the
UnifacModelEditor software installed in the Simulis installation directory.

Advice
Simulis

______________________________________________________________________________________

UNIFAC modified Dortmund: Available parameters

1 CH2
1
2 C=C
2
3 ACH
3
4 ACCH2
4
5 OH
5
6 CH3OH
6
7 H2O
7
8 ACOH
8
9 CH2CO
9
10 CHO
10
11 CCOO
11
12 HCOO
12
13 CH2O
13
14 CH2NH2
14
15 CH2NH
15
16 (C)3N
16
17 ACNH2
17
18 AR-CNC
18
19 CH2CN
19
20 COOH
20
21 CCL
21
22 CCL2
22
23 CCL3
23
24 CCL4
24
25 ACCL
25
26 CNO2
26
27 ACNO2
27
28 CS2
28
29 CH3SH
29
30 FURFURAL
30
31 DOH
31
32 I
32
33 BR
33
34 C=-C
34
35 DMSO
35
36 ACRY
36
37 CLCC
37
38 ACF
38
39 DMF
39
40 CF2
40
41 COO
41
42 CY-CH2
42
43 CY-CH2O
43
44 HCOOH
44
45 CHCL3
45
46 CY-CON-C
46
47 CON(AM)
47
48 CONR2
48
49 HCONR
49
50 ACCN
50
51 NCO
51
52 ACS
52
53 EPOXY
53
54 ANHYDRID
54
55 CARBONAT
55
56 SULFONE
56
57 AC-CHO
57
58 AC-COOH
58
59 AC-COO
59
60 OCCOH
60
61 CH2S
61
62 CYCONH-C
62
63 CY-COO-C
63
64 -O-O-
64
65 CFH
65
66 CFCL
66
67 CFCL2
67
68 CF2H
68
69 CF2CLH
69
70 CF2CL2
70
71 CF3H
71
72 CF3CL
72
73 CF4
73
74 ACETALS
74
75 ACNR2
75
76 ACNHR
76
77 FURAN
77
78 CY-C-NH
78
79 CY-C-NR
79
80 SIH2
80
81 SIO
81
82 OXIME
No parameter
1 parameter
2 parameters
3 parameters

Simulis

______________________________________________________________________________________

3.8. UNIFAC modied Lyngby (UNIFAC Larsen)
This model [LAR87] is a modification of the UNIFAC model proposed by Fredenslund and al.
[FRE75]. Two main modifications were brought:

Modification 1: Dependence of the binary interaction parameters with temperature
(
=
T
A
exp
m , n
m , n

( ) |
.
|
\
|
+ + + =
0
0
n , m 0 n , m n , m n , m
T T
T
T
ln T C T T b a A
n m
a
,
,
n m
b
,
and
n m
c
,
: binary interaction coefficients.

T
0
: 298.15 K

Modification 2: Different evaluation of the combinatory term
i
i
i
i C
i
x
w
1
x
w
ln ln + =
=
=
NOC
1 j
3 / 2
j j
3 / 2
i i
i
r x
r x
w

It is to note that this model was used by Fredenslund and al. [DAH91] as free excess enthalpy
model in the mixing rule MHV2 with the equation of state SRK [SOA72].

CH2.

The matrix of the binary interaction parameters between the groups defined in the UNIFAC
modified Larsen is supplied below. The user can consult it, even modify it, by using the
UnifacModelEditor software installed in the Simulis installation directory.

Advice
Simulis

______________________________________________________________________________________

UNIFAC modified Lyngby (UNIFAC Larsen): Available parameters

1 CH2
1
2 C=C
2
3 ACH
3
4 OH
4
5 CH3OH
5
6 H2O
6
7 CH2CO
7
8 CH=O
8
9 CCOO
9
10 CH2O
10
11 NH2
11
12 CH2NH
12
13 CH2N
13
14 ANH2
14
15 pyridine
15
16 CH2CN
16
17 COOH
17
18 CCl
18
19 CCl2
19
20 CCl3
20
21 CCl4
21
22 H2
22
23 O2
23
24 N2
24
25 CO
25
26 CO2
26
27 H2S
27
28 CH4
28
29 C2H2
29
30 C2H4
30
31 C2H6
31
32 C3H6
32
33 C3H8
33
34 C4H10
No parameter
1 parameter
2 parameters
3 parameters

Simulis

______________________________________________________________________________________

3.9. UNIFAC PSRK
This model [HOL91], [GME95], [FIS96], [CHE02], [HOR05] is a modification of the UNIFAC model
proposed by Fredenslund and al. [FRE75]. The main modification brought to the mathematical
model is the consideration of a dependence of the temperature for the binary interaction
parameters. This model was used as model of free excess enthalpy in the complex mixing rule
PSRK of the EOS SRK [SOA72].

CH2.

The matrix of the binary interaction parameters between the groups defined in the UNIFAC PSRK
is supplied below. The user can consult it, even modify it, by using the UnifacModelEditor software
installed in the Simulis installation directory.

Advice

Simulis

______________________________________________________________________________________

UNIFAC PSRK: Available parameters

1 CH2
1
2 C=C
2
3 ACH
3
4 ACCH2
4
5 OH
5
6 CH3OH
6
7 H2O
7
8 ACOH
8
9 CH2CO
9
10 CHO
10
11 CCOO
11
12 HCOO
12
13 CH2O
13
14 CNH2
14
15 CNH
15
16 (C)3N
16
17 ACNH2
17
18 PYRIDINE
18
19 CCN
19
20 COOH
20
21 CCL
21
22 CCL2
22
23 CCL3
23
24 CCL4
24
25 ACCL
25
26 CNO2
26
27 ACNO2
27
28 CS2
28
29 CH3SH
29
30 FURFURAL
30
31 DOH
31
32 I
32
33 BR
33
34 C=-C
34
35 DMSO
35
36 ACRY
36
37 CLCC
37
38 ACF
38
39 DMF
39
40 CF2
40
41 COO
41
42 SIH2
42
43 SIO
43
44 NMP
44
45 CCLF
45
46 CON (AM)
46
47 OCCOH
47
48 CH2S
48
49 MORPH
49
50 THIOPHEN
50
51 EPOXY
51
55 NH3
55
56 CO2
56
57 CH4
57
58 O2
58
59 AR
59
60 N2
60
61 H2S
61
62 H2
62
63 CO
63
65 SO2
65
66 NO
66
67 N2O
67
68 SF6
68
69 HE
69
70 NE
70
71 KR
71
72 XE
72
73 HF
73
74 HCL
74
75 HBR
75
76 HI
76
77 COS
77
78 F2
78
79 CL2
79
80 BR2
80
81 HCN
81
82 NO2
82
83 CF4
83
84 O3
84
85 CLNO
No parameter
1 parameter
2 parameters
3 parameters

Simulis

______________________________________________________________________________________

3.10. Three-phase vapor-liquid-liquid model
The calculation of fluid phase equilibria for vapor-liquid-liquid systems makes some difficulties arise
(appearance, disappearance of phases...) and generally requires the writing of specific unit
operations (Flash, Column). In order to face these problems, a specific strategy has been adopted
to calculate equilibrium constants between phases of such systems: a possible splitting of the liquid
phase is taken into account at the level of thermodynamics; it thus enables to calculate an
equilibrium constant between an overall liquid phase and a vapor phase.

The strategy developed in this approach consists in considering the liquid phase as a global entity,
the equilibrium constant being calculated between this global liquid phase and the vapor phase. As
a consequence, the equations corresponding to this global vapor-liquid balance can be written:

NC , 1 i 0 x K y
i i i
= = (1)

with: x
i
Global composition of component i in liquid phase
y
i
Composition of component i in vapor phase
K
i
Equilibrium constant of component i
NC Total number of components

If it is assumed that the liquid phase presents a demixion, the above system of equation is then
written:
NC , 1 i 0 x K y
I
i
I
i i
= = (2)

NC , 1 i 0 x K y
II
i
II
i i
= = (3)

with: x
i
I
Composition of component i in the liquid phase I
x
i
II
Composition of component i in the liquid phase II
y
i
Composition of component i in vapor phase
K
i
I
Equilibrium constant between the liquid I and the vapor phases for component i
K
i
II
Equilibrium constant between the liquid II and the vapor phases for component i

If (2) is substituted in (1), the following system of equations is then obtained:

I
i
I
i i i
x K x K = (4)

Moreover, this approach being mainly used for thermodynamic models based on activity coefficient
calculation, the system (4) becomes:

I
i
I
i i i
x x = (5)

with:
i
Activity coefficient of component i in the global liquid phase

i
I
Activity coefficient of component i in the liquid phase I

As the activity coefficient of component i in the global phase is the searched value, it is necessary
to know the activity coefficient of component i in the liquid phase i (
i
I
) and mole fraction in the
Simulis

______________________________________________________________________________________

liquid phase I of component i. These two values are obtained by solving the following system of
equation, which is an isothermal liquid-liquid flash:

Mass balance:

( ) 0 x x 1 x
II
i
I
i i
= i = 1, NC (6)

Equilibrium equation:

0 x x
II
i
II
i
I
i
I
i
= i = 1, NC (7)

Equation of summation:

= 0 x x
II
i
I
i
(8)

with: Liquid-liquid splitting rate

Thus, the resolution of this system makes it possible to obtain the searched values. After various
handling, the use of the equations (5), (6), (7) and (8) leads to the following expression:

( )
I
i
II
i
II
i
I
i
i
1

+
= (9)

From its expression, the activity coefficient of component i in the global phase takes into account a
possible splitting of the liquid phase. Obviously, if the liquid-liquid isothermal flash does not have a
solution, the coefficient
i
is obtained by using a traditional expression of activity coefficient
calculation (NRTL, UNIQUAC...).

Use:

This approach must be used with activity coefficient models and only with models that are likely to
describe a possible splitting of the liquid phase. This approach thus relates to the following models:
NRTL, UNIQUAC and UNIFAC. It is accessible as sub model of the option "activity coefficient
model".

Caution
This approach must not be used with a calculation model (flash, unit
operation) already taking into account a possible liquid phase splitting (for
example a 3-phase distillation column, a decanter, a 3-phase flash)

Simulis
Thermodynamics Standard state pure liquid fugacity- 55

______________________________________________________________________________________

4. STANDARD STATE PURE LIQUID FUGACITY
Standard state pure liquid fugacity is taken into account in calculation of phase equilibria and
thermodynamic properties when the thermodynamic approach selected is an heterogeneous
method, also called (see 1.2).

4.1. Standard
Fugacity of pure i component at temperature and pressure of the system (reference state) is here
expressed as:
( ) ( ) ( ) T P ) T ( P , T P , T f
0
i
0
i
V 0
i
L 0
i
=

where
i
0V
is the vapor fugacity coefficient of pure component i" calculated from an equation of
state at temperature T and pressure P equal to the vapor pressure P
i
0
(T). The influence of the
pressure on the fugacity of a liquid (Poynting correction) is here neglected because the application
field of this model is restricted to moderate pressure ; as for pure components vapor pressures they
are calculated from several equations which are selected at the pure components level (Antoine,
DIPPR, Lee-Kesler, Riedel-Planck-Miller,).

4.2. Standard with Poynting correction
expressed as:
( ) ( ) ( ) ( )
= T P P
RT
v
exp T P ) T ( P , T P , T f
0
i
L 0
i 0
i
0
i
V 0
i
L 0
i

where
i
0V
is the vapor fugacity coefficient of pure component i" calculated from an equation of
state at temperature T and pressure P equal to the vapor pressure P
i
0
(T). Pure components vapor
pressures are calculated from several equations which are selected at the pure components level
(Antoine, DIPPR, Lee-Kesler, Riedel-Planck-Miller).

4.3. Vapor pressure
simply expressed as:
( ) ( ) T P P T f
i
L
i
0 0
, =

Only the vapor pressures of pure components are required. They are calculated from several
equations which are selected at the pure components level (Antoine, DIPPR, Lee-Kesler, Riedel-
Planck-Miller,).

Simulis

______________________________________________________________________________________

4.4. Chao Seader
A model has been proposed by Chao and Seader [CHA61] to allow representing the phase
equilibria of systems involving hydrocarbons with light components: hydrogen, methane, nitrogen,
carbon dioxide and hydrogen sulfide. In their approach, the standard state pure liquid fugacity is
calculated as:

( ) ( ) P P T P T f
L
i
L
i
. , ,
0 0
=

with:
( ) ( ) 1 0 0
log ' log log
L L
L
i
+ =
( )
( ) ( )
r r r r r r r
r
L
P P T P T T T T T A
T
A
log log
2
9 8
2
7 6 5
3
4
2
3 2
1
0
0
+ + + + + + + + + =
( ) 6 . 0 P T log
r 14
3
r 13
r
12
r 11 10
) 1 (
L
+ + + + =

The values of the constants A
1
to A
14
used to compute the standard state pure liquid fugacity are
presented in the following table:

Simple fluid H
2
CH
4
N
2
CO
2
H
2
S
A
0
5.75748 1.96718 2.4384 2.7366 -30.061 3.0581
A
1
-3.01761 1.02972 -2.2455 -1.9818 6.141 -2.6492
A
2
-4.985 -0.054009 -0.34084 -0.51487 45.263 0.37458
A
3
2.02299 0.0005288 0.00212 0.042471 -27.303 -1.4647
A
4
0 0 -0.00223 -0.0028144 5.9152 0.45735
A
5
0.08427 0.008585 0.10486 -0.029475 0.36838 -0.95722
A
6
0.26667 0 -0.03691 0.021496 -0.67917 1.4273
A
7
-0.31138 0 0 0 0.15546 -0.50242
A
8
-0.02655 0 0 0 0 0.33859
A
9
0.02883 0 0 0 0.089563 -0.26678
A
10
-4.23893 0 0 0 0 0
A
11
8.65808 0 0 0 0 0
A
12
-1.22060 0 0 0 0 0
A
13
-3.15224 0 0 0 0 0
A
14
-0.025 0 0 0 0 0

Simulis

______________________________________________________________________________________

4.5. Grayson Streed
Grayson and Streed [GRA63] have bring some modifications to the Chao and Seader method
[CHA61] designed to represent phase equilibria of systems involving hydrocarbons with light
components: hydrogen, methane, nitrogen, carbon dioxide and hydrogen sulfide. In their model,
the standard state pure liquid fugacity is calculated as in the Chao and Seader model:

( ) ( ) P P T P T f
L
i
L
i
. , ,
0 0
=

with:
( ) ( ) 1 0 0
log ' log log
L L
L
i
+ =
( )
( ) ( )
r r r r r r r
r
L
P P T P T T T T T A
T
A
log log
2
9 8
2
7 6 5
3
4
2
3 2
1
0
0
+ + + + + + + + + =
( ) 6 . 0 P T log
r 14
3
r 13
r
12
r 11 10
) 1 (
L
+ + + + =

The values of the constants A
1
to A
14
used to compute the standard state pure liquid fugacity are
presented in the following table:

Simple fluid H
2
CH
4
N
2
CO
2
H
2
S
A
0
2.05135 1.50709 1.36822 2.7366 -30.061 3.0581
A
1
-2.10899 2.74283 -1.54831 -1.9818 6.141 -2.6492
A
2
0 -0.0211 0 -0.51487 45.263 0.37458
A
3
-0.19396 0.00011 0.02889 0.042471 -27.303 -1.4647
A
4
0.02282 0 -0.01076 -0.0028144 5.9152 0.45735
A
5
0.08852 0.008585 0.10486 -0.029475 0.36838 -0.95722
A
6
0 0 -0.02529 0.021496 -0.67917 1.4273
A
7
-0.00872 0 0 0 0.15546 -0.50242
A
8
-0.00353 0 0 0 0 0.33859
A
9
0.00203 0 0 0 0.089563 -0.26678
A
10
-4.23893 0 0 0 0 0
A
11
8.65808 0 0 0 0 0
A
12
-1.22060 0 0 0 0 0
A
13
-3.15224 0 0 0 0 0
A
14
-0.025 0 0 0 0 0

Simulis
Thermodynamics Complex mixing rules- 58

______________________________________________________________________________________

5. COMPLEX MIXING RULES
To extend the application field of equation of state to mixtures, mixing rules are required.
SolorzanoZavana [SOL96] have given some rules that must follow a mixing rule, reminded by
Gosh [GOS99]:
Simplistic in nature
Possessing not too many parameters
To be independent to the division of a component into identical subcontinents (i.e., not
suffering from Michelsen-Kistenmacher syndrome)
Satisfying the quadratic composition dependence of second virial coefficient constraint at
low density limit and that the Equation of State behaves like an activity coefficient model at
high densities
Predicting VLE of binary and multi component mixtures equally well
Capable of predicting VLE of non-polar, non-ideal and asymmetric mixtures satisfactorily
Predicting other properties like enthalpy, entropy, etc.
Capable of predicting liquid-liquid and vapor-liquid-liquid equilibria
Able to use the parameters of a model determined previously.
All the equations of state have their own mixing rules developed by their respective authors, which
are called standard mixing rules. They are presented in chapter relative to Equations of State.
Huron and Vidal [HUR79] were the first in proposing a formalism where the behavior of the whole
fluid domain was processed by an equation of state but the mixing rules used were based upon an
activity coefficient model. Unfortunately this approach did not allow for direct reuse of the binary
interaction parameters already existing for classical activity coefficient models. Michelsen then
proposed a formalism (known as MHV standing for Modified Huron-Vidal) slightly different from the
previous one since the reference state selected for calculation of excess free enthalpy (for the
mixing rules of the equation of state) is the zero pressure instead of a an infinite pressure.

Thermodynamic handling is just the same as for a normal equation of state, i.e.:

( ) ( )P z P T z z P T f
i i i
, , , , =
( ) ( ) ( )
P T o i i
i
H H P T H z z P T H
,
* *
, , , + =

This kind of mixing rules only can apply to cubic equations of state which general formulation can
be:

( )
2 2
wb ubv v
T a
b v
RT
P
+ +
=

Simulis

______________________________________________________________________________________

with:

u w
Van der Waals 0 0
Soave Redlich Kwong 1 0
Peng Robinson 2 -1

Parameter b of the equation of state is calculated with the usual mixing rule:

=
=
Nc
i
i i
b x b
1

Calculation of parameter a of the equation of state is performed following the procedure described
here. Setting:

( )
i i
ex
Ln x Ln RT G =

Michelsen proposed as reference state a pressure equal to zero, leading to:

0 P
e ex
0
G mod G

Choosing a reference pressure equal to zero makes it possible to reuse all the binary interaction
parameters previously published in the literature for the calculation of activity coefficients without
any change. That means that for a considered binary mixture, the calculation of a vapor-liquid
equilibrium (bubble and/or dew curves for instance) with this formalism must lead to the same
results as with a classical treatment. One must note that since a cubic equation of state is able
to use a complex mixing rule with any model to calculate excess free enthalpy, when this
model is a predictive one (a UNIFAC model for instance), the equation of state became then
fully predictive and its use is not anymore limited by the nature of the components neither
by the pressure or temperature domain.

These mixing rules can be used with all the cubic equations of state (see chapter Equations of
state): SRK, PR, SRKBM, PRBM, PR78, and PR78BM. One must note that if SRK or PR is
selected, the alpha function used is the function proposed by Mathias and Coppeman [MAT83]
and not the alpha functions proposed respectively by Soave or Peng and Robinson:
( ) ( ) ( ) ( )
2
3
3
2
2 1
1 1 1 1
(
+ + + =
r r r
T C T C T C T
Parameters C
1
, C
2
and C
3
are pure component parameters, regressed from vapor pressure of
components.
Note that if Tr is greater than 1 (if the mixture temperature is higher than the critical temperature of
the component), then the equation became:
( ) ( ) [ ]
2
1
1 1
r
T C T + =

Simulis

______________________________________________________________________________________

5.1. MHV1
This mixing rule has been proposed by Michelsen et al. [MIC90a], [MIC90b]. It is implicit when
solving .
( )
(
(
+
=
+ =

i
i
i
e
i
i i
b
b
Ln x
RT
x P T G
q
x
, 0 ,
1

with:
bRT
a
= and
RT b
a
i
i
i
=

5.2. MHV2
This mixing rule has been proposed by Michelsen et al. [MIC90b], [DAH90]. Obtaining requires
solving a second-degree equation. Its authors use it with the predictive activity coefficient model
based on group contribution UNIFAC Modified Lyngby, also known as UNIFAC Larsen (see
chapter Activity coefficient calculation models ) with the SRK cubic equation of state (see
chapter Equations of State ). Of course, this mixing rule can also be used with any cubic
equation of state and any activity coefficient model.
( ) ( )
( )
i
i
i
e
i i i i
b
b
Ln x
RT
x P T G
x q x q

+
=
= +
, 0 ,
2 2
2 1

with:
bRT
a
= and
RT b
a
i
i
i
=

5.3. PSRK
This mixing rule has been developed by Gmheling et al. [HOL91], [GME95], [CHE02]. These
authors use it with the predictive activity coefficient model based on group contribution UNIFAC
PSRK (see chapter Activity coefficient calculation models ) with the SRK cubic equation of state
(see chapter Equations of State ). Of course, this mixing rule can also be used with any cubic
equation of state and any activity coefficient model.

( )
(
(
+
=
+ =

i
i
i
e
i
i i
b
b
Ln x
RT
x P T G
q
x
, 0 ,
1

with:
bRT
a
= and
RT b
a
i
i
i
=

Simulis
Thermodynamics Specific thermodynamic models- 61

______________________________________________________________________________________

6. SPECIFIC THERMODYNAMIC MODELS
6.1. NBS/NRC Steam Tables (pure water)
For a faithful thermodynamic representation of water in the whole fluid range (vapor + liquid) the
equation of state of the NBS/NRC steam tables [HAA84] can be used.

