Chapter 4 From Phases to Method (Models) Selection

325

4.2.7.2 Ionic liquids

Ionic liquids are a new kind of solvent receiving considerable attention in the research
community. These solvents are in fact organic salts which remain liquid at room temperature. Like all salts, they are composed of a cation and an anion. The difference from the
usual salts is that these ions consist of organic chains, which may have different molar
masses. Due to their ionic character, they do not evaporate, and therefore remain in the
liquid phase. A liquid-liquid phase split may be observed, however, especially in the
presence of water or organic material. A large number of possible cation-anion combinations exist, so they can be customised to the intended application.
It is out of the scope of this book to discuss this topic. Several review papers exist in the
literature, and the interested reader is invited to consult the relevant papers directly [271, 272].
It may be of use to mention that an UNIFAC method has been dedicated to ionic liquids [273].

4.3 CONCLUSION: HOW TO CHOOSE A MODEL

4.3.1 The right questions
The practicing engineer requires a simple, unique model that will predict all possible types
of fluid behaviour. Hopefully, the discussions in this book will have convinced him that the
state of knowledge today does not allow such a simple approach.
In the absence of a simple model, the engineer will request a clear answer on which
model to choose for his/her application: some kind of expert system that provides a unique
answer, obviously including the appropriate parameters. Again, he/she may be faced with
disappointment: often, several methods are possible, and no best choice can be identified.
The only universal recommendation that can and should be made is that any model
must be compared with experimental data: these are to be taken as a guideline for
the choice of any theoretical approach.
In the same way as has been proposed in the past [274], this book suggests several entry
points to answer the question:

4.3.1.1 What is the property of interest?

This is extensively discussed in chapter 2. We may identify two types of properties:

Single phase properties, discussed in the first section of this fourth chapter. Figure 1.9
page 18, in the very first chapter of this book also illustrates which model can be used
depending on the process pressure-temperature location with respect to the phase
envelope.
Phase equilibrium properties, discussed in the second part of this fourth chapter. This
second type of property is generally much more difficult to calculate accurately.
Note that the simulation tools generally offer property packages that contain a
pre-defined selection of property-model combinations. An example of such combinations is

326

Chapter 4 From Phases to Method (Models) Selection

provided in table 4.7 hereinafter. This combination is often thermodynamically inconsistent

as it is rarely possible to have the same accuracy for different properties using the same
model. Yet, this situation is most often acceptable.

4.3.1.2 What is the fluid composition?

This issue is extensively discussed in the third chapter of this book, since the choice of model
parameters is directly related to the system composition. More specifically, one must be able
to distinguish entropic deviations from ideality (related to size asymmetry) and enthalpic
deviations (which are due to differing polarities and/or hydrogen bonding). In this fourth
chapter, a number of typical systems that may be of industrial interest have been investigated.

4.3.1.3 What are pressure and temperature conditions of the process?

There are two main families of fluid phase models: activity coefficient and equation of
state). Although equations of state can describe all fluid phase conditions (vapour, liquid,
supercritical), the use of activity coefficient models may have some practical advantages. As
discussed in section 2.2.2 (p. 52), the use of activity coefficients implies a heterogeneous
approach for calculating distribution coefficients, while a homogeneous approach is used
with equations of state. Table 4.6, taken from de Hemptinne and Behar [275], summarises
some advantages and disadvantages of both approaches.
Table 4.6 Heterogeneous and homogeneous approaches for vapour liquid distribution
coefficients calculation (taken from [275])
Homogeneous approach
Ki =

yi
xi

Advantages

Disadvantages

Ki =

iL
Vi

Heterogeneous approach
Ki =

) ( ) ( ) ( )
Vi ( y, P, T )

i P, T Pi T i T i x, T
P

High pressures.
Phase envelope calculation,
including the near-critical region

Improved accuracy because of the large

choice of models, in particular for
non-ideal mixtures

Limited by the choice of an

appropriate mixing rule

Limited to pressures below 1.0 MPa*

No phase envelope calculation
Requires the asymmetric convention in
case of supercritical components
Unable to take into account free-volume
effects in polymer-solvent systems

* there is no truly theoretical reason for this limit to 1.0 MPa: use of a Poynting correction can enlarge the validity
domain up to 1.5 MPa, but above this pressure, one of the components is often supercritical, resulting in the need to
use the asymmetric convention.