This equation of state allows to link or to calculate the following thermodynamic variables:
temperature ;
pressure ;
density, molar volume, compressibility factor ;
enthalpy, entropy ;
specific heat capacity at constant pressure (Cp), specific heat capacity at constant volume
(Cv) ;
speed of sound.

Application range:
0 < T (C) < 1 000
0 < P (bar) < 10 000

The calculations of the dynamic viscosity and of the thermal conductivity are also performed from
the equations obtained from the NBS/NRC steam tables (IAPS 1975, IAPS 1977).

Simulis

______________________________________________________________________________________

6.2. Water-hydrocarbon mixtures
Classical thermodynamic models such as equations of state with their mixing rules do not allow a
satisfactory representation of the particular and complex behavior of phase equilibria in water-
hydrocarbon mixtures (here, the term hydrocarbon should be taken in its most general meaning).

For temperature and pressure conditions that are far from the critical point of the mixture and for
water compositions less than 50 % (mole fraction), the following model gives satisfactory
calculations of vapor-liquid, liquid-liquid and vapor-liquid-liquid equilibria of such systems, by taking
especially into account the particular nature of water in these mixtures.

This model consists in a particular calculation of the water equilibrium constant and in a standard
calculation of the other equilibrium constants.

Thus, for a vapor-liquid-liquid equilibrium, assuming that a pure water phase exists, the water
equilibrium constant between the vapor phase and the liquid phase rich in hydrocarbons is
calculated using the following equation:

P x
P
K
sol
water
water
0
=

0
water
P : vapor pressure of water at the temperature of the system
P : total pressure of the system
sol
x : upper limit of the water solubility in hydrocarbons. This parameter depends on the
temperature and the nature of the hydrocarbons.

In any case, the composition of water in vapor phase is systematically considered as equal to the
ratio between the vapor pressure of water and the total pressure of the system.
Due to its structure, the specific nature of this calculation can be applied with all the equation of
state available in the library (SRK, PR, ANTOINE,).
To use this option, component water must necessarily be taken from the standard database
(Identification number 1921). Note that parameters (SOLA and SOLB below) taken into account in
the calculation of solubility of water in hydrocarbons can be easily modified by the user. The
expression and the default values of these constants are the following ones:

T
SOLB
SOLA Lnx
sol
= , with T in Kelvin and x
sol
in mol/mol
SOLA = 6.25043
SOLB = 4015.303

The default values of these constants are those obtained from the water solubility curve in
kerosene from the API Data book (API Data Book fig 9A1-4, 1982).

Simulis

______________________________________________________________________________________

6.3. Association in vapor phase
The chemical formula representing a given component does not always express the degree of
complexity of thermodynamic behavior for the considered molecule. As an example, acetic acid is
usually treated as a chemical compound with the formula CH
3
COOH. But we know, and numerous
experiences have proven it, that acetic acid, either in vapor and liquid phase, exists not only in the
form of a monomer (simple molecule) but also in the form of a dimer due to an hydrogen bonding
between two molecules of acetic acid. This is called the association or dimerization phenomenon
that essentially takes place in vapor phase.
Thus, a mixture of two molecules A and B can, according to their nature, also contain the following
species: A2, B2, AB, all these species being obviously in "chemical" equilibrium. Even if, at low
pressure, according to the Le Chatelier law, the formation of a dimer is negligible, as soon as the
pressure rises, the dimerization reactions become important and can induce wide deviation of the
thermodynamic behavior with respect to ideal gas.
The thermodynamic study of these systems is then quite complex because equilibrium chemical
reaction takes place, and it has to be taken into account.
The association phenomena essentially affect carboxylic acids for which direct dimerization (dimer
formed from monomers of the same species) and/or cross dimerization (dimer formed from two
monomers of different species) occurs. The corresponding chemical reactions and the associated
equilibrium constants are defined as follows:

Direct dimerization: 2 A A2 K
A
= f(T)
2 B B2 K
B
= f(T)
Cross dimerization: A + B AB
B A AB
K K K =

The parameters involved in the calculation of the equilibrium constants depending on the
temperature have been obtained from the DECHEMA books for the following carboxylic acids (the
values given thereafter have been obtained with pressure in mmHg. The equation used for the
calculation of the equilibrium constant being defined as follows: log
10
K = A
ii
+ B
ii
/ T, with T in
Kelvin):

Species A
ii
B
ii
Formic acid -10.743 3083
Acetic acid -10.421 3166
Acrylic acid -10.843 3316 *
Propionic acid -10.843 3316
Methacrylic acid -10.100 3040 *
Butyric acid -10.100 3040
Isobutyric acid -10.100 3040 *
Valeric acid -10.005 2993 *
Hexanoic acid -9.891 2943 *
Heptanoic acid -9.807 2900
* : Estimated values

Simulis

______________________________________________________________________________________

The Coefficients for the calculation of the equilibrium constant of the cross dimerization are
obtained as follows:

( ) 2
2
10
Log
A A
A
jj ii
ij
+
+
=
2
jj ii
ij
B B
B
+
=

Converting K from mmHg
-1
to atm
-1
is obtained from:
A
iiatm
= A
ii
* Ln(10) + Ln(760) B
iiatm
= B
ii
* Ln(10)

For any calculation, taking into account of the vapor phase association phenomenon is obtained by
specifying the "Association" sub-model in the option "Equation of state".

Caution

The model association in vapor phase is only valid for low or moderate pressures (lower
than few bars). Furthermore the dimerization of a species can only be taken into account if
the component is one of the list previously given and if dimerization parameters A and B have
been given as pure component properties. In any other cases, the component is assumed to
follow ideal gas behavior.

Simulis

______________________________________________________________________________________

6.4. Formaldehyde-methanol-water systems
Formaldehyde is an important intermediate in the chemical industry. As an example, formaldehyde
is used in the trioxane production, the polymer production or adhesives synthesis Formaldehyde
is very reactive and consequently usually handled in aqueous solutions with (or without) methanol.
As formaldehyde reacts with solvents, it is not possible to consider formaldehyde as a pure
substance.
Mixtures of formaldehyde with water or with methanol are particularly complex to model since
formaldehyde reacts with both components leading to a lot of products. Consequently, the
thermodynamic model must take into account not only the molecular interactions but also the
various chemical reactions occurring. One of the most advanced thermodynamic models on this
system was proposed by the Pr. Gerd Maurer [MAU92], [MAU99], [MAU00]. The last research
works of this team were implemented in the thermodynamic library of ProSim software.
Due to its very high reactivity, formaldehyde (FA) is never prepared as a pure substance, but is
produced, stored and used in aqueous or methanolic solutions. Concentration of formaldehyde
monomer in these solutions is very low since formaldehyde is mainly chemically solved, leading to
polymers with water and methanol. These reactions greatly influence the properties of solutions
containing formaldehyde. The main reactions are the following ones:
Formation of methylene glycol (MG)

( )H O CH HO O H O CH
2 2 2
+

Formation of polyoxymethylene glycols (MG
n
)

( ) ( ) ( ) O H H O CH HO H O CH HO H O CH HO
n n 2 2 2 1 2
+ +
(n 2)

Formation of hemiformal (HF)

( ) ( ) O H H O CH O CH OH CH H O CH HO
2 2 3 3 2
+ +

Formation of polyoxymethylene hemiformals (HF
n
)

( ) ( ) ( ) OH CH H O CH O CH H O CH O CH H O CH O CH
n n 3 2 3 2 3 1 2 3
+ +
(n 2)

The model developed by Maurer can be represented as follows:

MG + Me HF + W
FA + W MG
Gas
FA + W MG
MG
n-1
+ Me MG
n
+ W
MG + Me HF + W
HF
n-1
+ HF HF
n
+ Me
FA
FA Me
Me
Mg
Mg
W
W
HF
HF
Liq
MG + Me HF + W
FA + W MG
Gas
FA + W MG
MG
n-1
+ Me MG
n
+ W
MG + Me HF + W
HF
n-1
+ HF HF
n
+ Me
FA
FA Me
Me
Mg
Mg
W
W
HF
HF
Liq

Simulis

______________________________________________________________________________________

Vapor phase can be represented as an ideal gas, but chemical reactions producing methylene
glycol and hemiformal are taken into account in this phase. Liquid phase is represented as a
complex mixture with chemical reactions between water, methanol, formaldehyde, methylene
glycol, polymethylenes glycols and the polymethylene hemiformals. The non ideality of the liquid
phase is taken into account through a UNIFAC based activity coefficient model (in its original
version [FRE75]) to which Maurer added new groups and sub-groups with corresponding Van der
Walls and interaction parameters. Equilibrium constants of the chemical reactions to be considered
are those identified by Maurer et al.. Thermodynamic equilibria are represented by the following
equation:

( ) T P x , T x P y
i
_
i i i

|
|
.
|
\
|
=

Calculation of enthalpies is also done by the method described by Maurer et al. [MAU92].

Caution

In order to keep the possibility to describe kinetic controlled reactions, chemical reactions are
not described at the thermodynamic level. Consequently, these reactions must be described
at the level of the simulation environment using the thermodynamic properties server
(ProSimPlus for instance).

Simulis

______________________________________________________________________________________

6.5. Engels
The ENGELS model [ENG90] has been especially designed for the calculation of phase equilibrium
(vapor-liquid equilibrium) and thermodynamic properties (entropy and enthalpy) of aqueous
solutions of strong acids. The modeling of this kind of mixtures proves to be particularly critical
because the following physical phenomena have to be taken into account:
o acid dissociation in the liquid phase ;
o vapor-liquid equilibrium involving numerous azeotropes (water-HCl, water-HBr, water
HNO
3
, water-H
2
SO
4
, ) ;
o significant, even very important, heat of dilution (or enthalpy of mixing).

The classical thermodynamic models do not give a satisfying modeling of this phenomenon
therefore new theories have been proposed. So, ENGELS has assumed that the dissociation of the
electrolyte leads to the formation of a complex (or several complexes) in the liquid phase, following
this equilibrium reaction (theory of the solvation of ions):

m S + E C (1)

with S : solvent (water, )
m : solvation number (number of solvent molecules which upon dissociation of one
electrolyte particle are combined in the complexes)
E : electrolyte (HCl, HNO
3
, H
2
SO
4
,)
C : complex (consisting of ion and solvent molecules)
: number of products on dissociation of one electrolyte particle

From the reaction (1), the following equilibrium constant is obtained:

K =
x
c

c
x
L

L
m
x
E

E
(2)

with x: mole fraction
: activity coefficient

Mole fractions used in the calculation of the equilibrium constant with relation (2) are mole fractions
after solvation and are linked to the real mole fractions by the following relations:
x
L
= x
0
L
+ x
C
[x
0
L
(m + 1 - ) - m] (3)

x
E
= x
0
E
+ x
C
[x
0
E
(m + 1 - ) - 1] (4)

with:
x : mole fraction after solvation
x
0
: real mole fraction

The simultaneous solving of equations (2), (3) and (4) gives the mole fractions after solvation and
then all the thermodynamic properties necessary in ProSim (activity coefficient, enthalpy, ). It is
to be noted that the activity coefficients used in equation (2) are calculated using so-called local
composition models like NRTL and/or WILSON.
Simulis

______________________________________________________________________________________

Combining an adequate solvation model with a calculation model for activity coefficients based on
the concept of local composition gives a great flexibility concerning the simultaneous fitting of
equilibrium and enthalpy data. Thus, this model is particularly suitable to the treatment of aqueous
solutions of strong acid.

In order to generalize its use and since the theory makes it possible, this model has been extended
to the following solutions:
water-strong acid-inerts ;
water-multiple strong acids. In this case, only few tests have been done and so it is
recommended to stay in the range of important water concentrations and it is also
mandatory to have the same activity coefficients model for all the acids involved in the
mixture.

An automatic treatment is then carried out to determine the number of "reactions" to calculate and
numbers of "complex reactions" to take into account. Please note that the user does not have to
specify the presence of complex at the level of the components definition neither to give the
binary interaction coefficient. Everything is automatically managed, provided that the components
used are issued from standard databases.

Studied systems:

According to the calculation of the activity coefficients, either calculated using NRTL or using
WILSON, the studied mixtures are the following ones:

calculation of the activity coefficients using WILSON method:

o water-HBr (identification number: 1906 in Standard database)
o water-HI (identification number: 1907 in Standard database)
o water-HCl (identification number: 1904 in Standard database)
o water-NaCl (identification number: 1939 in standard database)

Calculation of the activity coefficients using NRTL method:

o water-HNO
3
(identification number: 1903 in Standard database)
o water-HF (identification number: 1905 in Standard database)
o water-H
2
SO
4
(identification number: 1901 in Standard database)

Application range:

All the concentration range (except for the water-NaCl binary). It has to be noted that this model
does not take into account the presence of the Coulombic strength in the infinite dilution domain,
which may give erroneous results for low compositions of electrolytes.

Pressure: 0 to 20 bars.

Simulis

______________________________________________________________________________________

6.6. Souers
This model [SHE84] allows calculation of phase equilibria for systems including hydrogen isotopes,
i.e. n-H
2
, HD, HT, n-D
2
, DT, n-T
2
. The approach is an heterogeneous one.
The equation of state selected for the vapor phase is the Virial equation:
B
P
RT
V + =
with:
=
i
ij j i
j
B y y B
( )
2
j i
ij
B B
B
+
=
i
b
i i
T
B B

|
.
|
\
|
=
20
, 0

The standard state pure liquid fugacity is calculated using equation:
|
|
.
|
\
|
=
RT
P B
P f
i i
i i
0
0 0
exp

The activity coefficient model used is the following one:
( )
|
|
.
|
\
|
=
RT
g
x T
E
i
i
exp ,
with:
=
j
E
ij j
E
i
G A x g
=
i j
ij j i
E
A x x G
2
1

( )
(
(
|
.
|
\
|
=
6
6 . 1
2 2
74 . 14
exp 1 . 12
T
A
j i ij

0 =
ii
A
Simulis

______________________________________________________________________________________

6.7. Chao-Seader
A model has been proposed by Chao and Seader [CHA61] to allow representing phase equilibria of
systems involving hydrocarbons with light components: hydrogen, methane, nitrogen, carbon
dioxide and hydrogen sulfide. To achieve this they have in particular proposed a specific
calculation of the standard state pure liquid fugacity (see chapter Standard state pure liquid
fugacity and Enthalpy Entropy ).

Application range:
Pressure: up to 2000 psia, but the calculation pressure must remain under 80% of the critical
pressure of the mixture.
Temperature: from 100F to 500F, but the pseudo reduced temperature of the liquid phase,
based on the average (molar) of the critical temperature of the components, must
remain under 0.93.

6.8. Grayson-Streed
Grayson and Streed [GRA63] have brought some modifications to the Chao and Seader method
[CHA61] by regressing data on wider conditions range. This leads to a different set of parameters
for the calculation of the standard state pure liquid fugacity (see chapter Standard state pure liquid
fugacity and Enthalpy Entropy). In particular, specific coefficients have been regressed for
hydrogen and methane to allow the use of this model in conditions very far from the critical points
of these components.

Application range:
Pressure: up to 3000 psia, but the calculation pressure must remain under 80% of the critical
pressure of the mixture.
Temperature: from 100F to 800F, but the pseudo reduced temperature of the liquid phase,
based on the average (molar) of the critical temperature of the components, must
remain under 0.93.

6.9. MHV2
MHV2 model [DAH91] is an equation of state approach which is predictive by group contributions
based on the mixing rules of Huron and Vidal modified by Michelsen. It combines SRK equation of
state [SOA72] with a free excess energy model; the UNIFAC version modified by Lyngby (UNIFAC
Larsen) [LAR87]. MHV2 model can be used to predict vapor-liquid equilibrium but also solubility of
gases at low and high pressure. This model presents a good predictive character for a wide range
of temperature and pressure. The used function ( ) T is not the originally proposed by Soave, but
the function proposed by Mathias and Coppeman [MAT83]:

( ) ( ) ( ) ( )
2
3
3
2
2 1
1 1 1 1
(
+ + + =
r r r
T C T C T C T

C
1
, C
2
and C
3
are parameters linked to the pure components, regressed from vapor pressure of the
components.
Simulis

______________________________________________________________________________________

It is reminded that MHV2 mixing rule can be used with any free excess enthalpy model (see
chapter Complex mixing rules). Furthermore, when a predictive activity coefficient model such as
UNIFAC is used, it is recommended to check the availability of the interactions between all the
groups involved in the mixture (see chapter Activity coefficient models).

6.10. PSRK
PSRK model (Predictive Soave Redlich Kwong) [HOL91], [GME95], [FIS96], [CHE02], [HOR05]
is an equation of state approach which is predictive by group contributions based on SRK equation
of state [SOA72]. The complex mixing rule developed by Gmehling et al. is based on the concept
developed by Michelsen (see chapter Complex mixing rules). The activity coefficient model used
with this mixing rule is the UNIFAC PSRK model (see chapter Activity coefficient models) which is
regularly updated. PSRK model can be used to predict vapor-liquid equilibrium but also solubility of
gases at low and high pressure. This model presents a good predictive character for a wide range
of temperature and pressure. The used function ( ) T is not the originally proposed by Soave, but
the function proposed by Mathias and Coppeman [MAT83]:

( ) ( ) ( ) ( )
2
3
3
2
2 1
1 1 1 1
(
+ + + =
r r r
T C T C T C T

C
1
, C
2
and C
3
are parameters linked to the pure components, regressed from vapor pressure of the
components.

It is reminded that PSRK mixing rule can be used with any free excess enthalpy model (see
chapter Complex mixing rules). Furthermore, when a predictive activity coefficient model such as
UNIFAC is used, it is recommended to check the availability of the interactions between all the
groups involved in the mixture (see chapter Activity coefficient models).

Simulis

______________________________________________________________________________________

6.11. Thermodynamic models applied to electrolyte solutions
6.11.1. Introduction
This paragraph presents several thermodynamic models applied to electrolyte solution
implemented in ProSim thermodynamic library. It is important to note that for each electrolyte
model, a great number of data are required in order to well represent a given system (reactions
stoichiometry, reactions equilibrium constant, heat of formation at infinite dilution, interaction
parameters, Henrys law,). Up to now, models parameters have been set in order to allow the
modeling of numerous systems. Nevertheless, due to the diversity and to the large number of
information needed, the list of these systems can not be exhaustively made. Consequently, the
treatment of some specific electrolytic solutions may require further fitting efforts (please consult
our support).

6.11.2. Some definitions
Some important definitions to bear in mind for applying electrolyte thermodynamic models are:
Phase: The physical state of one or more chemical species.
Electrolyte: A molecular or atomic species (gaseous, liquid, or solid) which has some
solubility in a solvent and reacts with it, to some significant extent, to one or more ionic
(charged) species. CO
2
(g), and NaCl(s) are examples of electrolytes.
Non Electrolyte: A molecular or atomic species (gaseous, liquid, or solid) which has some
solubility in a solvent and remains nearly totally in the molecular form (uncharged) when
dissolved in the solvent. Ar(g) and C
6
H
14
(l) are examples of non electrolytes.
Ionic species: A species dissolved in a solvent and possessing a charge. Charged species
are either termed cations (positive charge) or anions (negative charge). Na
+
(aq) and Cl
-
(aq) are examples of ionic species.
Molecular species: A species dissolved in a solvent and having no charge. CO
2
(aq) and
FeCl
3
(aq) are examples of molecular species.
Complex, ion pair: A species composed of both cationic and anionic portions. Complexes
can be charged or uncharged. FeCl
2+
(aq) and FeCl
3
(aq) are examples of complexes.
Strong electrolyte: A molecular or atomic species which completely dissociates to its
constituent base ions, leaving virtually no uncharged molecular forms of species in a
solvent. NaCl(s) and KCl(s) at room temperature are examples of strong electrolytes.
Weak electrolyte: A molecular or atomic species which partially dissociates into a solvent
to its constituent ions, leaving a significant concentration of the molecular form and/or other
complexes.
Electrolyte equilibrium: The thermodynamic equilibrium involving species, all of which are
in the solvent phase. An example of an electrolyte equilibrium is:
CO
2
(aq) + H
2
O (aq) H
+
(aq) + HCO
3
-
(aq)

Phase equilibrium: The thermodynamic description of the physical equilibrium between a
solvent phase and one other phase. The other phase can be, among others, gaseous,
liquid, or an independent solid. An example of a phase equilibrium is.

Ar (g) Ar (aq)

Apparent species: A molecule or an atomic species defined by the user. In the system
Water-HCl, water and hydrogen chloride are so-called apparent species.
Simulis

______________________________________________________________________________________

Real species: All the species existing in the mixture, additional species with respect to the
apparent species being created through electrolytic reactions. The list of real species in the
system Eau-HCl is: H
2
O, HCl, H
+
, Cl
-
, OH
-
. It has to be noted that each apparent species
belong to the list of real species.
Molality: The usual unit of concentrations for all species in the solvent phase other than the
solvent. Molality (abbreviated m) is defined as the moles of a species in a solvent phase
per kilogram of solvent (approximately 55.508 moles for water). Molality is a more
convenient unit of concentration than other concentration units (such as molarity), in that
molality is independent of temperature.
Solvent: For aqueous systems, this refers to water.
Solute: A substance dissolved into a solvent. NaCl, present in water as Na
+
(aq) and Cl
-
(aq), is an example of solute.
Thermodynamic properties: Aqueous-phase thermodynamic properties for all species other
than the solvent are usually expressed on partial molar quantities basis. This means that
the property is expressed per mole of solution. The properties of main interest in the field of
chemical engineering are the partial molal Gibbs free energy, the enthalpy, the entropy, the
heat capacity, and the volume. Each species in solution contributes to these mixture
properties. Each of the partial molar thermodynamic properties is the sum of a standard-
state term and an excess term. Thus, the general relationship for these properties can be
expressed as follows:

P
i
= P
0
i
+ P
E
i

Where:
i P
_
any thermodynamic partial molar property
0
_
i P
Standard state property
E
i P
_
Excess property
Standard-state (term): This refers to the thermodynamic value (
0
_
i P
) at a defined state (a
given concentration, temperature, and pressure). It is very important to note that the non
ideal (excess) contribution is depending from this standard state. For electrolytes systems
in a given solvent (except for the Engels model), the standard state refers to an
hypothetical solution in which all of the species are at infinite dilution. It is quite important to
realize that in almost all of the non electrolytic models, the standard state is a continuous
function of temperature and pressure but not a function of composition. Moreover, the
difference between the sum of standard-state values for the products of chemical reaction
multiplied by their stoichiometric coefficients and the sum of standard-state values for the
reactants multiplied by their stoichiometric coefficients is related directly to the
thermodynamic equilibrium constant for the corresponding reaction.
Reference state: This is the thermodynamic value (
R
i P
_
) in a specific standard state of
25C and 1 atm. As mentioned above, the standard state is a continuous function of
temperature and pressure. That means that for any choice of temperature and pressure
there is a standard-state value. The reference state, however, refers to a specific
temperature and pressure, as noted above. One of the principal purposes for a reference
state is that this state becomes the most common condition for experimental
measurements. Compilations of experimental data for electrolytes systems are usually
providing measurements in the reference-state of the following partial molar quantities: free
energy, enthalpy, entropy, heat capacity, and volume.
Simulis

______________________________________________________________________________________

Excess (term): This measures the deviation of a partial thermodynamic property from the
standard state. This term is usually depending on temperature, pressure, and composition.
This term can be related directly to the activity, and in turn, to the activity coefficients and
concentrations of the species in question.
Activity: The activity of a species (a
i
), is a thermodynamic property of the species which
relates directly to the excess Gibbs free energy (G
E
i
). Specifically,
( )
i
E
i
_
a ln RT G =

Where:
R : ideal gas constant
T : absolute temperature
Activity coefficient: The activity coefficient of a species i, noted (y
i
), is defined as the
thermodynamic property of the species which relates directly to the activity by the following
relationship:
i i i
m a =

Where:
m
i
: the concentration of the species in units of molality.

The activity coefficient is said to conform to the asymmetric convention. The asymmetric
convention states that the activity coefficient of the species approaches unity as the
concentration of the species approaches zero (infinite dilution). This is quite different from
the more familiar symmetric convention, in which the species activity coefficient
approaches unity as the species mole fraction approaches unity.

6.11.3. Mixed solvents UNIQUAC electrolytes (UQMS)
The representation of vapor-liquid equilibrium of electrolytic solutions is a complex operation,
because it involves physico-chemical phenomena such as partial or complete dissociation of salts,
electrostatic interaction between ions, ion solvation,. The calculation is even more complex if the
liquid phase is a solvent mixture, with different dielectric characteristics. Furthermore, the presence
of dissolved salt could have an important influence on the vapor phase composition (salt effect).
For all these reasons, classical activity coefficient models (NRTL, UNIQUAC...), also called
physical models, do not represent vapor-liquid equilibrium accurately when several solvents and
several salts are involved.

The UQMS model (extended version of UNIQUAC model) has been especially developed for the
thermodynamic treatment of mixed solvent/salts solutions. It assumed that the electrolytes are
completely dissociated. The calculation of the activity coefficient using this model includes the
following elements:

- a Debye-Huckel contribution, in order to take into account the electrostatic effects of
the ions in the solution;
- a combinatorial term which takes into account the shape and size differences for the
species present;
- a residual term which takes into account the interactions between the various species
present in the mixture. It is calculated from fitted parameters, called binary interaction
parameters which, in this case, depend on the composition.

Mathematical expressions used can be consulted in the literature [SAN86].

Simulis

______________________________________________________________________________________

It has to be noted that when there is no salt involved, the UQMS model is strictly equivalent to the
UNIQUAC model.

Use

All interaction parameters for ion-solvent and salt-solvent binaries as well as all information related
to chemical/physical equilibrium are "pre-coded", it is thus not necessary to provide them. On the
other hand, binary interaction parameters between solvents must be provided in the same way as
for UNIQUAC model.

Electrolytic reactions coded up to now for this model are given in the following table:

HClH[+]+Cl[-]
NaBrNa[+]+Br[-]
H2O+CO2H[+]+HCO3[-]
HCO3[-]H[+]+CO3[2-]
NH3+HCO3[-]H2O+NH2COO[-]
H2SO4H[+]+HSO4[-]
HSO4[-]H[+]+SO4[2-]
Na2SO42Na[+]+SO4[2-]
(NH4)2SO42NH4[+]+SO4[2-]
NaClNa[+]+Cl[-]
NH4ClNH4[+]+Cl[-]
NaOHNa[+]+OH[-]
NaC2H3O2Na[+]+CH3COO[-]
CuCl2Cu[2+]+2Cl[-]

NaHCO3Na[+]+HCO3[-]
Na2CO32Na[+]+CO3[2-]
CaF2Ca[2+]+2F[-]
KClK[+]+Cl[-]
NaFNa[+]+F[-]
CaCL2Ca[2+]+2Cl[-]
KIK[+]+I[-]
NaINa[+]+I[-]
KBrK[+]+Br[-]
K2CO32K[+]+CO3[2-]
HNO3+H2OH3O[+]+NO3[-]
2HNO3H2O+NO3[-]+NO2[+]
Mg(NO3)2Mg[2+]+2NO3[-]

Mixed solvents UNIQUAC electrolytes (UQMS) Chemical reactions taken into account

Application range
According to the original publication of this model, it applies to salt concentration up to 10 mol/kg
for 1:1 salts (NaCl, KCl,...) and 6,5 mol/kg for 2:1 salts (CaCl2,...).

Simulis

______________________________________________________________________________________

6.11.4. Sour Water UNIQUAC electrolytes (UQSW)
An other electrolytic version of the UNIQUAC model is the one described in [THO96], [THO99],
[PER99]. This model has been specially developed for electrolytes in aqueous solution with
different kind of equilibria: ionic, solid-liquid and vapor-liquid. The calculation of the activity
coefficient using this model includes the following elements:

a Debye-Huckel contribution, in order to take into account the electrostatic effects of ions in
the solution.
a combinatorial term which takes into account the shape and size differences for the species
present.
a residual term that takes into account interactions between the various species present. It is
calculated from fitted parameters, called binary interaction parameters which, are
temperature dependent but not composition dependent.

E
Huckel Debye
E
sidual Re
E
ial Combinator
E
G G G G

+ + =

Combinatorial and residual terms are similar to those of the standard UNIQUAC:

Combinatorial term:

) ln(
2
) ln(
i i
i i
i i
i
E
Combin
i
x q
z
x
i
x
RT
G

=

With:

Z : = 10 (coordination number)
Xi : mole fraction
i
: volume fraction
i
: surface area fraction

=
l
l l
i i
i
r x
r x

=
l
l l
i i
i
q x
q x

Residual term:

|
|
.
|
\
|
=

k
kl k
i
i i
E
sidual Re
ln q x
RT
G

Where:
|
.
|
\
|
=
T
u u
ll kl
kl
exp

u
kl
and u
ll
are interaction parameters which are generally considered as temperature dependent:

) 15 . 298 (
0
+ = T u u u
T
kl kl kl

The combinatorial and the residual terms of the UNIQUAC excess Gibbs energy function are based
on a symmetrical activity convention. However for the Debye-Hckel electrostatic term; the
symmetrical convention is used for water but the asymmetrical convention is used for the solutes.
Simulis

______________________________________________________________________________________

Electrostatic term:

|
|
.
|
\
|
+ + =
2
) 1 ln(
4
2
2 / 1 2 / 1
3
I b
I b I b
b
A
M x
RT
G
w w
E
Huckel Debye

With:
x
w
: water mole fraction
M
w
: water molar weight
A : Debye-Huckel parameter
b : supposed to be constant and equal to 1.50 (kg mol
-1
)
1/2

I : ionic strength

In this model, weak and strong electrolytes are taken into account, unlike the former one (UQMS).

Use

All the description parameters for the chemical reactions and/or physical equilibrium are "pre-
coded" and thus are not to be provided by the user.


H2O H[+] + OH[-]
H2O + NH3 NH4[+] + OH[-]
H2O + CO2 H[+] + HCO3[-]
HCO3[-] H[+] + CO3[=]
NH3 + HCO3[-] H2O + NH2COO[-]
HCl H[+] + Cl[-]
H2SO4 H[+] + HSO4[-]
HSO4[-] H[+] + SO4[=]
Na2SO4 2Na[+] + SO4[=]
(NH4)2SO4 2NH4[+] + SO4[=]
NaCl Na[+] + Cl[-]
NH4Cl NH4[+] + Cl[-]
NaOH Na[+] + OH[-]
(NH4)2CO3 2NH4[+] + CO3[=]-
(NH4)HCO3 NH4[+] + HCO3[-]
NaHCO3 Na[+] + HCO3[-]

Na2CO3 2Na[+] + CO3[=]
Na2SO4,10H2O Na2SO4 + 10 H2O
KCl K[+] + Cl[-]
K2SO4 2K[+] + SO4[=]
HNO3 + H2OH3O[+] + NO3[-]
NaNO3 Na[+] + NO3[-]
KNO3 K[+] + NO3[-]
(NH4)NO3 NH4[+]+ NO3[-]
K2CO3 2K[+] + CO3[=]
H2O + SO2 H[+] + HSO3[-]
HSO3[-] H[+] + SO3[=]
2HSO3[-] S2O5[=] + H2O
Na2S2O5 2Na[+] + S2O5[=]
Na2S2O5,7H2O 2Na[+] + S2O5[=] + 7H2O
Na2SO3 2Na[+] + SO3[2-]
Na2SO3,7H2O 2Na[+] + SO3[2-] + 7H2O

Sour Water UNIQUAC electrolytes (UQSW) Chemical reactions taken into account
Simulis

______________________________________________________________________________________

6.11.5. Sour Water (Edwards)
The representation of the thermodynamic properties and fluid phase equilibria of aqueous solutions
of electrolytes is particularly complex due to the nature of the phenomena involved: partial or total
dissociation, acid-base reactions, volatile components, This complexity is even more obvious for
the systems H
2
O-NH
3
-CO
2
-H
2
S (known as "SOUR WATER systems) where the dissociation of
weak electrolytes (NH
3
, CO
2
,) is strongly linked to the pH value. As a matter of fact, absorption
of acid gases (H
2
S, CO
2
,) will be easier if there is ammonia in the solution. Thus, it became
necessary to develop a specific model in order to take into account the involved phenomena, as
classical models were not adapted.

The SOUR WATER model [EDW75], [BEI89], [RUM92] has been specifically developed for
thermodynamic representation of the above described solutions. This model is based on the
following concepts:
partial dissociation of electrolytes
chemical equilibrium between ions and undissociated species
physical equilibrium between the species in vapor phase (all the components except ions)
and the undissociated molecules in liquid phase
non ideal behavior of the liquid phase.

These assumptions can be represented as follows:

un-dissociated
molecules
ions
Liquid phase
Vapor phase
T
P

The model automatically takes into account all information relating to the acido-basic reactions
associated to these components.
Moreover, the SOUR WATER model enables to take into account the contribution of strong
electrolytes to the behavior of the mixture.
The SOUR WATER model also enables to take into account non condensable gases that will be
considered as chemically inert. These components are : Argon ,Nitrogen, Oxygen, Hydrogen,
Carbon monoxide, Methane, Ethane, Propane, COS
Any other component will be considered as inert and possible interactions with water will not be
taken into account.
Activity coefficient calculation is based on the Pitzer method, modified by Edwards and Maurer.

Simulis

______________________________________________________________________________________

Use



H2O H[+] + OH[-]
H2O + NH3 NH4[+] + OH[-]
H2O + CO2 H[+] + HCO3[-]
HCO3[-] H[+] + CO3[=]
H2S H[+] + HS[-]
HS[-] H[+] + S[=]
H2O + SO2 H[+] + HSO3[-]
HSO3[-] H[+] + SO3[=]
HCN H[+] + CN[-]
HCl H[+] + Cl[-]
H2SO4 H[+] + HSO4[-]
HSO4[-] H[+] + SO4[=]
DEA + H2O DEAH[+] + OH[-]
2DEA + CO2 DEAH[+] + DEACOO[-]
MEA + H2O MEAH[+] + OH[-]
2MEA + CO2 MEAH[+] + MEACOO[-]
MDEA + H2O MDEAH[+] + OH[-]
Na2SO4 2Na[+] + SO4[=]
(NH4)2SO4 2NH4[+] + SO4[=]
NaCl Na[+] + Cl[-]
NaOH Na[+] + OH[-]
CH3COOH H[+] + CH3COO[-]

(NH4)2CO3 2NH4[+] + CO3[=]
NH4HCO3 NH4[+] + HCO3[-]
Na2CO3 2Na[+] + CO3[=]
Ca(OH)2 Ca[2+] + 2OH[-]
Ca(Cl)2 Ca[2+] + 2Cl[-]
Na2SO4,10H2O 2Na[+] + SO4[=] + 10 H2O
KCl K[+] + Cl[-]
K2SO4 2K[+] + SO4[=]
CH3COONa Na[+] + CH3COO[-]
CaCO3 Ca[2+] + CO3[=]
CaSO4 Ca[2+] + SO4[=]
CaSO4,2H2O Ca[2+] + SO4[=] + 2H2O
CaHCO3[+] Ca[2+] + HCO3[-]
CaCl[+] Ca[2+] + Cl[-]
FeSO4 Fe[2+] + SO4[=]
Fe2(SO4)3 2Fe[3+] + 3SO4[=]
Fe(OH)3 Fe[3+] + 3OH[-]
Fe(OH)2 Fe[2+] + 2OH[-]
FeSO4,7H2O Fe[2+] + SO4[=] + 7H2O
Na2SO3 2Na[+] + SO3[2-]
Na2SO3,7H2O 2Na[+] + SO3[2-] + 7H2O
HI H[+] + I[-]
I2 2I[-]

Sour Water (Edwards) Chemical reactions taken into account

Application range:
Temperature: 0 to 200C.
Pressure: 100 mbars to 50 bars.
Concentration: 0 to 10 in molality (number of moles per kg of water) for dissociating species
(NH
3
, CO
2
,).

Simulis

______________________________________________________________________________________

6.11.6. ULPDHS
ULPDHS model has been developed in 1992 by ACHARD [ACH92]. It combines a term of Debye-
Hckel type with a group contribution model, based on UNIFAC equation modified by Larsen et
coll. In 19897 and is based on the solvation concept. This model has advantage over the former
ones due to its predictive aspect due to its group contribution approach.

6.11.6.1. Modified UNIFAC Larsen with solvation - ULS

The UNIFAC model is composed of two terms:
1. Combinatorial term which described size and shape influence of functional group on the non
ideality of the solution
2. Residual term which correspond to intermolecular forces
The activity coefficient,
i
SR
is given by:

R
i
C
i
SR
i
ln ln ln + =

6.11.6.1.1. Combinatorial term

It relies on the theory developed by Flory and Huggins, assuming that the mixing of several liquid
species at constant temperature is performed without any enthalpy change. The only parameters
needed are the structural parameters of the molecules r
i
and q
i
.

They are computed for each molecule by dividing it into functional groups. Each subgroup k is
characterized by two parameters, one related to the volume - R
k
and one related to the surface -
Q
k
taken in the solution; r
i
and q
i
are computed by the following relations:

=
=
NG
1 k
k
) i (
k i
R . r

and
=
=
NG
1 k
k
) i (
k i
Q . q

with:
R
k
: volume parameter of subgroup k
Q
k
: surface parameter of subgroup k
) i (
k
: number of subgroup of kind k in the molecule i

NG : total number of groups

Achard first calculated the contributions R
k
and Q
k
from the relations defined by van der Waals
(Bondi, 1968) and the crystal radius of ions available in the literature (Weast, 1973 ; Bernard and
Busnot, 1984):

17 , 15
N . r .
.
3
4
R
A
3
c
c , k

=
and
9
A
2
c
c , k
510 , 2
N . r .
. 4 Q

=

The values 15,17 and 2,5 10
9
are normalization factors. They are defined as the volume and the
area of a CH
2
group in polyethylene molecule used as reference molecule.
Simulis

______________________________________________________________________________________

The volume and area parameters calculated like this were not able to adjust the model to
experimental activity data relative to strong electrolytes. That is the reason why the author takes
into account the ions solvation phenomenon: in an aqueous solution, ions are used to be solvated
by water molecules. The group like this constituted, also called cluster influences the mobility of the
ions. This mobility in an aqueous solution is also influenced by a number of physical factors:
influence of the charge: more charged is the ion, more mobile it is
influence of the size: more voluminous is the ion, less mobile it is
influence of the temperature: mobility increases with temperature
viscosity of the medium: less viscous is the medium, more mobile is the ion

The more mobile ion is the cation H
+
for which a particular mechanism with water occurs: the
"proton jump".

The number of molecules of water fixed around the ion is named "hydration number". It is the most
important at infinite dilution. It decreases when ionic strengths increase because the bulk between
the various clusters becomes important: the hydration number vary with concentration of
electrolytes. Achard, however only takes into account fixed hydration numbers. This model
probably overestimates the number of water molecules linked in a cluster at high concentration.

Structural parameters are then computed by the following relations:

1 k c , k h , k
R . nh R R + =

and

1 k c , k h , k
Q . nh Q Q + =

with:
R
k,h
: volume parameter of group k in the hydrated reference state
Q
k,h
: surface parameter of group k in the hydrated reference state
R
k,c
: volume parameter of group k in the crystal reference state
Q
k,c
: surface parameter of group k in the crystal reference state
nh
k
: hydration number of the cluster water - ion k
R
1
: volume parameter of water (R
1
=0.92)
Q
1
: surface parameter of water (Q
1
=1.40
r
c
: crystal radius()
N
A
: Avogadro number (mol
-1
)

In the case of ions, one can speak about groups or subgroups without distinction since each ion is
a subgroup and also a group by itself.

The combinatorial term in the modified UNIFAC of Larsen et al. (1987) is given by:

i
i
i
i C
i
x
1
x
ln ln

+
|
|
.
|
\
|
=

where
=
j
3
2
j j
3
2
i i
i
r x
r x

with:
i
: volume fraction of i ( - )
x
i
: mole fraction of i ( - )
Simulis

______________________________________________________________________________________

This expression makes use of mole fractions in a reference state which does not take into account
solvation, noted as ERNH. Mole fractions in the hydrated reference state have then to be
computed.

If we consider solvation (ERH), the number of moles of water is given by:

=
w
j j w
H
w
n . nh n n

where nhj is the hydration number of species j and n
water
is the number of moles of water in ERNH.
For the other species, number of moles is identical for each reference state.

The total number of moles in ERH is:
=
w j
j j T
H
T
n . nh n n

Thus, the mole fraction expression in ERH is:

for water:
=
=
=
N
2 i
i i
N
2 i
i i w
H
w
x . nh 1
x . nh x
x

for other species:
=
N
2 i
i i
i H
i
x . nh 1
x
x

This model preserves a theoretical meaning if
H
w
x
remains positive, that means that
N
2 i
i i w
x . nh x
>0. This is the major consequence which results from the constant hydration
number.

6.11.6.1.2. Residual term

Calculation of residual activity coefficient of component i is performed by summing the contributions
of all the groups in the solution minus the sum of the contributions of the groups in their reference
state.

The residual term is given by:

( )
=
k
) i (
k k
) i (
k
R
i
ln ln . ln

with:
) i (
k
: number of group of kind k in the molecule i

k
: residual activity coefficient of group k in the solution

) i (
k
: residual activity coefficient of group k in the reference solution i

The residual term of the activity coefficient of group k is given by:
Simulis

______________________________________________________________________________________

(
(
(
|
|
.
|
\
|
=

m
p
pm p
km m
m
km m k k
ln 1 . Q ln

where
=
p
pm p
km m
m
X Q
X Q

and
=
j p
j
) j (
p
j
j
) j (
m
m
x .
x .
X

with:
m
: surface fraction of subgroup m in the solution
X
m
: mole fraction of subgroup m in the solution
km
: interaction parameters between groups k and m

The residual activity coefficient of subgroup k in the reference solution,
k
i ( )
is computed by the
same way. Summation indices k, m and p refer only to the groups present in the solution of pure i.

mn is calculated for each pair of group m/n from interaction energies between groups:

( )
(
=
(

=
RT
a
exp
RT
u u
exp
mn nn mn
mn

with:
u
mn
: energy interaction between groups m and n (K)
a
mn
: interaction parameter between groups m and n (K)
R : perfect gas constant (J.mol
-1
.K
-1
or atm.cm
3
.K
-1
.mol
-1
)
T : temperature (K)

It is important to note that u
mn
=u
nm
whereas a
nm
is different from a
mn
.