The use of the heterogeneous approach, although very powerful for non-ideal mixtures,
is in principle limited to low pressure applications. It requires the use of:

Pure component property correlations. For database components, accurate correlations

exist. Otherwise, other methods should be employed, as discussed in section 3.1.1.2
(p. 109). A clear difficulty exists when one of the components is supercritical Henrys

Chapter 4 From Phases to Method (Models) Selection

327

law should be used in this case, leading to the much more complex asymmetric convention as explained in section 2.2.3.1.A (p. 63).
An activity coefficient model. In this case, a distinction is made between
predictive models (less accurate, but can be used without data, like the regular solution or
the Flory models) and correlative models (require many experimental data, or, equivalently, a well-furnished parameter database, e.g. NRTL or UNIQUAC). This is
discussed in section 3.4.2.6 (p. 188). Note that UNIFAC is a very powerful alternative
when no data exist, and that COSMO-RS or COSMO-SAC can now be used to create
quite accurate pseudo-experimental values for liquid phase activity coefficients.
Today, there is a clear trend in favour of the homogeneous approach, both because it
allows a coherent description of all fluid phases (and thus describes critical points), and
because new, powerful equations of state have become available:

The traditional limitations of the cubic equations of state have been overcome by the
GE-based mixing rules (section 3.4.3.4.E.b, p. 214). This approach requires a large
number of data for fitting and validation. The PSRK method, which uses UNIFAC
can be considered predictive. The PPR78 approach, which uses a Van Laar type GE
model is also predictive but can only be applied to mixtures of non-polar compounds
and supercritical gases.
Molecular based equations offer improved predictivity (SAFT is discussed as an
example here, in section 3.4.3.5, p. 216). Its use with group contributions is now
extensively studied by several research groups, and it is expected that this method will
become increasingly used in the future.

4.3.2 Decision tree

Nevertheless, it may be useful to provide a decision tree for vapour-liquid phase equilibrium
calculations, as has already been attempted by other authors [275, 276]. It might help the
beginning engineer in his search. In the figure 4.59, we aim at finding an approach that is
suited for pre-studies. For more advanced studies, a full analysis of key components as
discussed in chapter 3, yielding a more accurate method, is needed.
In figure 4.59, the reader will be guided through a number of key questions, labelled with a
greek letter, and further explained below (comments to figure 4.59). At the end of each selection
process, the letter helps positioning the reader in table 4.7 for additional elements regarding the
choice of the thermodynamic method. This table provides some complementary information
regarding the choice of single-phase properties. For cubic EoS (CEOS), the importance to verify
either the alpha function or the mixing rule parameters is stressed using either the or kij
symbol followed by an exclamation mark. Some cases, that are particularly difficult to model,
are indicated with a red arrow inviting the engineer to search for additional data.
The meaning of the colours is as follows: yellow means heterogeneous approach, green
means homogeneous approach (with an equation of state). Generally, the high pressure
(equation of state, green) approaches are more complex, but also applicable at low pressure.
The significance of the keywords used, both in table 4.7 and in figure 4.59, is provided in
table 4.8.

CEOS-GE
CPA
SRKKD

C
S 4.2.5.
PPR78
CEOS
alpha; kij!

No

No

PPR78
CEOS
kij!

I
S 4.2.2.

Critical Yes

PPR78
CEOS

J
S 4.2.2.

BK10

K
S 4.2.2.

Yes

1:
pseudo?

CEOS
alpha!

L
S 4.2.2.

No

CEOS
kij(T)!

GS

M
S 4.2.3.

Supercritical gases

Low
pressure

Yes

hydrocarbons and
their associated gases

2: size
asymmetry?

2:
P > 0.1 MPa

3:
No
close to critical

Yes

watch for data

watch for data

SAFT
Lattice-Fluid
Free Volume

watch for data

Flory
UNIQUAC

H
S 4.2.2.

Close Yes
boiling

3:
azeotropy?

Risk for LLE?

CEOS-GE
SAFT
PSRK
GCA

High

Yes

G
S 4.2.7.1

pressure

2:
P > 1 MPa

F
S 4.2.7.

Low

No

Entropic

Yes

1:
only HC?

Risk for LLE?

UNIQUAC
NRTL
UNIFAC

High

E
S 4.2.6.

pressure

D
S 4.2.6.

Low

2:
P > 1 MPa

No

1: size
asymmetry?

Decision tree for vapour-liquid equilibrium calculations.

Figure 4.59

SW

Henry
Pitzer

e-NRTL
e-UNIQUAC
e-UNIFAC
Pitzer

No

B
S 4.2.4.

1:
reactive?

No

1:
water+ HC?

no salts

1:
electrolyte?