Simulis

______________________________________________________________________________________

6.11.6.2. Pitzer Debye Hckel contribution PDH -
In this expression, mole fractions are ERNH mole fractions. The activity coefficient expression of
this contribution is based on an asymmetrical convention and is given by:
(
(
(
|
|
|
|
.
|
\
|
+
+
|
|
.
|
\
|
+
|
|
.
|
\
|
=

2
1
x
2
3
x
2
1
x
2
i
2
1
x
2
i
2
1
s
PDH *
i
I . 1
I . 2 I . z
I . 1 ln .
z . 2
. A .
M
1000
ln

where
2
3
s
2
2
1
s A
T . k . D
e
.
1000
d N . . 2
3
1
A
|
|
.
|
\
|
|
.
|
\
|
=

with:
A
: Debye Hckel constant (in CGS unit system)

N
A
: Avogadro number (mol
-1
)
d
s
: density of solvent (g.cm
-3
)
e : electron charge (4.802654 10
-10
eu)
k
boltz
: Boltzman constant (1.38048 10
-16
erg.K
-1
.molecule
-1
)
D
s
: dielectric constant of the solvent
I
x
: ionic strength of the solution in mole fraction scale
: minimum distance between two opposite charge ion

A
must be expressed in the CGS system of units.

is a parameter fitted to experimental data. Pitzer (1980) and Chen et al. (1982) assume that this
parameter is constant and equal to 14,9 in mole fraction scale. In fact, its value depends on the
electrolyte.

The characterization of the non ideality of the mixture is made with an hydrated reference state for
the ULS part of the model and with a non hydrated reference state for the PDH term. Thus, it is
necessary to determine short range activity coefficient contribution with a non hydrated reference
state in order to access to the global activity coefficient.

Achard (1992) established the following inter-conversion equations:

for water:
H
w
H
w w w
x . x . =

for other species :
( )
j
nh
H
j
H
j
H
j
H
j
j j
x .
x .
x .
=
for j
water

The global activity coefficient is then computed with the following expression:

LR
i
SR
i i
ln ln ln + =

Use


Simulis

______________________________________________________________________________________


H2O H[+] + OH[-]
H2O + NH3 NH4[+] + OH[-]
H2O + CO2 H[+] + HCO3[-]
HCO3[-] H[+] + CO3[=]
H2S H[+] + HS[-]
HS[-] H[+] + S[=]
H2O + SO2 H[+] + HSO3[-]
HSO3[-] H[+] + SO3[=]
HCN H[+] + CN[-]
HCl H[+] + Cl[-]
H2SO4 H[+] + HSO4[-]
HSO4[-] H[+] + SO4[=]
Na2SO4 2Na[+] + SO4[=]
(NH4)2SO4 2NH4[+] + SO4[=]
NaCl Na[+] + Cl[-]
NaOH Na[+] + OH[-]
(NH4)2CO3 2NH4[+] + CO3[=]
(NH4)2CO3 2NH4[+] + CO3[=]

Na2CO3 2Na[+] + CO3[=]
Ca(OH)2 Ca[2+] + 2OH[-]
Ca(Cl)2 Ca[2+] + 2Cl[-]
Na2SO4,10H2O 2Na[+] + SO4[=] + 10 H2O
KCl K[+] + Cl[-]
K2SO4 2K[+] + SO4[=]
CH3COONa Na[+] + CH3COO[-]
CaCO3 Ca[2+] + CO3[=]
CaSO4 Ca[2+] + SO4[=]
CaSO4,2H2O Ca[2+] + SO4[=] + 2H2O
CaHCO3[+] Ca[2+] + HCO3[-]
CaCl[+] Ca[2+] + Cl[-]
FeSO4 Fe[2+] + SO4[=]
Fe2(SO4)3 2Fe[3+] + 3SO4[=]
Fe(OH)3 Fe[3+] + 3OH[-]
Fe(OH)2 Fe[2+] + 2OH[-]
FeSO4,7H2O Fe[2+] + SO4[=] + 7H2O
KOH K[+] + OH[-]
NaBr Na[+] + Br[-]
NaNO3 Na[+] + NO3[-]
HI H[+] + I[-]
I2 2I[-]

ULPDHS Chemical reactions taken into account
Simulis

______________________________________________________________________________________

6.11.7. Amines and acid gases
Aqueous solutions of Alkanolamines are widely used in absorption / stripping operations to remove
acid gases, primarily hydrogen sulfide (H
2
S) and carbon dioxide (CO
2
), from a variety of source
gases. Deshmuk and Mather [DES81] developed a thermodynamic model dedicated to this kind of
mixtures. Weiland et al. [WEI93] fitted this model to numerous public phase-equilibrium data for
CO
2
and H
2
S in aqueous solutions of monoethanolamine, diethanolamine, diglycolamine and N-
methyldiethanolamine, which has been implemented in ProSim Thermodynamics Library.

In the system H2S-CO2-amine-water, the following 12 species are supposed to exist in solution:

H
2
S, HS
-
, S
2-
, CO
2
, HCO
3
-
, CO
3
2-
, RRRNCOO
-
, RRRN, RRRNH
+
, H
2
O, H
+
and OH
-
.

Here, RRRN represents the amine and the R, R and R groups may be mobile protons or
hydrocarbon groups depending on the amine in question. Below are the equilibrium chemical
reactions relevant to acid-gas alkanolamine systems:

Dissociation of alkanolamine

RRRNH
+
RRRN + H
+

Dissociation of water

H
2
O H
+
+ OH
-

Dissociation of hydrogen sulfide

H
2
S H
+
+ HS
-

Dissociation of bisulfide ion
HS
-
H
+
+ S
2-

Hydrolysis of carbon dioxide

CO
2
+ H
2
O H
+
+ HCO
3
-

Dissociation of bicarbonate ion

HCO
3
-
H
+
+CO
3
2-

Carbamate formation (except tertiary amines)

CO
2
+ 2 RRRN RRRNH
+
+ RRRNCOO
-

The vapor and liquid phases are connected by isofugacity equations and thus the following
relations apply:

For solutes:
=
i i i
V
i i
H m P y
For water:
=
sat V
w w w
V
w w
P a P y
, 0

with:
V
i
: fugacity coefficient
i
y : vapor mole fraction
P : pressure of the system
Simulis

______________________________________________________________________________________

i
H : Henrys constant for component i in pure water
w
a : activity of water
: Poyntings factor
0
w
P : saturation pressure of water
i
m : molality (kmol/kg)
i
: activity coefficient

The Deshmukh-Mather model is basically a method for calculating the excess Gibbs free energy
function using an activity coefficient approach, and it is based on an extension of the Debye-Hckel
theory. As suggested by Edwards et al. [EDW75] the form of equation for activity coefficients of the
solutes species is:

( )

+
+
=
w j
j ij
i
i
m
BaI
I z A

2
1
304 . 2
ln
2
1
2
1
2

where:

A : Debye-Hckel limiting slope

B : function of the temperature and the dielectric constant of the solvent
a : adjustable parameter measured in Angstrm units which roughly
corresponds to the effective size of the hydrated ions
I : ionic strength (

=
j
j j
z m
2
2
1
)

i
z : absolute charge of j
th
ionic species
ij
: parameter for the interaction of species i with species j

Fugacity coefficients are calculated using the Peng-Robinson equation of state [PEN76]..

Simulis
Thermodynamics Enthalpies Entropies- 88

______________________________________________________________________________________

7. ENTHALPIES - ENTROPIES
7.1. Enthalpies
Beside phase equilibria, calculation of enthalpies also appears to be very important not only for
calculation of heat exchanged in a process, but also for calculation of adiabatic flashes and
multistage separation processes such as distillation and absorption.

7.1.1. Enthalpy basis
Three enthalpy bases are available:

Enthalpy of pure i component, standard state (ideal gas 25C)
In this case:
hi* (298 K) = 0

H* = 0, liquid state, 25c, 1 atm
In this case, the origin of the enthalpies is zero for a pure component in liquid state at 25C and
1 atm. With respect to previous basis this one is a translation equal to heat of vaporization of
the considered component. Consequently it is recommended to use this enthalpy basis only
when all the components can exist in liquid state at 25 C at provided that the coefficients used
to compute the liquid specific heat are available for all the components present in the mixture.

H* =
0
f
H , ideal gas, 25C, 1 atm
For all the components, the enthalpy basis is the value of the standard enthalpy of formation at
25C for this component. The use of this enthalpy basis is recommended when dealing with a
reactive systems (it is used by default for electrolytes models presented previously).
Please note that the selection of an enthalpy basis is reflected on the entropy basis.

7.1.2. Ideal gas state fluid enthalpy (H*)
The ideal gas state fluid enthalpy is obtained from the specific heat of pure components at zero
pressure, noted Cpi*. The Specific heat of an ideal gas is a temperature monotonic growing
function; several empirical equations to compute ideal gas specific heat are available at the level of
the pure component description. The enthalpy of ideal gas i component at temperature T, with
respect to reference temperature, T
0
= 298 K, is given by:

( )

=
T
T
*
pi
*
i
o
dT C T h

For an ideal gas mixture of n components, there is no mixing heat. Thus, the enthalpy of such a
mixture is:

( )
( )
=
=
n
1 i
T
*
i
h
i
z z , T
*
H

Simulis

______________________________________________________________________________________

7.1.3. Homogeneous approach (equation of state)
In this case, the enthalpy of a real fluid is calculated from the ideal gas state enthalpy of the pure
component and an equation of state available for the whole fluid domain. LEE-KESLER equation of
state with or without PLOCKER mixing rules (LKP) generally gives a better modeling of the
enthalpies compared with other equations of state. This option can be accessed in the field
"Enthalpy calculation" as an option of a thermodynamic model under the title:

H* = 0, ideal gas, 25C, 1 atm and (H - H*) liq by LKP
H* = 0, ideal gas, 25C, 1 atm and (H - H*) liq by LK
H* = 0, ideal gas, 25C, 1 atm and (H - H*) by LKP
H* = 0, ideal gas, 25C, 1 atm and (H - H*) by LK

In the first two cases, only the enthalpy departure of the liquid phase is calculated using LKP
(respectively LK), the enthalpy departure of the vapor phase being calculated with the equation of
state selected in the thermodynamic profile. In the last cases, the enthalpy departure for both liquid
and vapor phases are calculated using LKP equation of state (respectively LK).

The general formulation to calculate enthalpy of a real fluid (vapor, liquid or supercritical) is the
following:

( ) ( ) ( ) z , P , T H H z , T H z , P , T H
* *
+ =

where (H-H*) is the correction of enthalpy (molar enthalpy departure) of a fluid of composition z at
temperature T and pressure P with respect to enthalpy of ideal gas H* at same temperature,
pressure and composition. This correction is obtained from an equation of state (SRK, PR, LKP,
BWRS,) from the equation:

( ) dP
T
V
T V H H
z , P
P
0
z , P , T
*
|
.
|
\
|

The thermodynamic path used to calculate enthalpy of a real fluid is illustrated in the following
figure:
Thermodynamic path for the calculation of the enthalpy of a real fluid
Equation Of State approach
1
10
100
1000
-7000 -6000 -5000 -4000 -3000 -2000 -1000 0 1000 2000
Enthalpy
P
r
e
s
s
u
r
e
H*(T1,P=0)
T1 T2
(H-H*)
T1,P1
P1
P2

Simulis

______________________________________________________________________________________

7.1.4. Heterogeneous approach ( )
All the models described hereafter have been established assuming that the standard reference
state is always the enthalpy of the fluid in ideal gas state. The correcting term for a vapor is
calculated from an equation of state. For pure liquid components, the correcting term is usually
calculated by differentiation of standard state fugacities. When reliable experimental data are used
to determine the standard state fugacity, derivatives with respect to temperature at constant
pressure give pure liquid enthalpies with the same accuracy to the one obtained from calorimetric
data.

The enthalpy of a liquid mixture cannot be calculated with sufficient precision without experimental
data specific to this solution. Although it always remains possible to differentiate the expression of
excess free enthalpy (activity coefficient model) with respect to temperature to get the enthalpy of a
mixture, such a procedure demonstrates to be poorly accurate because the dependency of
temperature on binary interaction parameters used to model the non ideality of liquid phases is
usually not well known. Better results can be obtained when vapor-liquid equilibrium data are
available on a wide range of temperature or when some mixture enthalpy data can be used to
determine the influence of temperature on binary interaction parameters. Hopefully, mixing
enthalpy usually represent a minor contribution to the total enthalpy for non-electrolytic liquid
mixtures. For engineering calculations, it is generally sufficient to estimate roughly the mixing
enthalpy or to neglect it.

7.1.4.1. Vapor phase
The general expression for calculation of the enthalpy of a real gas is the same as the method
presented in the previous chapter for an homogeneous approach:

( ) ( ) ( )
y , P , T
* V * V
H H y , T H y , P , T H + =

H* being the enthalpy of the fluid in an ideal gas state calculated from the equation:

( ) dT C T h
*
pi
T
T
*
i
i
=

and (H-H*) being the correction of enthalpy (molar enthalpy departure) of a fluid of composition z at
temperature T and pressure P with respect to enthalpy of ideal gas H* at same temperature and
composition. This contribution is obtained from an equation of state with the equation:

dP
y ,
T
V
T V
y ,
*
H H
P
p
o P , T
V
|
|
.
|
\
|
= |
.
|
\
|

7.1.4.2. Liquid phase
7.1.4.2.1. General case
The enthalpy of a liquid mixture when an heterogeneous approach has been selected is the
following one:
( ) ( ) ( ) x , P , T h P , T
i
h
i
x x , P , T h
E OL
n
1 i
L
+ =

=

In this equation, the first term is the enthalpy of the ideal liquid mixture. The second term is the
excess enthalpy or mixing enthalpy. In most cases very few information are available to estimate
this last term, but hopefully its contribution to the total enthalpy of a liquid is generally low. This
Simulis

______________________________________________________________________________________

term is generally neglected. The calculation of this term from the selected activity coefficient model
is the following one:

( )
( )
n P
i
Nc
i
i
E
T
x P T
n RT x P T h
,
1
2
, , ln
, , |
.
|
\
|
=

=

Caution
In order to take into account the excess enthalpy contribution, the option
standard with Poynting correction must be selected at the level of pure
liquid fugacity standard state selection.

As a standard, the enthalpy of pure liquid i component is obtained by summing the enthalpy of pure
fluid in ideal gas state at the same temperature hi*(T) with a corrective term calculated from
differentiation of standard state liquid fugacity fi0L (T,P). The fundamental thermodynamic
relationship is the following:

( ) ( )
( )
P
L 0
i 2 *
i
L 0
i
T
P , T f Ln
RT T h P , T h
|
|
.
|
\
|
=

The more general expression of standard state liquid fugacity, except in the case of specific models
such as Chao-Seader [CHA61] or Grayson-Streed [GRA63], is the following one (for further details,
see chapter "Pure liquid standard state fugacity"):

( ) ( ) ( ) ( ) ( ) ( )
= T P P
RT
v
exp . T P . T P , T P , T f
0
i
L 0
i 0
i
0
i
V 0
i
L 0
i

By differentiation of this expression with respect to temperature and putting the results in the
expression above to calculate tge enthalpy of pure liquid i component, the following expression is
obtained:

( ) ( ) ( ) ( ) { } ( )
( ) P - P
dT
L 0 v
T - v

dT
dP
v - v T - T h - P T, h T h P T, h
0
i
P
i 0L
i
0
i 0L
i
0V
i
*
i
0
i
0V
i
*
i
L 0
i
|
|
.
|
\
|
+
+ =

The second term of this expression corresponds to the correction of enthalpy for a vapor at the
equilibrium at temperature T with respect to ideal gas at this temperature. This correction is
calculated from equation of state selected in the thermodynamic profile, using the following
expression:

( ) dP
T
v
T v h h
P
V 0
i V 0
i
P
0
, P , T
*
i
V 0
i
0
i
0
i

)
|
|
.
|
\
|

where
V
i
v
0
is the molar volume of vapor i component

Simulis

______________________________________________________________________________________

The third term represents the quantity ( ) ( ) { }
0 0 0 0
, ,
i
V
i i
L
i
P T h P T h corresponding to the contribution
linked to phase change, i.e. heat of vaporization (changing its sign), because according to the
Clausius-Clapeyron relation:

( ) ( ) T Hv
dT
dP
v v T
i
0
i L 0
i
V 0
i
=

Finally, the last term represents pressure influence on liquid enthalpy, i.e. the quantity
( ) ( ) { }
0 0 0
, ,
i
L
i
L
i
P T h P T h . Since use of this kind of models is limited to moderate pressures, this
term can be neglected.

The thermodynamic path used to calculate enthalpy of a real fluid is illustrated in the following
figure.

Consequently, calculation of liquid enthalpy according to this thermodynamic path requires
knowledge of:
pure components ideal gas heat capacities Cpi*(T)
pure components vapor pressure laws Pi
0
(T)
an equation of state able to model the vapor phase behavior in order to calculate the molar
volumes v
i
0V
(T,Pi
0
)and residual enthalpies (h
i
0V
- hi*)
T,Pi0

an equation allowing to calculate molar volumes of pure liquid components at their boiling
point v
i
0L
(T,Pi
0
)

When the influence of temperature on the vaporization enthalpy of each of the pure components is
not known, another thermodynamic path can be considered. The use of liquid specific heat in the
calculation can then be considered. The expression is then the following:
0
h
H
i
v
(T)
( ) ) T ( P - P
T
V
T V
0
i
L 0
i L 0
i
|
|
.
|
\
|
h
i
*
(T)
h
i
0V
(T,P
i
0
(T)) - h
i
*
(T)

T
298K
h* = 0
P
Pi
0
(T)
P = 0
P
Simulis

______________________________________________________________________________________

( ) ( ) ( ) ( )
( ) ( ) P - P
T
v
T - dT C Teb H -
Teb h - P , Teb h dT Cp P T, h
0
i
P
0L
i 0L
i
Sat
P
T
Teb
i V
i
*
i i
0V
i
*
i
Teb
298.15
L 0
i
L
i
i
i
i
|
|
.
|
\
|
|
|
.
|
\
|
+ +
+ =

This expression takes into account liquid specific heat assuming a maintained saturated state. In
other words, this quantity corresponds to the energy required to perform a temperature change
while maintaining a saturated liquid state. Unfortunately, this quantity is difficult to measure and
makes use of the previous relation not easy. However, there are two other kinds of liquid specific
heats which are respectively the isobaric specific heat (C
P
L
) corresponding to enthalpy change with
respect to temperature at constant pressure and the saturated liquid state specific heat (C
p
L
)
corresponding to the enthalpy change with respect to temperature for a saturated liquid. These
three liquid specific heats are linked together by the following equations:

P
L
P

dT
dH
C |
.
|
\
|
=

dT
dP

dT
dV
T V C
T
dH
C
L
0
P
L
L L
p
L L
P
|
|
.
|
\
|
(
(
|
|
.
|
\
|
+ =
=

dT
dP
V C C
L
0
L L
p
SatL
p

|
|
.
|
\
|
=

Thus:

dT
dP

dT
dV
T C C
L
0
P
L
L
p
SatL
p
|
|
.
|
\
|
|
|
.
|
\
|
=

From previous relations, it is possible to link the liquid specific heat at maintained saturated state to
the isobaric liquid specific heat which is a well known property, which can be measured easily.

Furthermore, in conditions far away from the critical point of the pure component, the three specific
heats can be assumed to be equal:

L
p
SatL
p
L
p
C C C

So, the previous relation applied to a multicomponent system becomes:

( ) ( ) ( ) ( ) ( )
( )
( ) P - P
T
T - x
dT C x Teb H x -
Teb h - P , Teb h x Teb h x P T, h
0
i
P
0L
i 0L
i i
N
1 i
L
p
T
Teb
i
N
1 i
i V i
N
1 i
i
*
i i
OV
i i
N
1 i
i
*
i i
N
1 i
L 0
i
i
i
|
|
.
|
\
|
|
|
.
|
\
|

+
+
+ =

=
= =
= =

Simulis

______________________________________________________________________________________

In this case, the thermodynamic path for calculation of liquid enthalpy is the following one:

0
P
h
1 atm
dT Cp
T
T
L
i
b
Tb(1atm)
T
h
i
*
(T)
298K
h* = 0
h
i
0V
(T
b
,1) - h
i
*
(T
b
)

P
H
i
v
(T
b
)
( ) 1 - P
T
V
T V
L 0
i L 0
i
|
|
.
|
\
|
Simulis

______________________________________________________________________________________

7.1.4.2.2. Special case of Chao-Seader and Grayson-Streed methods

For chemical systems including "non-condensable" components in a supercritical state with respect
to temperature and pressure of the mixture, the expression presented in the previous paragraph for
the calculation of the reference fugacity cannot be used. Then, the relations used to calculate the
liquid enthalpy of the mixture are obtained by differentiation with respect to temperature of the
Chao-Seader or Grayson-Streed equations (see chapter relative to "standard state pure liquid
fugacity").

From Chao-Seader correlation we can get:

P
OL
P
OL
T
i
Ln
T
i
f Ln
|
|
|
.
|
\
|

=
|
|
|
.
|
\
|

( ) ( )
P
1
P
O
L
P
OL
T
i
Ln
'
T
i
Ln
T
i
Ln
|
|
|
.
|
\
|

+
|
|
|
.
|
\
|

=
|
|
|
.
|
\
|

( )
( )
( )
(
(
(
+ +
+ + + + + + +
=
ri
2
ri ri 9 8
ri
2
ri 7 ri 6 5
3
ri 4
2
ri 3 ri 2
ri
1
0 0
iL
P Log P T A A
P T A T A A T A T A T A
T
A
A
10 Ln Ln

( ) ( )
( )
(
+ + + + + +
=
|
|
.
|
\
|

=
|
|
.
|
\
|

2
ri 9 ri ri 7 6
2
ri 4 ri 3 2
2
ri
1
ci
P
ri
0
iL
ci
P
0
iL
P A P T A 2 A T A 3 T A 2 A
T
A
T
10 Ln
T
Ln
T
1
T
Ln

( )
( )
(
+ + + + = 6 P A T A
T
A
T A A 10 Ln Ln
ri 14
3
ri 13
ri
12
ri 11 10
0
iL

( )
(
+ =
|
|
.
|
\
|

2
ri 13
2
ri
12
11
Li
P
0
iL
T A 3
T
A
A
T
10 Ln
T
Ln

( )

ri
T A 3
ri
T
A
A
'
i ri
P A
ri
P
ri
T A 2 A
ri
T A 3
ri
T A 2 A
ri
T
A

ci
T
10 Ln
T
i
f Ln
2
13
2
12
11
2
9
7 6
2
4 3 2
2
1
P
OL
(
(
(
|
|
|
.
|
\
|
+ + +
+ + + +
=
|
|
|
.
|
\
|

Simulis

______________________________________________________________________________________

7.2. Entropies
Calculation of entropies is useful in particular in the design of compressors, turbines, but also to
calculate chemical equilibria. The selected enthalpy basis also induce the entropy basis. For all the
property models, the entropy of a fluid is calculated as the sum of the ideal gas state fluid entropy
noted S*, and a corrective term.

7.2.1. Ideal gas state fluid entropy
Ideal gas state fluid entropy is obtained from ideal gas specific heat of pure components, Cp
i
*,
through the following equation:

=
T
T
i
i
P
P
Ln R dT
T
Cp
P T s
0
0
* 0
*
) , (

Consequently, the entropy of a mixture of ideal gases can be obtained from the expression:

( ) ( )
i i i i
z Ln z R P T s z z P T S
n
i
n
i

= =
=
1 1
, * , ,
0 *

The last term of this expression accounts for the mixing entropy of a mixture of ideal gases. This
last expression can be written:

( ) ( )
i i i
z P T s z z P T S
n
i
, , , ,
* *
1
=
=

where ( )
i i
z P T s , ,
*
is partial molar entropy of i component in a mixture of ideal gases, given by the
expression:

( )

=
T
T
i
i
i
P
P
z Ln R dT
T
Cp
P T s
0
0
*
*
,

7.2.2. Homogeneous approach (equation of state)
In this case, real fluid entropy is calculated from ideal gas state entropy of the fluid and an equation
of state available in all the fluid domain (SRK, PR, LKP,).

According to this model, the general formulation to calculate real fluid entropy (vapor, liquid or
supercritical fluid) is the following one:

( ) ( ) ( )
z P T
S S z T S z P T S
, ,
* *
, , , + =

where term ( )
z P T
S S
, ,
*
is the correction of entropy (molar entropy departure) of a fluid of
composition z at temperature T and pressure P with respect to entropy of ideal gas S* at same
temperature, pressure and composition. This correction is obtained from an equation of state from
expression:

( ) dP
T
V
P
R
S S
z P
P
z P T
|
.
|
\
|
,
0
, ,
*

Simulis

______________________________________________________________________________________

7.2.3. Heterogeneous approach ( )
Reference state is always for liquid and vapor phases the entropy of the ideal gas state fluid
entropy. The corrective term for a vapor is calculated from an equation of state. For liquid pure
components, the corrective term is calculated from standard state fugacities.

Excess entropy, which is the correction of entropy with respect ideal mixture, is neglected.

7.2.3.1. Vapor phase
The general expression for the calculation of the entropy of a real gas is the same as the method
previously presented for an homogeneous approach and can be estimated using the following
expression:

( ) ( ) ( )
y P T
V
S S y T S y P T S
, ,
* *
, , , + =

where S* is the entropy of the fluid at ideal gas state, and (S - S*) the molar entropy departure of a
vapor of composition y, at temperature T and pressure P with respect to entropy of ideal gas S* at
the same temperature, pressure and composition.

This term is obtained from an equation of state with expression:

( ) dP
T
V
P
R
S S
y P
P
y P T
|
.
|
\
|
,
0
, ,
*

7.2.3.2. Liquid phase
7.2.3.2.1. General case

Entropy of a liquid mixture is calculated from expression:

( ) ( ) ( ) x P T S x P T S x P T S
E L L
, , , , , ,
0
+ =

where
E
S is the excess entropy and
L
S
0
is the entropy of the ideal mixture given by:

( ) ( )
i
x Ln
i
x R P T
i
s
i
x x P T S
n
i
L
n
i
L

= =
=
1
0
1
, , ,
0

where
L
i
s
0
is liquid entropy of pure component i at temperature and pressure of the mixture. The
excess entropy term
E
S is neglected since its contribution to total entropy of the liquid is generally
low.

The entropy of pure liquid i component is obtained by summing entropy of pure fluid in ideal gas
state at the same temperature ( ) P T
i
s
L
,
0
and a corrective term calculated from the expressions of
the standard state fugacities (for further details, refer to chapter " Standard state pure liquid
fugacities"). The fundamental thermodynamic relationship is the following one:

( ) ( )
( ) ( )
P
L
i
L
i
i
L
i
T
P T f
RT
P
P T f
R P T s P T s
|
|
.
|
\
|
=
, ln ,
ln , ,
0 0
* 0 0

Simulis

______________________________________________________________________________________

The general expression to calculate entropy of a liquid mixture is then the following:

( ) ( )
( ) ( )
( ) x P T S
P
P T f
R
T
P T f
RT x x P T S x P T S
E
L
i
P
L
i
i
Nc
i
L
, ,
,
ln
, ln
, , , ,
0 0
1
*
+
+
|
|
.
|
\
|
=

=

Depending on the thermodynamic model used to calculate the standard state fugacity several
formulations are obtained for entropy.

Except in the case of specific models such as Chao-Seader [CHA61] or Grayson-Streed [GRA63],
the expression of the standard state pure liquid fugacity is the following one (for further details, see
chapter "Pure liquid standard state fugacity"):

( ) ( ) ( ) ( ) ( ) ( )
= T P P
RT
v
exp . T P . T P , T P , T f
0
i
L 0
i 0
i
0
i
V 0
i
L 0
i

This equation leads to the following expression for the liquid entropy of a pure i component:

( ) ( ) ( ) ( ) { } ( ) ( )
0
0 0
0 0 0 0 0 0 0 0
, , , ,
* *
i
P
L
i i L
i
V
i i i i
V
i
o
i i
L
i
T
v
dT
dP
v v P T s P T s P T s P T s
|
|
.
|
\
|
+ =

The second term of this expression corresponds to the correction of entropy for a vapor at the
equilibrium at temperature T with respect to ideal gas at same temperature and pressure ( ) T P
i
0
.
This correction is calculated from equation of state selected in the thermodynamic profile, using the
following expression:
( ) dP
T
v
P
R
S S
P
L
i
P
P T i
V
i
i
i
|
|
.
|
\
|
0
0
,
* 0 0
0
0

The third term is the variation of entropy linked to physical state change
( ) ( ) { }
( )
T
T H
P T s P T s
vi
i
V
i i
L
i

=
0 0 0 0
, , . Because, according to the Clausius-Clapeyron relation:

( ) ( ) T Hv
dT
dP
v v T
i
0
i L 0
i
V 0
i
=

Finally, the last term represents the influence of the pressure on the liquid entropy, i.e. the quantity
( ) ( ) { }
0 0 0
, ,
i
L
i
L
i
P T s P T s . This term can be neglected.

Taking into account previous remarks in the equation of liquid entropy (in particular neglecting
excess entropy and pressure influence on liquid entropy), the following expression to calculate
liquid entropy of a mixture of x composition can be retained:

( ) ( )
( )
( ) ( ) ( ) ( )
( )
(

+ =

=
T
T H
P T s T P T s
P
T P
R x x P T S x P T S
vi
i i
V
i
i
i
Nc
i
L
, , ln , , , ,
* 0 0 0
0
1
*

The calculation of liquid entropy following this thermodynamic path requires knowledge of:

pure components ideal gas heat capacities Cpi*(T)
pure components vapor pressure laws Pi
0
(T)
Simulis

______________________________________________________________________________________

an equation of state able to model the vapor phase behavior in order to calculate the molar
volumes v
i
0V
(T,Pi
0
)and residual entropies (s
i
0V
- s
i
0*
)
T, Pi0
.
an equation allowing to calculate molar volumes of pure liquid components at their boiling
point v
i
0L
(T, P
i
0
).

7.2.3.2.2. Special case of Chao-Seader and Grayson-Streed methods

From Chao-Seader [CHA61] and Grayson-Streed [GRA63] correlations, the following expression
can be obtained:

( )
(
(
(
(
|
|
.
|
\
|
+ +
+ + + + + +
=
|
|
.
|
\
|
2
ri 13
2
ri
12
11
2
ri 9 ri ri 7 6
2
ri 4 ri 3 2
2
ri
1
ci
P
L 0
i
T A 3
T
A
A '
P A P T A 2 A T A 3 T A 2 A
T
A
T
10 ln
T
f ln

Simulis
Thermodynamics Molar volume and liquid density - 100

______________________________________________________________________________________

8. MOLAR VOLUME AND LIQUID DENSITY
8.1. With equation of state
The user can calculate the liquid molar volume (and then the density) by using an equation of state
(Soave Redlich Kwong [SOA72], Peng Robinson [PEN76], Redlich Kwong [RED49], Lee
Kesler Plcker [LEE75], [PLO78], or Benedict Webb Rubbin Modified Starling Nishiumi
[STA71], [STA72], [NIS75], [NIS77], [NIS80], [NIS83])
However, it is recommended to be very careful when calculating liquid molar volumes with
equations of state and in particular with cubic equations of state: Cubic equations of state with two
parameters can not, in fact, represent both the volumetric behavior and the vapor tension with a
satisfactory accuracy [ABB89]. For more information, the reader is invited to refer to the chapter
Equation of state.

8.2. Ideal Mixture
In this case, the molar volume of the mixture is calculated from pure component properties. The
mixing rule is the following:

si
Nc
i
i
V x V

=
=
1

with:
V : molar volume of the mixture
Vsi : molar volume at saturation of the component i
Xi : mole fraction of component i

8.3. Helgeson
The Helgeson equation of state [HEL74a], [HEL74b], [HEL76], [HEL81], [TAN86] can be used for
the calculation of standard molar volume of electrolyte solutions:
T
P
Q
T P
a a
P
a a V |
.
|
\
|
|
.
|
\
|
+ |
.
|
\
|
|
|
.
|
\
|
+
+ +
|
|
.
|
\
|
+
+ =

1
1 1 1 1
4 3 2 1
0

P
T
Y |
.
|
\
|
2
1

P
T
Y
X |
.
|
\
|
=

T
P
Q |
.
|
\
|
2
1

: dielectric constant of the solvent
: constant pressure term for a solvent (2600 bar for water)
: constant temperature term for a solvent (228 K for water)

: Born coefficient
Simulis

______________________________________________________________________________________

8.4. API 6A2.22
This correlation expresses the density of a mixture with respect to its standard density and its
pseudo-critical coordinates. It was developed by API [API82] for hydrocarbon mixtures and its
formulation is the following:
( )
( )
( )
r
r r
P , F 60 C
P , T C
P , F 60
=

with:
: mixture density (kg/m

3
)
Tr : reduced temperature of the mixture
Pr : reduce pressure of the mixture
C : API corrective factor

The critical coordinates (Tc and Pc) are estimated using Kay rules.

The liquid density at 60F is estimated by calculating the average density of pure components
weighted with mass fractions.

A correlation was established in order to represent the API 6A2.22 graph, with the corrective factor
as a function of reduced temperature and reduced pressure.

( ) [ ] ( ) ( ) ( ) ( ) 1.1676 P ln * 0.0780 * 0.2014 P ln * 0.2928 - * 0.7776 - P ln * 0.3173
r r
2
r
+ + + + =
r r
T T C

Graphical results of this correlation are presented hereafter:
Simulis

______________________________________________________________________________________

0,60
0,65
0,70
0,75
0,80
0,85
0,90
0,95
1,00
1,05
1,10
1,15
1,20
1,25
0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
Tr ( - )
C

(

-

)
Saturated Liquid
Pr = 1
Pr = 1,5
Pr = 2
Pr = 2,5
Pr = 3
Pr = 4
Pr = 5
Pr = 6
Pr = 8
Pr = 10
Pr = 15
Pr = 20
Pr = 25
Pr = 30

API 6A2.22 Correlation Corrective factor C as function of the reduced temperature

Simulis

______________________________________________________________________________________

8.5. COSTALD
The COSTALD (COrresponding STAtes Liquid Density) [HAN79] method was originally developed
for the calculation densities of liquefied gases. Its use is however fairly general.

( ) [ ]
m
Rm m Rm sm
s
M
T f 1 V . V 1
=
+ =
4
1 k
k
k Rm
a 1 V avec ( )
3 / 1
Rm
T 1 =

( )

=
|
|
.
|
\
|
=
4
1 k Rm
1 k
Rm k
Rm
1 T
T b
T f

1
a = -1.52816
1
b = -0.296123
2
a = 1.43907
2
b = 0.386914
3
a = -0.81446
3
b = -0.0427258
4
a = 0.190454
4
b = -0.0480645

( ) ( ) ( )

+ =
3 / 2
si i
3 / 1
si i si i sm
V x . V x
4
3
V x
4
1
V

with:

Rm
T : reduced temperature of the mixture [K]
si
V : caracteristic molar volume of component i [cm
3
/mol]
sm
V : caracteristic molar volume of the mixture [cm
3
/mol]
m
M : molar weight of the mixture [g/mol]
s
: density of the mixture at saturation pressure [kg/m
3
]
m
: acentric factor of the mixture:
=
i
i i m
x [-]

The characteristic molar volumes are calculated from a known density at a temperature T
1
:

( ) ( )
1
Ri i
1
Ri
1
i
ls
i
si
T f 1 V
M
V

=
with:

si
V : molar volume caractristique of component i [cm
3
/mol]
i
M : molar weight of component i [g/mol]
1
i
ls
: density of component i at temperature
1
T and saturation pressure [kg/m
3
]
i
: acentric factor of component i [-]
1
Ri
V : value of the function
R
V for the component i at temperature
1
T
( )
1
Ri
T f : value of the function ( )
R
T f for the component i at temperature
1
T

Simulis

______________________________________________________________________________________

For pressures greater than the saturation pressure, the density is calculated by taking into account
the correction of pressure, as described by Thomson and al. [TH082]:

s
s
P B
P B
ln C 1
1
+
+
C = 0.0861488 + 0.0344483
m

=
+ =
4
1 k
k
k
cm
a 1
P
B
( )
3 / 1
Rm
T 1 =

a
1
= 9.070217 a
2
= 62.45326 a
3
= 135.1102
a
4
= exp (4.79594 + 0.250047
m
+ 1.14188
m
2
)

with:
cm
P : mixture pseudo-critical pressure [bar]
s
P : saturation pressure of mixture at T [bar]
P : pressure [bar]
m
: acentric factor of the mixture [-]
Rm
T : reduced temperature of the mixture [-]
s
: density at saturation pressure [g/cm
3
]
: density at T and P [g/cm
3
]

The saturation pressure of a mixture is defined as the vapor tension of a pure component that has
the same critical coordinates as the mixture; it is calculated here from the generalized Riedel vapor
pressure equation:
( )
m Rm
cm
s
10
, T f
P
P
log =
with:
s
P : saturation pressure of the mixture [bar]
cm
P : pseudo-critical pressure of the mixture [bar]
( )
m Rm
, T f : Riedel function
m
: acentric factor of the mixture [-]

( )
) 1 (
Rm m
) 0 (
Rm m Rm
P P , T f + =
07608141 . 0 T log 8031817 . 5 P
Rm 10
) 0 (
Rm
+ =
86601 . 4 P
) 1 (
Rm
=
6
Rm Rm 10
Rm
T T log 736 . 96
T
0 . 36
0 . 35 + =
03721754 . 0 T log
Rm 10
+ =
Simulis

______________________________________________________________________________________

8.6. Rackett modified for pure components and ideal mixtures
For each component, the use of Rackett modified correlation [RAC70], [SPE72] is forced for the
calculation of the liquid density at saturation:
( )
|
.
|
\
|
+
= =
7 / 2
r
T 1 1
RA
c
c
s
s
Z
P
RT
V
1

if Z
RA
is missing, then Z
RA
= Z
C

if Z
C
is missing, then Z
RA
= 0.29056 0.0877

with:
s
: liquid density of the component at saturation
s
V : liquid molar volume of the component at saturation
R : perfect gas constant
T
c
: critical temperature
P
c
: critical pressure
T
r
: reduced temperature
Z
RA
: Rackett compressibility factor
Z
c
: critical compressibility factor
: acentric factor

The liquid molar volume at saturation is obtained with the following mixing rule:
i
Nc
1 i
i
V x V

=
=

Simulis

______________________________________________________________________________________

8.7. Rackett modified for mixtures
The Rackett modified equation is applied to mixtures:

( ) ( )
7 / 2
1 1
1
1
r
T
RAm
ci
ci
Nc
i
i
bp
Z
P
T
x R
+
=
|
|
.
|
\
|
=

Mixing rules are the following:
=
=
Nc
i
RA i RA
i m
Z x Z
1

mc
r
T
T
T =
= =
=
Nc
i
Nc
j
cij j i mc
T T
1 1

=
=
Nc
j
cj j
ci i
i
V x
V x
1

( )
ij cj ci cij
k T T T = 1
( )
3
3 1 3 1
3 1 3 1
2
1
(
(
(
+
=
cj ci
cj ci
ij
V V
V V
k
with:
bp
: liquid density of the mixture at bubble temperature
R : perfect gas constant
x
i
: mole fraction of component i
T
ci
: critical temperature of component i
P
ci
: critical pressure of component i
Vci : critical molar volume of component i
i
RA
Z : Rackett compressibility factor for component i
T : temperature

Simulis

______________________________________________________________________________________

8.8. Novotny and Sohnel
Novotny and Sohnel [NOV88] suggested a correlation that allows calculating the liquid density of
aqueous solutions of inorganic substances. They identified the correlation coefficients for over 300
inorganic substances. The equations used are the following:

2
2
3
2
3
2
3
2
t Fc t Ec Dc Cct Bct Ac
w
+ + + + + + =

2
3
2 1
10 . 174 , 6 10 . 0438 , 2 65 , 999 t t
w

+ =

with:
: density of the mixture in kg/m
3

w
: density of water in kg/m
3

c : concentration in mol/l
t : temperature in C
A, B, C, D, E, F : coefficients, specific to each system

Simulis
Thermodynamics Transport properties - 108

______________________________________________________________________________________

9. TRANSPORT PROPERTIES
9.1. liquid viscosity
9.1.1. Pure mixing rules
3
i
3
1
i i m
x
|
|
.
|
\
|
=

with:
m
: liquid viscosity of the mixture (Pa.s)
i
: liquid viscosity of component i (Pa.s)
i
x : mole fraction of component i

9.1.2. CLASSICAL mixing rules
|
.
|
\
|
=

i i
x
i
M
ln exp
with:
m
: liquid viscosity of the mixture
i
: viscosity of pure component i at mixture temperature
x
i
: mole fraction of the component

9.1.3. ELY-HANLEY method (TRAPP method)
The calculation of the viscosity suggested by Ely and Hanley [ELY81], [ELY83] is applicable to
systems that include hydrocarbons and some of their derivatives (low polar) as well as to
component such as N
2
, CO, CO
2
, H
2
, H
2
S. This method is not recommended when water is
involved and should be used with caution when reduced temperature is above 0,925.