A
S 4.2.5.

Yes

Salts

Yes

Yes

No

Enthalpic

No

328
Chapter 4 From Phases to Method (Models) Selection

1:
electrolyte?

1:
electrolyte?

Explanation

An aqueous phase is present, that contain no other polar component, and no salt. In some applications, it may be considered pure
water (use a decant option). This will still let water dissolve in the other phases, but the aqueous phase is approximated as a pure
component. In some cases, it may be important to know the true composition of the aqueous phase, in which case the empirical or
Henry-constant models discussed in section 4.2.4 (p. 293) can be used. The CPA EoS is well-suited for this problem. Yet, any cubic
EoS can also be used here, provided that the alpha function is validated and a complex mixing rule (at least two binary interaction
parameters: kij and kji as in the SRKKD Eos or a GE-based mixing rule as discussed in section 3.4.3.4.E.b (p. 214). These models are
also used for physical treatment of acid gases (section 4.2.5.3, p. 310).

The presence of electrolytes (salts) will strongly affect the result: in the presence of these ionic species, electrolyte models, briefly
introduced in section 3.4.2.5 (p. 186), can be used with some success (Pitzer is most often used for complex electrolyte systems). At
high pressures, an equation of state should be used. The Soreide and Whitson equation (SW) is here recommended although it can
only handle NaCl salt, and no other polar component than water.

Close boiling systems often lead to the presence of azeotropes (useful or not). This is discussed in section 4.2.2.1 (p. 271) and requires
validation on experimental data. The cubic EoS, which can be recommended in this case, must be well-tuned to both pure component vapour
pressures (the so-called alpha function) and mixture bubble pressures (key binaries), as discussed in some details in section 3.4.3.4 (p. 204).

For mixtures that exhibit entropic non-idealities at high pressure conditions, an equation of state that takes into account free
volume is required, as liquid-liquid phase split may be observed. The SAFT or Lattice-Fluid EoS (Sanchez-Lacombe) are designed
for these systems.

For mixtures that exhibit entropic non-idealities and moderate pressures, below 1 MPa, the Flory theory provides a fully
predictive scheme, but it is most often combined with a local composition model, as in the UNIQUAC theory (which requires
interaction parameters). The equations of state in item G is also adequate in this case.

Water hydrocarbon mixtures are complex mixtures because of their very different chemical affinities. The properties of the
aqueous phase require specific models (choose yes), as explained in detail in section 4.2.4 (p. 293). If other strongly polar
components are present, mutual solubilities between the hydrocarbon and aqueous liquids strongly increase, and the right branch
should be chosen (choose no), as discussed in section 4.2.6 (p. 316).

This question refers to the presence of supercritical gases in the system (see section 4.2.3, page 288). The answer is yes when a
significant amount of H2, N2 is present in the system. If so, the traditional wisdom is to recommend the Grayson-Streed (GS) method,
but it is generally safer (especially for equilibria with heavy ends) to use a cubic EoS on the condition that temperature-dependent
interaction parameters (kij) are available. Methane can in some cases be considered as strongly supercritical (especially at high
temperature), but may also lead to close-to-critical conditions, as discussed in G below, when temperature is low.

When it is attested that the mixture is non-ideal, a distinction should be made between enthalpic and entropic deviations from
ideality (discussion in section 3.4.2.1, page 173). Entropic deviations results from mixtures with molecules of strongly different sizes
or shapes (size asymmetry); enthalpic deviation is related to different interaction energies between the species.

The first, basic, question is related to the presence of other than hydrocarbons (except gases) in the mixture. The branch on the
right corresponds to non-polar systems where the three parameter corresponding states principle can be applied. This branch is also
well adapted to petroleum cuts. Non-hydrocarbons gases (CO2, H2S) may also be described on the hydrocarbon branch.
For mixtures that contain non-hydrocarbons (that include heteroatoms, i.e. O, S, N), the other branch should be chosen.

Comments to figure 4.59.

2:
P > 1 MPa

3:
azeotropy?

Label

2:
P > 1 MPa

1:
water+ HC?

asymmetry?

2: size

1: size
asymmetry?

1:
only HC?

Question

Chapter 4 From Phases to Method (Models) Selection

329

2:
P > 1 MPa

2:
P > 1 MPa

3:
close to critical

1:
reactive?

2:
P > 0.1 MPa

1:
pseudo?

1:
pseudo?

Explanation

In the case the heavy end is paraffinic, for example (wax treatment), it is recommended to use a cubic EoS, for which the validity of
the alpha function has been extended to heavy components (as in PR78).

In some cases, very low pressure calculations are needed, which means that the liquid is a heavy component. Very often, petroleum
pseudo-components are used (typically for vacuum distillation). In this case, the automated API nomograph BK10 (which is nothing
but an improved Raoults law) is traditionally recommended.

If pressure is larger than 0.1 MPa, and no specific azeotropic condition is feared, the traditional cubic EoS can be used without great
danger. This is the case for stabilization columns, for example.

In some cases, chemical reactions in the aqueous phase strongly affect the vapour-liquid equilibrium (e.g. amine treatment).
Specific packages (that include simultaneous phase and chemical equilibrium calculations) must be used for these reacting systems.
They very often use the electrolyte version of NRTL or UNIQUAC as discussed in section 3.4.2.5 (p. 186). Some simulators propose
a special sour gas package for acid gas + water mixtures.

The process may be focusing on components that are close to their critical points (either gases, as CO2 or H2S, or light
hydrocarbons). Only a homogeneous method with an equation of state can be used. Cubic EoS are particularly well-suited because
their very construction makes that the pure component critical point is exact. For mixtures, the prediction should be used with
caution. The PPR78 EoS has been designed for this type of problems. The other properties (enthalpic or density), require a high
quality virial EoS (as recommended by NIST, see also section 3.4.3.3, p. 199).

In the presence of a mixture of very polar components (as for example discussed in section 4.2.6, p. 316), the activity coefficient
models are limited in pressure. At pressures higher than 1 MPa, an equation of state should be used. A cubic EoS can do the job if an
appropriate activity coefficient model is included in the GE-type mixing rule (as in the case of the PSRK EoS). The SAFT model is
increasingly used in this context.

In the presence of a mixture of very polar components (as for example discussed in section 4.2.6, p. 316), it is generally
recommended to use an activity coefficient model, with well-documented binary interaction parameters, on the condition that
pressure is not too high. UNIQUAC and NRTL are often used indifferently, and UNIFAC (section 3.4.2.4.C, p. 184: the Dortmund
version is considered better) is preferred when no parameters are available. Note that it is often possible to fill automatically the
UNIQUAC or NRTL parameter matrix using UNIFAC. In case of risk of liquid-liquid phase split, it is essential to validate the model
with experimental data, because a slight change in conditions may have a great effect on LLE. The vapour phase is often considered
ideal, but the Hayden-OConnell virial coefficient can be needed for hydrogen-bonding systems. Sometimes, special approaches are
required (hexamer forming of HF, for example). The equations of state discussed under label E are increasingly used for low pressure
calculations.

Comments to figure 4.59 (contd).

Label

Question

330
Chapter 4 From Phases to Method (Models) Selection

331

Chapter 4 From Phases to Method (Models) Selection

Table 4.7 Model Choice depending on the Result of the Selection Process in Figure 4.59
Fugacity
(equilibrium)
e-NRTL,
e-UNIQUAC
A

Enthalpy/entropy
Correlation
+ include excess

e-UNIFAC
Special Sour
Packages

Density

Watch for parameters

Specific

No other polar
component than water

Specific
SW
CEOS -GE

CPA

CPA

CEOS with specific

mixing rules

CEOS with specific

mixing rules

UNIQUAC, NRTL

Correlation
+ include excess
properties

UNIFAC

Correlation

CEOS -GE

CEOS -GE

Requires parameter fit

SAFT

SAFT

Group contribution
methods may make this
model predictive

GCA

Often used for biofuel

applications

VTPR

Predictive, hence less

accurate; more recent
version of PSRK

SAFT
GCA
VTPR

VTPR

Requires parameter fit

Aqueous phase: use
water; hydrocarbon
phase: use API

Correlation

Good for mixed

solvents
Most simulators offer
specific solutions (e.g.
SRKKD) for water
+ hydrocarbons
Watch for parameters,
especially when using
excess enthalpy

Predictive, hence less

accurate

PSRK
F

Only NaCl; no other

polar component than
water

CEOS -GE
C

Predictive

Specific

Pitzer

Comments

UNIQUAC,
Flory

Correlation

Correlation

No LLE

SAFT

SAFT

SAFT

Group contribution
methods may make this
model predictive

Correlation

Group contribution
methods may make this
model predictive

Lattice Fluid
(Sanchez-Lacombe)
UNIFAC
Free Volume

Predictive

332

Chapter 4 From Phases to Method (Models) Selection

Table 4.7 Model Choice depending on the Result of the Selection Process in Figure 4.59 (contd)
Fugacity
(equilibrium)