The basic assumption is the following [ELY81], [ELY83]:
) , ( ) , ( T T
X mel
=

The mixture is taken as a hypothetical pure component called x.
F T T
X
). , ( ) , (
0 0 0
=

The viscosity of this pure component is equal to the multiplication of the reference fluid viscosity
(methane) by a corrective factor:
F is calculated as follow:

3 / 2
0 ,
2 / 1
,
2 / 1
0
. .

|
|
.
|
\
|
=
X O X
X
h f
M
M
F

0 , 0 ,
1
0 , 0 ,
ij
h
ij
f
j
x
i
x h f
j i
X X
=
0 0 , , ij
h
j
x
i
x
x
h
j i

=

Simulis

______________________________________________________________________________________

0 , 0 , 0 ,
.
j i ij
f f f = ( )
3
3 / 1
0 ,
3 / 1
0 , 0 ,
8
1
ji i ij
h h h + =

( )
i i i i
c
ci
i
V T
T
T
f , ,
* *
0 ,
0
0 ,
= ( )
i i i i
c
ci
i
V T
V
V
h , ,
* *
0 ,
0
0 ,
=

( ) ( ) ( )
+ +
+ =
i i i i i i i
V T F V T , . 1 , ,
0
* *
0 ,

( ) ( ) ( ) [ ]
ci
c
i i i i i i i
Z
Z
V T G V T
0
0
* *
0 ,
. , . 1 , ,
+ +
+ =
( ) ( ) 5 . 0 . ) ( . ,
1
1 1 1

|
|
.
|
\
|
+ + + =
+
+
+ + +
i
i
i i i
V
T
d
c T Ln b a V T F

( ) ( ) ( ) ) ( . . . ,
2 2 2 2
+ + + + +
+ + + =
i i i i i
T Ln d V c b V a V T G

( ) [ ] 5 . 0 ; max ; 2 min
ri i
T T =
+
( ) [ ] 5 . 0 ; max ; 2 min
ri i
V V =
+

ci
i
ri
T
T
T =
i
ci
ri
V
=

Furthermore:

3 / 8
0
1
0
2
3 / 4 2 / 1
0
2 / 1
, , , ,
0

(
=

x
h
x
f
ij
h
ij
f
ij
M
j
x
i
x
x
M
j i

j i
j i
ij
M M
M M
M
+
=
. 2

Constant table:

a
1

= 0.090569 a
2
= 0.394901
b
1
= -0.862762 b
2
= -1.023545
c
1
= 0.316636 c
2
= -0.932813
d1 = -0.465684 d2 = -0.754639

The correlation for the calculation of the reference fluid (methane) viscosity is descried hereafter:

( )
|
|
.
|
\
|
=
0 ,
0 , 0 0 0 0
, . ,
X
X
f
T
h T

( )
0
). , ( ). ( ) ( ,
0 0 0 0 0
) 2 (
0 0
) 1 (
0 0 0 0
X T T T T + + =

Simulis

______________________________________________________________________________________

( ) |
.
|
\
|
+
+
(
(
|
|
.
|
\
|
|
|
.
|
\
|
=
R c
R b a
Z
Z
f
T f
T
X
c
c
X
V
X
X X
X
X
. 1
.
. . . 1
2 / 1
0
0 ,
0 ,
0

with: 5 . 1 =
ci
Z
i
x
cx
Z
i
=
|
|
|
|
.
|
\
|
|
.
|
\
|
=

ci
V
ci
V
i
x R
i
min
1

and a = 0.16129 b = -4.51613 c = -5.35484

=
|
.
|
\
|
=
9
1
3
4
0 0
) 1 (
0
. ) (
n
n
n
T C T
2
4
0
3 2 1 0
) 2 (
0
. ) (
(
|
|
.
|
\
|
+ =
b
T
Ln b b b T
(
(
|
|
.
|
\
|
+ +
|
|
.
|
\
|
+
|
|
.
|
\
|
+
|
|
.
|
\
|
+ = 1 . . 1 . exp . exp ) , (
2
0
7
0
6
5
5 . 0
0
0 1 . 0
0
2 / 3
0
4
3
0
2
1 0 0 0
T
a
T
a
a
T
a
a
T
a
a T
c

with:
a
1
= -1.0239160427E+1 b
1
= 1.696985927E+0 c
1
= 2.907741307E+6
a
2
= 1.7422822961E+2 b
2
= -1.3337234608E-1 c
2
= -3.312874033E+6
a
3
= 1.7460545674E+1 b
3
= 1.4 c
3
= 1.608101838E+6
a
4
= -2.8476328289E+3 b
4
= 1.68E+2 c
4
= -4.331904871E+5
a
5
= 1.3368502192E-1 c
5
= 7.062481330E+4
a
6
= 1.4207239767E+2 c
6
= -7.116620750E+3
a
7
= 5.0020669720E+3 c
7
= 4.325174400E+2
c
8
= -1.445911210E+1
c
9
= 2.037119479E-1

9.1.4. PETRO method
9.1.4.1. Hydrocarbon mixture: Twu [TWU85]
The kinematic viscosity at 210F is obtained with the following formulation:
2
2
2
b
0
2
b
2
f 2 1
f 2 1
T
450
ln
T
450
ln
|
|
.
|
\
|
+
|
|
.
|
\
|
+ =
|
|
.
|
\
|
+

( )
2 / 1
b
2
2
T
SG
1141 . 21 SG x f

=
2 / 1
b
T
7394 . 56
99873 . 1 x =
Simulis

______________________________________________________________________________________

= SG SG SG

Similarly, the kinematic viscosity at 100F with the following formulation:
2
1
1
b
1
b
1
2 1
f 2 1
T
450
ln
T
450
ln
|
|
.
|
\
|
+
|
|
.
|
\
|
+ =
|
|
.
|
\
|
+

( )
2 / 1
b
2
1
T
SG
1141 . 21 SG x 33932 . 1 f

=

The relation between two kinematic viscosities at two different temperatures is the following:

( ) ( ) T ln B A Z ln ln + =
|
.
|
\
|

+ + =
2
51 . 0 84 . 1 47 . 1
e 7 . 0 Z
( )
( )
2 1
2 1
T ln T ln
Z ln ln Z ln ln
B
=
( )
1 1
T ln T ln B Z ln ln Z ln ln + =

The relation between kinematic viscosity and dynamic viscosity is the following:
6
10 *
=

with:
: dynamic viscosity (Pa.s)
: kinematic viscosity (cSt)
: density (kg/m
3
)
T : temperature (K)
T
b
: normal boiling point (K)
SG : specific gravity

9.1.4.2. Particular case: Water-Hydrocarbon model
( )
3
3 / 1
hc hc
3 / 1
w w wet
x x + =
with:
wet
: viscosity of the mixture (Pa.s)
w
: viscosity of water calculated from the database (Pa.s)
hc
: viscosity of the hydrocarbon mixture (Pa.s)
w
x : mole-fraction of water in the mixture
hc
x : mole-fraction of hydrocarbons in the mixture

Simulis

______________________________________________________________________________________

9.2. Vapor viscosity
9.2.1. Pure mixing rules
( )
( )

=
i
2
1
i i
i
2
1
i i i
m
Mw y
Mw y

with:
m
: vapor viscosity of the mixture (Pa.s)
i
: vapor viscosity of component i (Pa.s)
i
y : mole-fraction of component i

9.2.2. Classic mixing rules
9.2.2.1. Calculation of viscosity of a gazeous mixture at low pressure
If the selected equation of state is that of perfect gas, the BROKAW mixing rule [BRO69] is used:

ij j
y
i
i
y
j
i
M
=
*
*

With
2 / 1
*
*
. .
|
|
.
|
\
|
=
j
i
ij ij ij
A S

S
ij
= 1 if I and j non polar
In other cases:
2 # 2 #
# #
25 . 0 1 25 . 0 1
25 . 0 1
j j i i
j i j i
ji ij
T T
T T
S S

+ + + +
+
= =

( )
( )
(
(
(
(
(
|
|
.
|
\
|
+
+
+ +
+ =
ij
ij ij
ij
ij ij
ij ij ij
m
m M
M
M M
M m A
1
. 1
1 2
1 . .
2 / 1 45 . 0
45 . 0
2 / 1

( )( )
25 . 0
1
1 . 1
4
(
(
+ +
=
ij ij
ij
M M
m

Simulis

______________________________________________________________________________________

j
i
ij
M
M
M =
i
i
T k
T
.
#
=

K : Boltzmann constant

i
: energy parameter

i
: polarity parameter

Required data:
For each component
M : molar weight
*
: viscosity of component i
for the calculation of energy and polarity parameters:

T
c
P
c
: critial pressure
V
c
: critical density
: acentric factor
T
b
: normal boiling point temperature
D
: dipolar moment
L
: density
T
: reference temperature

9.2.2.2. Calculation of viscosity of a gaseous mixture at high pressure
When the selected equation of state is different from the perfect gas equation of state, the
calculation of viscosity of a gaseous mixture is conducted using the DEAN-STIEL model [DEA65]:

( ) ( ) ( ) [ ]
858 . 1 *
111 . 1 exp 439 . 1 exp 08 . 1 .
M M
r r M M M
=

M
*: viscosity of the gaseous mixture at low pressure, computed with BROKAW mixing rules (see
previous section).

M
c
r
V
V
M
M
=
2 / 1
3 / 2 6 / 1
.
M
c c
M
M
T
M M

=
PRAUSNITZ-GUNN mixing rules [PRA58]:

i
M
i
y M
i
M
=
i
i
M
c c
T
i
y T

=
Simulis

______________________________________________________________________________________

i
i
M
c c
Z
i
y Z

=
i
i
M
c c
V
i
y V

=

M
M M
M
c
c c
c
V
T R Z
P
. .
=
Application field
It is recommended to use this method only with non polar or low polar gas systems.

Required data
M : molar weight
T
c
V
c
: critical density
Z
c
M
*
: viscosity of the gaseous mixture at low pressure
V
M
: density of the gaseous mixture

The calculation of the viscosity suggested by Ely and Hanley [ELY81], [ELY83] is applicable to
systems that include hydrocarbons and some of their derivatives (low polar) as well as to
component such as N
2
, CO, CO
2
, H
2
, H
2
S. This method is not recommended when water is
involved and should be used with caution when reduced temperature is above 0,925.

The basic assumption is the following [ELY81], [ELY83]:
) , ( ) , ( T T
X mel
=

The mixture is taken as a hypothetical pure component called x.
F T T
X
). , ( ) , (
0 0 0
=

The viscosity of this pure component is equal to the multiplication of the reference fluid viscosity
(methane) by a corrective factor:
F is calculated as follow:

3 / 2
0 ,
2 / 1
,
2 / 1
0
. .

|
|
.
|
\
|
=
X O X
X
h f
M
M
F

0 , 0 ,
1
0 , 0 ,
ij
h
ij
f
j
x
i
x h f
j i
X X
=
0 0 , , ij
h
j
x
i
x
x
h
j i

=

0 , 0 , 0 ,
.
j i ij
f f f = ( )
3
3 / 1
0 ,
3 / 1
0 , 0 ,
8
1
ji i ij
h h h + =

Simulis

______________________________________________________________________________________

( )
i i i i
c
ci
i
V T
T
T
f , ,
* *
0 ,
0
0 ,
= ( )
i i i i
c
ci
i
V T
V
V
h , ,
* *
0 ,
0
0 ,
=

( ) ( ) ( )
+ +
+ =
i i i i i i i
V T F V T , . 1 , ,
0
* *
0 ,

( ) ( ) ( ) [ ]
ci
c
i i i i i i i
Z
Z
V T G V T
0
0
* *
0 ,
. , . 1 , ,
+ +
+ =
( ) ( ) 5 . 0 . ) ( . ,
1
1 1 1

|
|
.
|
\
|
+ + + =
+
+
+ + +
i
i
i i i
V
T
d
c T Ln b a V T F

( ) ( ) ( ) ) ( . . . ,
2 2 2 2
+ + + + +
+ + + =
i i i i i
T Ln d V c b V a V T G

( ) [ ] 5 . 0 ; max ; 2 min
ri i
T T =
+
( ) [ ] 5 . 0 ; max ; 2 min
ri i
V V =
+

ci
i
ri
T
T
T =
i
ci
ri
V
=

Furthermore:

3 / 8
0
1
0
2
3 / 4 2 / 1
0
2 / 1
, , , ,
0

(
=

x
h
x
f
ij
h
ij
f
ij
M
j
x
i
x
x
M
j i

j i
j i
ij
M M
M M
M
+
=
. 2

Constant table:

a
1

= 0.090569 a
2
= 0.394901
b
1
= -0.862762 b
2
= -1.023545
c
1
= 0.316636 c
2
= -0.932813
d1 = -0.465684 d2 = -0.754639

The correlation for the calculation of the reference fluid (methane) viscosity is descried hereafter:

( )
|
|
.
|
\
|
=
0 ,
0 , 0 0 0 0
, . ,
X
X
f
T
h T

( )
0
). , ( ). ( ) ( ,
0 0 0 0 0
) 2 (
0 0
) 1 (
0 0 0 0
X T T T T + + =

( ) |
.
|
\
|
+
+
(
(
|
|
.
|
\
|
|
|
.
|
\
|
=
R c
R b a
Z
Z
f
T f
T
X
c
c
X
V
X
X X
X
X
. 1
.
. . . 1
2 / 1
0
0 ,
0 ,
0

Simulis

______________________________________________________________________________________

with: 5 . 1 =
ci
Z
i
x
cx
Z
i
=
|
|
|
|
.
|
\
|
|
.
|
\
|
=

ci
V
ci
V
i
x R
i
min
1

and a = 0.16129 b = -4.51613 c = -5.35484

=
|
.
|
\
|
=
9
1
3
4
0 0
) 1 (
0
. ) (
n
n
n
T C T
2
4
0
3 2 1 0
) 2 (
0
. ) (
(
|
|
.
|
\
|
+ =
b
T
Ln b b b T
(
(
|
|
.
|
\
|
+ +
|
|
.
|
\
|
+
|
|
.
|
\
|
+
|
|
.
|
\
|
+ = 1 . . 1 . exp . exp ) , (
2
0
7
0
6
5
5 . 0
0
0 1 . 0
0
2 / 3
0
4
3
0
2
1 0 0 0
T
a
T
a
a
T
a
a
T
a
a T
c

with:
a
1
= -1.0239160427E+1 b
1
= 1.696985927E+0 c
1
= 2.907741307E+6
a
2
= 1.7422822961E+2 b
2
= -1.3337234608E-1 c
2
= -3.312874033E+6
a
3
= 1.7460545674E+1 b
3
= 1.4 c
3
= 1.608101838E+6
a
4
= -2.8476328289E+3 b
4
= 1.68E+2 c
4
= -4.331904871E+5
a
5
= 1.3368502192E-1 c
5
= 7.062481330E+4
a
6
= 1.4207239767E+2 c
6
= -7.116620750E+3
a
7
= 5.0020669720E+3 c
7
= 4.325174400E+2
c
8
= -1.445911210E+1
c
9
= 2.037119479E-1

Simulis

______________________________________________________________________________________

9.2.4. PETRO method
9.2.4.1. Hydrocarbon mixture at low pressure: Yoon and Thodos [YOO70]
( ) ( ) ( ) ( )
He He H H NP NP m
* * x * * x * * x *
2 2
+ + =
( ) 1 e 4 . 19 e 4 . 20 T 10 . 46 10 *
R R
T 058 . 4 T 449 . 0 618 . 0
R
5
NP
+ + =

(non polar gases)
( ) 1 e 19 e 20 T 65 . 47 10 *
R R
2
T 995 . 3 T 858 . 0 657 . 0
R
5
H
+ + =

(Hydrogen)
( ) 1 e 9 . 17 e 9 . 18 T 57 . 52 10 *
R R
T 182 . 5 T 144 . 1 656 . 0
R
5
He
+ + =

(Helium)
6 / 1
4
C
3
C
m
P M
T
|
|
.
|
\
|
=

with:
: viscosity of the mixture at low pressure (Pa.s)

T
R
: reduced temperature of the mixture T
R
= T / T
C

T : temperature (K)
T
C
: critical temperature of the mixture computed with Kays rules (K)
M : molar weight
P
C
: critical pressure of the mixture computed with Kays rules (atm)

9.2.4.2. Influence of the pressure: Dean and Stiel (API 11B1.4) [DEA65], [API82]
( )
|
.
|
\
|
=

858 . 1
R R
11 , 1 439 . 1 5
m
*
e e 10 * 8 . 10

*
: viscosity of the mixture at low pressure (Pa.s)

R
: reduced density

9.2.4.3. Particular case : Water-hydrocarbon model
2 / 1
hc hc
2 / 1
w w
2 / 1
aq hc hc
2 / 1
w w w
wet
MW y MW y
MW y MW y
+
+
=
with:
wet
w
: viscosity of water calculated from the database (Pa.s)
hc
: viscosity of the hydrocarbon mixture (Pa.s)
w
y : mole-fraction of water in the mixture
hc
y : mole-fraction of hydrocarbons in the mixture
w
MW : molar weight of water
hc
MW : molar weight of the hydrocarbon mixture

Simulis

______________________________________________________________________________________

9.3. Liquid thermal conductivity
9.3.1. PURE mixing rules
2
i
i
i
2
m
w

=

with:
m
: liquid thermal conductivity of the mixture (W/m.K)
i
: liquid thermal conductivity of component i (W/m.K)
i
w : mass fraction of component i

9.3.2. CLASSIC mixing rules
The mixing rules used are those of VREDEVELD [VRE77]:

( )
2 / 1
2
i i
i
M
x

=

with:
i
: liquid thermal conductivity of component i
x
i
: mole-fraction of component i

The thermal conductivity calculation suggested by Ely and Hanley [ELY81], [ELY83] can be applied
to systems that include hydrocarbons and some of their derivatives (low polar) as well as to
component such as N
2
, CO, CO
2
, H
2
, H
2
S. It is not recommended to use this method if there is
water and one must be cautious when reduced temperature in above 0,925.

The method is as follow:

( ) ( ) ( ) T T T
mel mel mel
, , ,
" '
+ =

- ( ) T
mel
,
'
: external contribution (collision effects)

( ) ( )

F T T
mel
. , ,
0 0
'
0
'
= (same assumption as for viscosity)

3 / 2
0 ,
2 / 1
0 ,
2 / 1
0
. .

|
|
.
|
\
|
=
X X
X
h f
M
M
F

3 / 8
0
2
3 / 4
0
2 / 1
0
2 / 1
0 , , , , x
h
x
f
ij
h
ij
f
ij
M
j
x
i
x M
j i
X
|
.
|
\
|
=

- ( ) T
mel
,
"
: internal contribution

Simulis

______________________________________________________________________________________

( )

=
i j
ij j i mel
T x x T ) , ( . ,
" "

) , 0 ( ) , 0 (
) , 0 ( ). , 0 ( 2
) , (
" "
" "
"
T T
T T
T
j i
j i
ij

=

i
i
pi i
M
T
R T C f T
) (
.
2
5
) ( ) , 0 (
0
0
int
"

|
.
|
\
|
=

with f
int
= 1.32 R = 1.987

Correlation for the calculation of thermal conductivity of the reference fluid (methane)

( ) [ ]

X T T T T . ) , ( ). ( ) ( ,
0 0 0 0 0
) 2 (
0 0
) 1 (
0 0 0
'
0
+ + =

2 / 3
0
0 ,
0 ,
. ) ( . 1
(
(
|
|
.
|
\
|
|
|
.
|
\
|
=
cX
c
V
X
X X
X
Z
Z
f
T f
T
X
X

) ( .
4
15
) (
0
) 1 (
0
0
0
) 1 (
0
T
M
R
T =

=
|
.
|
\
|
=
9
1
3
4
0 0
) 1 (
0
. ) (
n
n
n
T C T

2
4
0
3 2 1 0
) 2 (
0
) ( . ) (
(
+ =
b
T
Ln b b b T

( )
(
(
|
|
.
|
\
|
+ +
|
|
.
|
\
|
|
|
.
|
\
|
+
(
+ = . 1 1 exp exp
2
0
7
0
6
5
5 . 0
0
0 1 . 0
0
2 / 3
0
4
3
0
2
1 0 , 0 0
T
a
T
a
a
T
a
a
T
a
a T
c

with:

a
1
= -7.1977082270E+0 b
1
= -0.252762920E+0 c
1
= 2.907741307E+6
a
2
= 8.5678222640E+1 b
2
= 0.334328590E+0 c
2
= -3.312874033E+6
a
3
= 1.2471834689E+1 b
3
= 1.12 c
3
= 1.608101838E+6
a
4
= -9.8462522975E+1 b
4
= 0.168E+3 c
4
= -4.331904871E+5
a
5
= 3.5946850007E-1 c
5
= 7.062481330E+4
a
6
= 6.9798412538E+1 c
6
= -7.116620750E+3
a
7
= -8.7288332851E+2 c
7
= 4.325174400E+2
c
8
= -1.445911210E+1
c
9
= 2.037119479E-1

Simulis

______________________________________________________________________________________

Reference fluid equation of state (p, atm ; , mol/L ; T, Kelvin)

( ) ( )
2 17 2
15
10
9
1

+ =

= =

e
n
T
n
a
n
T
n
a p
n n

a
1

= RT a
2
= N
1
T + N
2
T
1/2
+ N
3
+ N
4
/T + N
5
/T
2

a
3
= N
6
T + N
7
+ N
8
/T + N
9
/T
2
a
4
= N
10
T + N
11
+ N
12
/T
a
5

= N
13
a
6
= N
14
/T + N
15
/T
2

a
7
= N
16
/T a
8
= N
17
/T + N
18
/T
2

a
9

= N
19
/T
2
a
10
= N
20
/T
2
+ N
21
/T
3

a
11

= N
22
/T
2
+ N
23
/T
4
a
12
= N
24
/T
2
+ N
25
/T
3

a
13
= N
26
/T
2
+ N
27
/T
4
a
14
= N
28
/T
2
+ N
29
/T
3

a
15
= N
30
/T
2
+ N
31
/T
3
+ N
32
/T
4

i Ni i Ni
1 -1.184347314485E-2 17 1.071143181503E-5
2 7.540377272657E-1 18 -9.290851745353E-3
3 -1.225769717554E+1 19 1.610140169312E-4
4 6.260681393432E+2 20 3.469830970789E+4
5 -3.490654409121E+4 21 -1.370878559048E+6
6 5.301046385532E-4 22 1.790105676252E+2
7 -2.875764479978E-1 23 1.615880743238E+6
8 5.011947936427E+1 24 6.265306650288E-1
9 -2.821562800903E+4 25 1.820173769533E+1
10 -2.064957753744E+5 26 1.449888505811E-3
11 1.285951844828E-2 27 -3.159999123798E+1
12 -1.106266656726E+0 28 -5.290335668451E-6
13 +3.060813353408E-4 29 1.694350244152E-3
14 -3.174982181302E-3 30 8.612049038886E-9
15 5.191608004779E+0 31 -2.598235689063E-6
16 -3.074944210271E-4 32 3.153374374912E-5

= 0.0096 R = 0.08205616

Simulis

______________________________________________________________________________________

9.3.4. EZRA K. T. KAM method
Kam developed a method for the calculation of the liquid thermal conductivity azeotropic mixtures
with accuracy [KAM93]. This method is based on the characterization factor model, originally
proposed by Barret [BAR29]. The characterization factor used in the process is defined by
resolving simultaneously the two equations presented below. At the end of the resolution, the
characterization factor and the liquid thermal conductivity are obtained, the first depending on the
composition and not being a constant. This method can also be used for the binaries or the
mixtures that do not have azeotropes.

( ) ( ) [ ]
=
=
Nc
1 i
i i m
w sinh sinh

( ) ( ) ( ) [ ]
=
=
Nc
1 i
i i m
sinh w sinh ln

with:
i
: liquid thermal conductivity of component i
i
w : mass fraction of component i

Simulis

______________________________________________________________________________________

9.3.5. PETRO method
9.3.5.1. Hydrocarbons mixture at low pressure: Sato Riedel [REI87]
( )
( )
(
+
+
=
3 / 2
3 / 2
3
1 20 3
1 20 3 10 . 64 , 2
br
r
m
T
T
M

with:
m
: thermal conductivity of the mixture at low pressure (W/m.K)
M : molar weight of the mixture
T
r
r
= T / T
C

T
br
: reduced dew normal temperature of the mixture T
br
= T
b
/ T
C

T
C
: critical temperature of the mixture calculated with Kays rules (K)
T
b
: normal boiling temperature of the mixture calculated with Kays rules (K)

9.3.5.2. Influence of the pressure: API 12A4.1 [API82]
*
*
C
C
=
with:
*
: thermal conductivity of the mixture calculation pressure (W/m.K)
C, C
*
: correction factors, calculated at P and 1 atm respectively:
( )
r
2
r
r r
P * 2 . 0 exp
T * 054 . 2
T * 764 . 7 P * 065 . 0 77 . 17 C + =
T
r
r
= T / T
C

P
r
: reduced pressure of the mixture P
r
= P / P
C

T
C
P
C
: critical pressure of the mixture calculated with Kays rules (K)
Simulis

______________________________________________________________________________________

Thermal conductivity factor of Liquid Hydrocarbons at High Pressures
6
7
8
9
10
11
12
13
14
15
0 1 2 3 4 5 6 7 8 9 10 11 12
Reduced Pressure, Pr
C
o
n
d
u
c
t
i
v
i
t
y

F
a
c
t
o
r
,

C
Tr = 0,4
Tr = 0,5
Tr = 0,6
Tr = 0,7
Tr = 0,8
Tr = 0,9
Tr = 1,0

9.3.5.3. Particular case: Water-hydrocarbon model
( )
2 / 1
2
hc hc
2
w w
wet
w w
1

+
=
with:
wet
: thermal conductivity of the mixture (W/m.K)
w
: thermal conductivity of water calculated from the database (W/m.K)
hc
: thermal conductivity of the hydrocarbon mixture (W/m.K)
w
w : mass fraction of water in the mixture
hc
w : mass fraction of hydrocarbon in the mixture
Simulis

______________________________________________________________________________________

9.3.6. API 12A3.2 method
9.3.6.1. Hydrocarbons mixture at low pressure: API 12A3.2 [API06]
( )
( ) T 10 364 . 5 10 961 . 9 MeABP
6 3 2904 . 0
m

=
avec :
m
: Thermal conductivity of the mixture at low pressure (Btu/ft.h.F)
MeABP : Mean average boiling point (R)
T : Mixture temperature (F)

9.3.6.2. Influence de la pression : API 12A4.1 [API82]
The same method as the one described in the PETRO method chapter is used.

9.3.6.3. Cas particulier modle eau hydrocarbures
The same method as the one described in the PETRO method chapter is used.

Simulis

______________________________________________________________________________________

9.4. Vapor thermal conductivity
( )
( )

=
i
3
1
i i
i
3
1
i i i
m
Mw y
Mw y

with:
m
: vapor thermal conductivity of the mixture (W/m.K)
i
: vapor thermal conductivity of component i (W/m.K)
i
y : mole fraction of component i

9.4.2.1. Gaseous mixture at low pressure
When the selected equation of state is that of perfect gas, the MASON-SAXENA [MAS58] is used.
The WASSILJEWA mixing rule [WAS04] is selected:
|
|
|
|
.
|
\
|
j
ij j
*
i i
A y
y
"
V
i
M

with:

i
*
V
: thermal conductivity of a pure gas at low pressures
2 / 1
j
i
2
4 / 1
j
i
2 / 1
V *
j
V *
i
ij
M
M
1 8
M
M
1
A
(
(
|
|
.
|
\
|
+
(
(
(
|
|
.
|
\
|
|
|
.
|
\
|
+
=
i
*
V
: viscosity of pure gas at low pressure

Required data
M : molar weight
*
i
: viscosity of pure component at low pressure
*
i
: thermal conductivity of a pure gas at low pressures

Simulis

______________________________________________________________________________________

9.4.2.2. Gaseous mixture at high pressure
If the selected equation of state is different from the perfect gas equation of state, the STIEL-
THODOS correlation [STI64] is used:
M
r
< 0.5 ( )
( ) [ ]
5
c M
r
8 *
M M
M
M
Z T
1 535 . 0 exp
10 * 0 . 14

=

0.5
M
r
2 ( )
( ) [ ]
5
c M
r
8 *
M M
M
M
Z T
069 . 1 67 . 0 exp
10 * 1 . 13

=

2
M
r
2.8 ( )
( ) [ ]
5
c M
r
8 *
M M
M
M
Z T
016 . 2 115 . 1 exp
10 * 976 . 2
+
=

M
r
2.8 ( )
5
c M
8
r
8
*
M M
M
M
Z T
10 * 376 . 8 10 * 24 . 87

+
=

with:
M
*: liquid conductivity of a gaseous mixture at low pressure
M
c
r
V
V
M
M
=
6 / 1
4
c
3
M c
M
M
M
P
M T
T
|
|
.
|
\
|
=

Prausnitz-Gunn mixing rules

=
i
c i c
i M
T x T
=
i
c i c
i M
V x V

=
i
c i c
i M
Z x Z
M
M M
M
c
c c
c
V
T R Z
P
. .
=

Required data
M : molar weight
T
c
V
c
: critical molar volume
Z
c
*
M
: thermal conductivity of a gaseous mixture at low pressure
M
V : molar volume of a gaseous mixture

Simulis

______________________________________________________________________________________

The thermal conductivity calculation suggested by Ely and Hanley [ELY81], [ELY83] can be applied
to systems that include hydrocarbons and some of their derivatives (low polar) as well as to
component such as N
2
, CO, CO
2
, H
2
, H
2
S. It is not recommended to use this method if there is
water and one must be cautious when reduced temperature in above 0,925.

The method is as follow:

( ) ( ) ( ) T T T
mel mel mel
, , ,
" '
+ =

- ( ) T
mel
,
'
: external contribution (colliding effects)

( ) ( )

F T T
mel
. , ,
0 0
'
0
'
= (same assumption as for viscosity)

3 / 2
0 ,
2 / 1
0 ,
2 / 1
0
. .

|
|
.
|
\
|
=
X X
X
h f
M
M
F

3 / 8
0
2
3 / 4
0
2 / 1
0
2 / 1
0 , , , , x
h
x
f
ij
h
ij
f
ij
M
j
x
i
x M
j i
X
|
.
|
\
|
=

- ( ) T
mel
,
"
: internal contribution

( )

=
i j
ij j i mel
T x x T ) , ( . ,
" "

) , 0 ( ) , 0 (
) , 0 ( ). , 0 ( 2
) , (
" "
" "
"
T T
T T
T
j i
j i
ij

=

i
i
pi i
M
T
R T C f T
) (
.
2
5
) ( ) , 0 (
0
0
int
"

|
.
|
\
|
=

with f
int
= 1.32 R = 1.987

Correlation for the calculation of thermal conductivity of the reference fluid (methane)

( ) [ ]

X T T T T . ) , ( ). ( ) ( ,
0 0 0 0 0
) 2 (
0 0
) 1 (
0 0 0
'
0
+ + =

2 / 3
0
0 ,
0 ,
. ) ( . 1
(
(
|
|
.
|
\
|
|
|
.
|
\
|
=
cX
c
V
X
X X
X
Z
Z
f
T f
T
X
X

) ( .
4
15
) (
0
) 1 (
0
0
0
) 1 (
0
T
M
R
T =

=
|
.
|
\
|
=
9
1
3
4
0 0
) 1 (
0
. ) (
n
n
n
T C T
Simulis

______________________________________________________________________________________

2
4
0
3 2 1 0
) 2 (
0
) ( . ) (
(
+ =
b
T
Ln b b b T

( )
(
(
|
|
.
|
\
|
+ +
|
|
.
|
\
|
|
|
.
|
\
|
+
(
+ = . 1 1 exp exp
2
0
7
0
6
5
5 . 0
0
0 1 . 0
0
2 / 3
0
4
3
0
2
1 0 , 0 0
T
a
T
a
a
T
a
a
T
a
a T
c

with:

a
1
= -7.1977082270E+0 b
1
= -0.252762920E+0 c
1
= 2.907741307E+6
a
2
= 8.5678222640E+1 b
2
= 0.334328590E+0 c
2
= -3.312874033E+6
a
3
= 1.2471834689E+1 b
3
= 1.12 c
3
= 1.608101838E+6
a
4
= -9.8462522975E+1 b
4
= 0.168E+3 c
4
= -4.331904871E+5
a
5
= 3.5946850007E-1 c
5
= 7.062481330E+4
a
6
= 6.9798412538E+1 c
6
= -7.116620750E+3
a
7
= -8.7288332851E+2 c
7
= 4.325174400E+2
c
8
= -1.445911210E+1
c
9
= 2.037119479E-1

Reference fluid equation of state (p, atm ; , mol/L ; T, Kelvin)

( ) ( )
2 17 2
15
10
9
1

+ =

= =

e
n
T
n
a
n
T
n
a p
n n

a
1

= RT a
2
= N
1
T + N
2
T
1/2
+ N
3
+ N
4
/T + N
5
/T
2

a
3
= N
6
T + N
7
+ N
8
/T + N
9
/T
2
a
4
= N
10
T + N
11
+ N
12
/T
a
5

= N
13
a
6
= N
14
/T + N
15
/T
2

a
7
= N
16
/T a
8
= N
17
/T + N
18
/T
2

a
9

= N
19
/T
2
a
10
= N
20
/T
2
+ N
21
/T
3

a
11

= N
22
/T
2
+ N
23
/T
4
a
12
= N
24
/T
2
+ N
25
/T
3

a
13
= N
26
/T
2
+ N
27
/T
4
a
14
= N
28
/T
2
+ N
29
/T
3

a
15
= N
30
/T
2
+ N
31
/T
3
+ N
32
/T
4

Simulis

______________________________________________________________________________________

i Ni i Ni
1 -1.184347314485E-2 17 1.071143181503E-5
2 7.540377272657E-1 18 -9.290851745353E-3
3 -1.225769717554E+1 19 1.610140169312E-4
4 6.260681393432E+2 20 3.469830970789E+4
5 -3.490654409121E+4 21 -1.370878559048E+6
6 5.301046385532E-4 22 1.790105676252E+2
7 -2.875764479978E-1 23 1.615880743238E+6
8 5.011947936427E+1 24 6.265306650288E-1
9 -2.821562800903E+4 25 1.820173769533E+1
10 -2.064957753744E+5 26 1.449888505811E-3
11 1.285951844828E-2 27 -3.159999123798E+1
12 -1.106266656726E+0 28 -5.290335668451E-6
13 +3.060813353408E-4 29 1.694350244152E-3
14 -3.174982181302E-3 30 8.612049038886E-9
15 5.191608004779E+0 31 -2.598235689063E-6
16 -3.074944210271E-4 32 3.153374374912E-5

= 0.0096 R = 0.08205616

9.4.4. PETRO method
9.4.4.1. Hydrocarbon mixture at low pressure: Roy and Thodos [ROY70]

( ) ( )
( ) ( ) ( ) [ ]
( ) ( )
( )
2 3 2
3 2
int
int
10 82 . 1 10 21 . 5
039 . 0 191 . 1 152 . 0
2412 . 0 exp 0464 . 0 exp 757 . 8
6
1
4
3
210
M M C
T T T T f
T Cf
T T
r r r r
r
r r tr
tr
C
P
M
C
T

+ =
+ =
=
=
(
(
+ =
=

with:
T
r
: reduced temperature T
r
= T / T
C

T : temperature (K)
T
C
M : molar weight
P
C
: critical pressure of the mixture calculated with Kays rules (bar)

The function f(T
r
) used is the one proposed by Roy and Thodos [REI87] for saturated
hydrocarbons.

Simulis

______________________________________________________________________________________

The C constant formulation presented above is the one proposed by Reid and al. [REI87]. The one
used in the software is described hereafter:
Coefficient "C" used in the calculation of the gas thermal conductivity
by the Roy and Thodos model
0
5
10
15
20
25
30
35
40
0 20 40 60 80 100 120 140 160
Mw (g/mol)
C
C
ProSim formulation
C = 0,003458(Mw)
2
+ 0,01688(Mw) - 0,03098
C = 0,3013(Mw) - 5,8749

9.4.4.2. Influence of the pressure: Stiel and Thodos [STI64]
( ) [ ] 50 . 0 10 1 e 0 . 14 z
R
8 535 . 0 5
c
*
R
< =

( ) [ ] 00 . 2 50 . 0 10 069 . 1 e 10 . 13 z
R
8 67 . 0 5
c
*
R
< < =

( ) [ ] 80 . 2 00 . 2 10 016 . 2 e 976 . 2 z
R
8 155 . 1 5
c
*
R
< < + =

6 / 1
4
C
3
C
P M
T
|
|
.
|
\
|
=
with:
*
T
C
M : molar weight
P
C
: critical pressure of the mixture calculated with Kays rules (atm)

9.4.4.3. Particular case: Water-Hydrocarbons model

3 / 1
hc hc
3 / 1
w w
3 / 1
hc hc hc
3 / 1
w w w
wet
MW y MW y
MW y MW y
+
+
=
with:
wet
w
: thermal conductivity of water calculated from the database (W/m.K)
Simulis

______________________________________________________________________________________

hc
: thermal conductivity of the hydrocarbons mixture (W/m.K)
w
y : mole fraction of water in the mixture
hc
y : mole fraction of hydrocarbons in the mixture
w
MW : molar weight of water
hc
MW : molar weight of the hydrocarbon mixture

9.5. Surface tension
i
i
i m
x =

with:
m
: surface tension of the mixture (dyn/cm)
i
: surface tension of component i (dyn/cm)
i

Macleod and Sudgen mixing rule [MAC23], [SUD24] is used:

4
L 0
i
4 / 1
L i
i
L
M
M
V x
V
1
(
=

with:

M
: surface tension of the mixture

i
: surface tension of pure component i

i

L
i
V
0
: liquid molar volume of pure component i in cm
3
/mol

L
M
V : liquid molar volume of the mixture in cm
3
/mol

Recommendation
This correlation is applied to non-aqueous liquid mixtures

9.5.3. Winterfeld-Scriven-Davis mixing rule
The Winterfeld Scriven Davis mixing rule [WIN78] is as follow:

( )( )( )
2 / 1
j i
L 0
j j
L 0
i i
L
M
j i
M
V x V x
V
1
2
=

with:

M
: surface tension of the mixture
Simulis

______________________________________________________________________________________

i
: surface tension of pure component i

L
i
V
0
: liquid molar volume of pure component i

L
M
V : liquid molar volume of the mixture

i

9.5.4. PETRO mixing rule
9.5.4.1. Hydrocarbon mixture: API 10A3.1 [API82]
( )
K
T
T T
7 . 673
232 . 1
C
m
(

=
with:
m
T
C
: critical temperature of component (R) calculated with Kays rules
T : calculation temperature (R)
K : Watson characterization factor

9.5.4.2. Particular case: Water-Hydrocarbons model
hc hc w w wet
x x + =
with:
wet
w
: surface tension of water calculated from the database (dyn/cm)
hc
: surface tension of the hydrocarbons mixture (dyn/cm)
w
x : mole fraction of water in the mixture
hc
x : mole fraction of hydrocarbons in the mixture

Simulis
Thermodynamics Nomenclature - 133

______________________________________________________________________________________

10. NOMENCLATURE

Capital letters
A Margules binary interaction parameters
C
p
specific heat
G Gibbs free energy
H enthalpy
K phase equilibrium constant
M, MW molar weight
P pressure
P
0
vapor pressure
R perfect gas constant
S entropy
T temperature
V molar volume
Z compressibility factor (=PV/RT)
H
V
latent heat of vaporization

Small letters
a,b equation of state parameters
f equivalent reduce temperature factor of the component (Ely-Hanley method)
f fugacity
g equilibrium radial distribution function
g bond energy (NRTL model)
g partial molar Gibbs free energy
h equivalent reduced volume factor of component (Ely-Hanley model)
h partial molar enthalpy
k binary interaction parameter (for equation of state)
q Van der Waals area parameter
q' modified Van der Waals area parameter
r Van der Waals volume parameter
u bond energy (UNIQUAC and modified UNIQUAC models)
v molar volume of i component
x liquid mole-fraction
y vapor mole-fraction
z mixture mole fraction (liquid or vapor)

Subindexes
c critical
b normal boiling point
i,j binary in a mixture
l,i,j,k component subindex
M mixture
mel mixture
0 reference fluid
r reduce
for calculation of viscosity
for calculation of thermal conductivity
w for water or aqueous phase
hc for hydrocarbon phase

Simulis
Thermodynamics Nomenclature - 134

______________________________________________________________________________________

Exponents
E excess
L liquid
0 standard state pure component
V vapor
(r) reference
(1) ou (0) simple fluid
* ideal gas
for calculation of viscosity
for calculation of thermal conductivity

Greek letters
temperature dependant term in cubic equation of state
density
Pitzer acentric factor
' modified Pitzer acentric factor
energy parameter
dielectric constant of a solvent
activity coefficient
solubility parameter
fugacity coefficient
Wilson binary interaction parameter
thermal conductivity
viscosity
viscosity
surface tension
energy form factor
parameter in non-correspondence factor for viscosity
size form factor (calculation of viscosity: Ely-Hanley model

Simulis
Thermodynamics Bibliography - 135

______________________________________________________________________________________

11. BIBLIOGRAPHY

[ABB89] ABBOTT, M. M., Thirteen ways of looking at the van der Waals equation, Chem. Eng.
Progress, February, 25-37 (1989)

[ABR75] ABRAMS D.S., J.M. PRAUSNITZ, "Statistical thermodynamics of liquid mixtures : a new
expression for the excess Gibbs energy of partly or complete miscible systems", A.I.Ch.E. J., 21, 3,
116-128 (1975)

[ACH92] ACHARD C., Modlisation des proprits dquilibre de milieux biologiques et
alimentaires laide de modles prdictifs, Thse de luniversit Blaise Pascal (1992)

[AND78] ANDERSON T.F., J.M. PRAUSNITZ, "Application of the UNIQUAC equation to calculation
of multicomponent phase-equilibria. 1-Vapor-liquid equilibria", I.E.C. Process Des. Dev., 17, 4, 552-
560 (1978)

[ANT88] ANTOINE C., C.R. 107, 681, 836 (1888)

[API82] API Data Books (1982)

[API06] API Technical Data Books 40
th
Anniversary Edition (2006)

[BAB82] BABCOCK P.D., "Thermodynamic data base design and structure for the 1980's",
CHEMCOMP 1982, Proceeding Symposium, Anvers (Belgique), Survey Papers 13-20 (1982)

[BAR29] BARRETT T., International Critical Tables, vol.5, pp. 288-289, McGraw-Hill, New York
(1929)

[BEI89] BEILING V., B. RUMPF, F. STEPP, G. MAURER, Fluid Phase Equilibria, 53, pp. 251-259
(1989).

[BEN40] BENEDICT, M., WEBB, G.B., RUBIN, L.C. An empirical equation for thermodynamic
properties of light hydrocarbons and their mixtures, J. Chem. Phys., 8, 334 (1940)

[BOS80] BOSTON J.F., MATHIAS, P.M., Phase Equilibria in a Third-Generation Process Simulator
Proceedings of the 2nd International Conference on Phase Equilibria and Fluid Properties in the
Chemical Process Industies, West Berlin (17-21 March 1980), pp. 823-849

[BRO69] BROKAW R.S., "Molecular parameters for normal fluids", Ind. Eng. Chem. Process Des.
Dev., 8, n2, 240-253 (1969)

Simulis
Thermodynamics Bibliography- 136

______________________________________________________________________________________

[CAR72] CARNAHAN N. F., K. E. STARLING, A.I.CH.E. J., 18, P 1184 (1972)

[CHE02] CHEN J., FISCHER K., GMEHLING J., Modification of PSRK mixing rules and results for
vapor liquid equilibria, enthalpy of mixing and activity coefficients at infinite dilution, Fluid Phase
Equilibria 200, pp 411-429 (2002)

[CHA61] CHAO K.C., J.D. SEADER, "A general correlation for vapor-liquid equilibria in hydrocarbon
mixtures", A.I.Ch.E. J., 7, 598-605 (1961)

[COW78] COWARD I., D.R. WEBB, "Computational difficulties with the Chao-Seader correlation",
Comp. and Chem. Eng., 177-187 (1978)

[DAH90] DAHL S., MICHELSEN, M.L., AIChE J. 36, pp. 1829-1836 (1990)

[DAH91] DAHL S., A. FREDENSLUND, P. RASMUSSEN, The MHV2 Model : a UNIFAC-Based
Equation of State Model for Prediction of Gas Solubility and Vapor-Liquid Equilibria at Low and High
Pressures, Ind. Eng. Chem. Res., 30, pp. 1936-1945 (1991).

[DEA65] DEAN D.E., L.I. STIEL, A.I.Ch.E. J., 11, 526 (1965)

[DES81] DESHMUKH, R. D., MATHER A. E.,A Mathematical Model for Equilibrium Solubility of
Hydrogen Sulfide and Carbon Dioxide in Aqueous Alkanolamine Solutions, Chem. Eng. Sci, 36, pp
355-362 (1981)

[EDW75] EDWARDS T. J., G. MAURER, J. NEWMAN, J. M. PRAUSNITZ, AIChE Journal, Vol. 24,
n 6, pp. 966-976 (1975).

[ELY81] ELY James F., H.J.M. HANLEY, "Prediction of transport properties. 1-Viscosity of fluids
and mixtures" Ind. Eng. Chem. Fundam., 20, 323-332 (1981)

[ELY83] ELY James F., H.J.M. HANLEY, "Prediction of transport properties. 2-Thermal conductivity
of pure fluids and mixtures", Ind. Eng. Chem. Fundam., 22, 90-97 (1983)

[ENG90] ENGELS H., Phase Equilibria and Phase Diagrams of electrolytes, Chemistry Data
Series, Vol. XI, Part 1, DECHEMA (1990)

[FIS96] FISCHER K., GMEHLING J., Further development, status and results of the PSRK
method for the prediction of vapor liquid equilibria and gas solubilities, Fluid Phase Equilibria
121, pp 185-206 (1996)

Simulis

______________________________________________________________________________________

[FRE75] FREDENSLUND A., R.L. JONES, J.M. PRAUSNITZ, "Group contribution estimation of
activity coefficients in non-ideal liquid mixtures", A.I.Ch.E. J., 21, 5, 1086-1099 (1975)

[GME03] GMEHLING J., Potential of thermodynamic tools (group contribution methods, factual
data banks) for the development of chemical processes, Fluid Phase Equilibria, vol. 210, pp. 161-
173 (2003)

[GME93] GMEHLING J., JIDING L., SCHILLER M., "A modified UNIFAC model. 2. Present
parameter matrix and results for different thermodynamic properties", Ind. Eng. Chem. Res., 32,
178-193 (1993)

[GME95] GMEHLING J., From UNIFAC to modified UNIFAC to PSRK with the help of DDB, Fluid
Phase Equilibria 107, pp 1-29 (1995)

[GOS99] GHOSH P., Prediction of Vapor-Liquid Equilibria Using Peng-Robinson and Soave-
Redlich-Kwong Equations of State, Chem. Eng. Technol. 22, pp. 379-399 (1999)

[GRA63] GRAYSON H.G., C.W. STREED, "Vapor-liquid equilibria for high temperatures, high
pressure, hydrogen-hydrocarbon systems", 6th World Petroleum Congress, Section 7, Paper
20PD7 (1963)

[GUN71] GUNN R.D., T. YAMADA, A.I.Ch.E. J., Vol. 17, 1341 (1971)

[GUN73] GUNN R.D., T. YAMADA, "Saturated liquid molar volumes. The Rackett's equation",
A.I.Ch.E. J., Vol. 18, n2, 234 (1973)

[HAA84] HAAR L., GALLAGHER J.S., KELL J. H., NBS/NRC Steam Tables, Washington:
Hemisphere Publishing Corporation (1984)

[HAN79] HANKINSON R.W., G.H THOMSON, AIChE Journal, vol. 25, N4, pp 653-663, (1979)

[HAY75] HAYDEN J.G., O'CONNEL J.P., "A generalized method for predicting second virial
coefficients", I.E.C. Process Des. Dev., 14, 3, 209-216 (1975)

[HEL74a] Helgeson, H. C., and Kirkham, D.H., Am. J. Sci, 274, 1089 (1974)

[HEL74b] Helgeson, H. C., and Kirkham, D.H., Am. J. Sci, 274, 1199 (1974)

[HEL76] Helgeson, H. C., and Kirkham, D.H., Am. J. Sci, 276, 97 (1976)

[HEL 81] Helgeson, H. C., Kirkham, D.H. and Flowers, G.C., Am. J. Sci, 281, 1249 (1981)
Simulis

______________________________________________________________________________________

[HIL24] HILDEBRAND J.H, R.L. SCOTT, The solubility of nonelectrolytes, Reinhold Publishing
Corp., New York (1924, 1936, 1950)

[HIL70] HILDEBRAND J.H., J.M. PRAUSNITZ, R.L. SCOTT, "Regular and related solutions", Van
Nostrand Reinhod, New York (1970)

[HOL91] HOLDERBAUM T., GMEHLING J., PSRK: A group contribution equation of state based
on UNIFAC, Fluid Phase Equilibria, 70 pp 251-265 (1991)

[HOR05] HORSTMANN S, JABLONIEC A., KRAFCZYK J., FISCHER K., GMEHLING J., PSRK
group contribution equation of state: comprehensive revision and extension IV, including critical
constant and -function parameters for 1000 components, Fluid Phase Equilibria, pp 157-164, 227
(2005)

[HUR79] HURON M.J., J. VIDAL, "New mixing rules in single equations of state for representing
vapor-liquid equilibria of strongly non-ideal mixtures", Fluid Phase Equilibria, 3, 255-271 (1979)

[JAU04] JAUBERT J.N., MUTELET F., VLE predictions with the Peng-Robinson equation of state
and temperature dependant Kij calculated through a group contribution method, Fluid Phase
Equilibria, vol. 224, pp. 285-304 (2004)

[JAU05] JAUBERT J.N., VITU S., MUTELET F., Extension of the PPR78 model (Predictive 1978,
Peng-Robinson EOS with temperature dependant
ij
k
calculated through a group contribution
method) to systems containing aromatic components, Fluid Phase Equilibria, vol. 237, pp. 193-211
(2005)

[JAU06] JAUBERT J.N., VITU S., MUTELET F., Extension of the PPR78 model (Predictive 1978,
Peng-Robinson EOS with temperature dependant
ij
k
calculated through a group contribution
method) to systems containing naphtenic components, Fluid Phase Equilibria, vol. 243, pp. 9-28
(2006)

[KAB85] KABADI V. N. and R. P. DANNER, A Modified Soave-Redlich-Kwong Equation of State
for Water-Hydrocarbon Phase Equilibria, Ind. Eng. Chem. Process Des. Dev., 24, 537-541 (1985)

[KAM93] KAM E.K.T, "Prediction of thermal conductivity of binary azeotropic liquid mixtures",
Chemical Engineering and Science, vol. 48, N 12, pp. 2307-2312 (1993)

[KOE85] KOEHRET B. et JOULIA X., "Dveloppement des programmes de simulation de procds
chimiques. Le simulateur ProSim", L'Actualit Chimique, 6, 63-70 (1985)

Simulis

______________________________________________________________________________________

[LAR87] LARSEN B. L., P. RASMUSSEN, A. FREDENSLUND, A Modified UNIFAC Group
Contribution Model for Prediction of Phase Equilibria and Heats of Mixing, Ind. Eng. Chem. Res.,
26, pp. 2274-2286 (1987).

[LEE75] LEE B.I. and KESLER M.G., "A generalized thermodynamic correlation based on three-
parameter corresponding data", AIChE J., 21, 3, 510-527 (1975)

[LET73] LETSOU A., L.I. STIEL, AIChE J., 19, 409 (1973)

[MAC23] MACLEOD D.B. : Trans. Faraday Soc., 19, 38 (1923)

[MAD81] MADDOX R.N., J.H. ERBAR, "Equilibrium calculations by equation of state", Oil and Gas
Journal, Fv. 2, 75-78 (1981)

[MAR95] MARGULES S.B., Akad. Wiss. Wian Math. Naturviss, 104, 1834 (1895)

[MAS58] MASON E.A., "Thermal conductivity of multicomponent gas mixtures", J. Chem. Phys., 28,
1000 1001 (1958)

[MAT83] MATHIAS, P.M., COPEMAN, T.W., Fluid Phase Equilibria 13, pp. 91-108 (1983)

[MAU92] LIU Y.Q., H. Hasse and Gerd Maurer, Enthalpy Change on Vaporization of Aqueous and
Methanolic Formaldehyde Solutions, AIChE Journal, Vol. 38, N 11, pp 1693-1702 (1992)

[MAU99] ALBERT Michael, Baudilio COTO GARCIA, Cornelius KREITER and Gerd MAURER,
Vapor-Liquid and Chemical Equilibria of Formaldehyde-Water Mixtures, AIChE Journal, Vol. 45,
N 9, pp 2024-2033 (1999)

[MAU00] ALBERT Michael, Baudilio COTO GARCIA, Christian KUHNERT, Roger PESCHLA and
Gerd MAURER, Vapor-Liquid Equilibrium of Aqueous Solutions of Formaldehyde and Methanol,
AIChE Journal, Vol. 46, N 8, pp 1676-1687 (2000)

[MIC90a] MICHELSEN M. L., A Method for Incorporating Excess Gibbs Energy Models in Equation
of State, Fluid Phase Equilibria, 60, pp. 42-58 (1990).

[MIC90b] MICHELSEN M. L., A Modified Huron-Vidal Mixing Rule for Cubic Equation of State,
Fluid Phase Equilibria, 60, pp. 213-219 (1990).

[MIC90c] MICHELSEN M. L., KISTENMACHER, H, Fluid Phase Equilibria, 58, pp. 213-219 pp. 229-
230 (1990).

Simulis

______________________________________________________________________________________

[MIC04] MICHELSEN M. L., MOLLERUP J. M., Thermodynamic Models: Fundamentals &
Computational Aspects, TIE-LINE Publications (2004)

[MIL65] MILLER D.C., "A single reduced equation for the estimation of vapor-pressure", J. Phys.
Chem., 69, n9, 3209 (1965)

[NAK76] NAKAMURA R., G. J. F. BREEDVELD and J. M. PRAUSNITZ, "Thermodynamic
Properties of Gas Mixtures Containing Common Polar and Nonpolar Components", Ind. Eng.
Chem., Process Des. Dev., Vol. 15, N 4, pp. 557-564 (1976)

[NIS75] NISHIUMI H., An Improved Generalized B.W.R. Equation of State Applicable to Low
Reduced Temperatures, J. Chem. Eng. Japan, 8, 356 (1975).

[NIS77] NISHIUMI H., Correlation of the Binary Interaction Parameter of the Modified Generalized
B.W.R. Equation of State, J. Chem. Eng. Japan, 10, 176 (1977).

[NIS80] NISHIUMI H., Thermodynamic Property Prediction of C10 to C20 Paraffins and their
Mixtures by the Generalized B.W.R. Equation of State, J. Chem. Eng. Japan, 13, 74 (1980).

[NIS83] NISHIUMI H., Vapor-Liquid Equilibrium Calculation of Systems Containing Hydrogen by
Exended B.W.R. Equation of State, J. Chem. Eng. Japan, 16, 449 (1983).

[NOV88] NOVOTNY P., SHNEL O., Densities of binary Aqueous Solutions of 306 Inorganic
Substances, J. Chem. Eng. Data, 33, 49-55 (1988)

[NUL70] NULL H.R., "Phase equilibrium in process design", Wiley interscience, New York (1970)

[OEL81] OELLRICH L., U. PLOCKER, J.M. PRAUSNITZ, H. KNAPP, "Equation of state methods
for computing phase equilibria and enthalpies", I.C.E., 21, 1, 1-16 (1981)

[PEN76] PENG Y.D., D.B. ROBINSON, "A new two constant equation of state", I.E.C. Fundam, 15,
1, 59-64 (1976)

[PEN78] PENG D.Y., ROBINSON D.B., The characterization of the heptanes and heavier fractions
for the GPA Peng-Robinson programs, Gas processors association, Research Report PR-28
(1978)

[PER99] PEREDA S., K.THOMSEN, P. RASMUSSEN, Chem. Eng. Sci. Vol.55 pp.2663-2671
(1999)

Simulis

______________________________________________________________________________________

[PIT55] PITZER, K.S, LIPMANN, D.Z., CURL, Jr R.F., HUGGINS, C.M., PETERSEN, D.E.,
Compressibility factor, vapour pressure and entropy of vaporization, J. Am. Chem. Soc., 77, 3433
(1955)

[PLO76] PLCKER U., H. KNAPP, "Save time in computing density", Hydrocarbon processing,
199-201 (1976)

[PLO78] PLOCKER U., H. KNAPP, J. PRAUSNITZ, "Calculation of high pressure vapor-liquid
equilibria from a corresponding-states correlation with emphasis on asymmetric mixtures", Ind.Eng.
Chem. Process Des. Dev., 17, 3, 324-332 (1978)

[POL00] POLING B. E., PRAUSNITZ J. M., OCONNELL J. P., The properties of Gases and
Liquids, Mc Graw Hill, 5th ed.(2000)

[PRA58] PRAUSNITZ J.M., R.D. GUNN, "Volumetric properties of non-polar gaseous mixtures",
A.I.Ch.E. J., 4, 430-435 (1958)

[PRA77] PRAUSNITZ J.M., "State of the art review in phase equilibria", Phase equilibria and fluid
properties in the chemical industry, ACS Symposium Series 60, 11-61 (1977)

[PRA99] PRAUSNITZ J.M., LICHTENTHALER R.N., AZEVEDO E., Molecular Thermodynamicsof
Fluid Phase Equilibria, 3
rd
Edition, Prentice Hall PTR (1999)

[RAC70] Rackett, J. Chem. Eng. Data, vol. 15, pp 514 (1970)

[RED49] REDLICH O., KWONG I.N.S., Chem. Rev., 44, 233 (1949)

[REI77] REID R.C., J.M. PRAUSNITZ, B.E. POLING, "The properties of gases and liquids", Fouuth
ed., Mc Graw Hill Book Compagny, New York (1977)

[REI87] REID R. C., J. M. PRAUSNITZ, B. E. POLING, "The properties of Gases and Liquids", 4th
edition (1987)

[REN68] RENON H., J.M. PRAUSNITZ, "Local compositions in thermodynamic excess functions for
liquid mixtures", A.I.Ch.E. J., 14, 3, 135-144 (1968)

[REY62] REYNES E.G., G. THODOS, "A reduced state vapor-pressure relationship and its
applications to hydrocarbons", Vol. 8, n3, 357 (1962)

[ROY70] ROY D., G. THODOS, "Thermal conductivity of Gases", I&EC Fundamentals, vol. 9, N1,
pp71-79 (1970)
Simulis

______________________________________________________________________________________

[RUM92] RUMPF B., G. MAURER, Fluid Phase Equilibria, 81, pp. 241-260 (1992).

[SAN86] SANDER B., A. FREDENSLUND, P. RASMUSSEN, Chem. Eng. Sci., Vol. 41, n 5,
pp. 1171-1183 (1986).

[SAN94] SANDLER S.I., Models for thermodynamic and phase equilibria calculations (1994)

[SCA31] SCATCHARD G., Chem. Rev., 8, 321 (1931)

[SHE84] SHERWOOD A.E., SOUERS P.C., Thermodynamics of liquid hydrogen solutions,
Nuclear Technology Fusion, Vol. 5 (1984)

[SOA72] SOAVE G., "Equilibrium constants from a modified Redlich-Kwong equation of state",
Chem. Eng. Sci., 27, 6, 1197-1203 (1972)

[SOL96] SOLORZANOZAVALA M., BARRAGANAROCHE, F., BAZUA, E.R, Fluid Pahse Equilibria
122 pp 99-116 (1996)

[SPE72] Spencer and Danner, J. Chem. Eng. Data; vol 17, pp. 236 (1972)

[STA71] STARLING K. E., Thermo Data Refined for LPG, Part 1 : Equation of state and computer
prediction, Hydro. Process., 101-104 (1971).

[STA72] STARLING K. E., HAN M. S., Thermo Data Refined for LPG, Part 14 : Mixtures, Hydro.
Process., 129-132 (1972).

[STI64] STIEL L.T., G. THODOS, "The thermal conductivity of non-polar substances in the dense
gaseous and liquid regions", A.I.Ch.E. J., 10, 26-29 (1964)

[SUD24] SUDGEN S. : Journal of Chemical Society, 1177 (1924)

[TAN86] Tanger, J. C., IV, Calculation of the standard partial molal thermodynamic properties of
aqueous ions and electrolytes at high pressures and temperatures, Ph. D. dissertation, University of
California, Berkeley, 1986

[TAR79] TARAKAD R.R., C.F. SPENCER, S.B. ADLER, "A comparison of eight equations of state
to predict gas phase density and fugacity", I.E.C. Process Des. Dev., 18, 726-739 (1979)

[THO82] THOMSON G.H, K.R. BROBST, R.W. HANKINSON, AIChE Journal, vol. 28, N4, pp 671-
676 (1982)
Simulis

______________________________________________________________________________________

[THO96] THOMSEN K., P. RASMUSSEN, R.GANI, Chem. Eng. Sci. Vol.51 N 14 pp.3675-3683
(1996)
[THO99] THOMSEN K., P. RASMUSSEN, Chem. Eng. Sci. Vol.54 pp.1787-1802 (1999)

[TUC] THE UNIFAC CONSORTIUM, http://134.106.215.86/UNIFAC/

[TWU85] TWU Chorng H., "Internally Consistent Correlation for predicting Liquid Viscosities of
Petroleum Fractions", Ind. Eng. Chem. Process Des. Dev., 24, 1287-1293 (1985)

[TWU88] TWU, C. H. and BLUCK, D., An Extension of modified Soave-Redlich-Kwong equation of
state to Water-Petroleum Fraction systems, Paper presented at the AIChe Meeting. (1988)

[VID97] VIDAL J., Thermodynamique : application au gnie chimique et lindustrie prtrolire,
Editions Technip (1997)

[WAS04] WASSILJEWA A., Physik. Z., 5, 737 (1904)

[WEI87] WEIDLICH, V., GMEHLING, J, A Modified UNIFAC Model: 1. Prediction of VLE,
E
h hE,
and
Ind. Eng. Chem. Res., 26, 1372-1381 (1987)

[WEI93] WEILAND Ralph H., Tanmoy CHAKRAVARTY and Alan E. MATHER, Solubility of Carbon
Dioxide and Hydrogen Sulfide in Aqueous Alkanolamines, Ind. Eng. Chem. Res., 32, pp 1419-1430
(1993)

[WIL64] WILSON G.M., "Vapor-liquid equilibrium. XI. A new expression for the excess free energy
of mixing", J. Am. Chem. Soc. 86, 127-133 (1964)

[WIN78] WINTERFELD P.H., SRIVEN L.E., DAVIS H.T. : AIChE Journal, 24, 1010, (1978)

[YOO70] YOON Poong and Georges THODOS, AIChE Journal, vol. 16, N2, pp 300-304 (1970)

Thermodynamics Models

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Thermodynamics Models

Uploaded by

Copyright:

Available Formats

Simulis

Thermodynamics Table of content - 1

Thermodynamics Table of content - 2

Thermodynamics Table of content - 3

Thermodynamics Table of content - 4

Thermodynamics Equations of state - 8

Thermodynamics Equations of state - 9

Thermodynamics Equations of state - 10

Thermodynamics Equations of state - 11

Thermodynamics Equations of state - 12

Thermodynamics Equations of state - 13

Thermodynamics Equations of state - 14

Thermodynamics Equations of state - 15

Thermodynamics Equations of state - 16

Thermodynamics Equations of state - 17

Thermodynamics Equations of state - 18

Thermodynamics Equations of state - 19

Thermodynamics Equations of state - 20

Thermodynamics Equations of state - 21

Thermodynamics Equations of state - 22

Thermodynamics Equations of state - 23

Thermodynamics Equations of state - 24

Thermodynamics Equations of state - 25

Thermodynamics Equations of state - 26

Thermodynamics Equations of state - 27

Thermodynamics Equations of state - 28

Thermodynamics Equations of state - 29

Thermodynamics Equations of state - 30

Thermodynamics Equations of state - 31

Thermodynamics Equations of state - 32

Thermodynamics Equations of state - 33

Thermodynamics Equations of state - 34

Thermodynamics Equations of state - 35

Thermodynamics Equations of state - 36

Thermodynamics Equations of state - 37

Thermodynamics Equations of state - 38

Thermodynamics Equations of state - 39

Thermodynamics Activity coefficients models calculation- 40

Thermodynamics Activity coefficients models calculation- 41

Thermodynamics Activity coefficients models calculation- 42

Thermodynamics Activity coefficients models calculation- 43

Thermodynamics Activity coefficients models calculation- 44

Thermodynamics Activity coefficients models calculation- 45

Thermodynamics Activity coefficients models calculation- 46

Thermodynamics Activity coefficients models calculation- 47

Thermodynamics Activity coefficients models calculation- 48

Thermodynamics Activity coefficients models calculation- 49

Thermodynamics Activity coefficients models calculation- 50

Thermodynamics Activity coefficients models calculation- 51

Thermodynamics Activity coefficients models calculation- 52

Thermodynamics Activity coefficients models calculation- 53

Thermodynamics Activity coefficients models calculation- 54

Thermodynamics Standard state pure liquid fugacity- 55

Thermodynamics Standard state pure liquid fugacity- 56

Thermodynamics Standard state pure liquid fugacity- 57

Thermodynamics Complex mixing rules- 58

Thermodynamics Complex mixing rules- 59

Thermodynamics Complex mixing rules- 60

Thermodynamics Specific thermodynamic models- 61

Thermodynamics Specific thermodynamic models- 62

Thermodynamics Specific thermodynamic models- 63

Thermodynamics Specific thermodynamic models- 64

Thermodynamics Specific thermodynamic models- 65

Thermodynamics Specific thermodynamic models- 66