Enthalpy/entropy

Density

CEOS

Lee Kesler

Lee Kesler (API)

PPR78

Lee Kesler

Lee Kesler (API)

Comments
Check alpha parameter
on vapour pressures;
Evaluate mixing rules
(kij) on mixture data
Close to the critical
point, it is extremely
difficult to have
accurate predictions of
the single phase
properties
Check alpha parameter
on vapour pressures;
Evaluate mixing rules
(kij) on mixture data

CEOS alpha, kij

Lee Kesler,
MBWR

Lee Kesler
MBWR

CEOS,
PPR78

Lee Kesler

Lee Kesler (API)

BK10

Lee Kesler

Lee Kesler (API)

For pseudo-components
only

PR (SRK), alpha
PPR78

Lee Kesler

Lee Kesler (API)

Check alpha parameter

on vapour pressures

PR (SRK), kij

Lee Kesler

Lee Kesler

Evaluate mixing rules

(kij) on mixture data (a
temperature dependent
kij is often essential)

GS

Lee Kesler

Lee Kesler

Not for hydrogen

solubility in heavy
components

333

Chapter 4 From Phases to Method (Models) Selection

Table 4.8
Keyword

Keywords for Models

Description

Section
of this book

Page

API

API correlations: these are very similar to those

presented in section 3.1.1.2

3.1.1.2

109

Aqueous phase:
use water

Specific water density correlation, as proposed

by NIST (steam tables)

3.4.3.3.C

200

BK10

Improved Antoine correlations

CPA

Cubic Plus Association

3.4.3.5.B

218

e-NRTL,

Electrolyte NRTL

3.4.2.5

186

e-UNIFAC

Electrolyte UNIFAC

3.4.2.5

186

e-UNIQUAC

Electrolyte UNIQUAC

3.4.2.5

186

Flory

Flory activity coefficient model

3.4.2.3.B

180

GS

Grayson Streed

4.2.3

290

GCA

Group Contribution with Association equation

of state

3.4.3.5.B

218

Lattice Fluid
(Sanchez-Lacombe)

Lattice fluid Equation of State

3.4.3.6

219

Lee Kesler

Lee & Kesler method

3.4.3.3.C

202

Correlation

When considering the liquid phase, it may

be interesting to use library correlations for the
pure component, with an ideal mixing rule
(see section 2.2.2.2, p. 60). Most simulators offer
well-validated correlations

3.1.1

109

Correlation
+ include excess
(UNIQUAC, NRTL)

In addition to using library correlations,

for strongly non-ideal mixtures, the excess
property must be added, as calculated using
NRTL or UNIQUAC and eq (2.101), p. 62

MBWR

Modified Benedict Webb & Rubin EoS

3.4.3.3.C

203

NRTL

Activity coefficient model

3.4.2.2.C

177

Pitzer

Activity coefficient model

3.4.2.5

186

PPR78

Predictive Peng-Robinson with temperature

dependent kij. (Van Laar introduced in the PR EoS,
using a gE-mixing rule).

3.4.3.4.E

214

CEOS

Cubic Equation of State: Peng Robinson or

Soave-Redlich Kwong equations of state are used
indifferently

3.4.3.4

204

CEOS alpha

It is important to validate the alpha function of

cubic equations of state. The Twu correlation
generally improves the results

3.4.3.4.B

206

CEOS kij

A simple mixing rule can do it, but well-adjusted

binary interaction parameters are needed

3.4.3.4.E

212

334

Chapter 4 From Phases to Method (Models) Selection

Table 4.8 Keywords for Models (contd)

Keyword

Description

Section
of this book

Page

CEOS -GE

A complex mixing rule is needed, possibly using

several kij, but a GE-type mixing rule is best

3.4.3.4.E

212

PSRK

Predictive SRK (UNIFAC introduced in the

SRK EoS, using a GE mixing rule)

3.4.3.4.E

212

SAFT

Statistical Associating Fluid Theory

3.4.3.5.A

216

Soreide&Whitson

Equation of State

4.2.4

294

special Sour packages

Special, simulator-dependent, packages

specific

Special, simulator-dependent, packages

SRK

Soave Redlich Kwong (see above)

3.4.3.4

204

SRKKD

SRK with the Kabadi-Danner mixing rule

4.2.4

295

UNIFAC

Activity coefficient model

3.4.2.4.C

184

UNIFAC Free Volume

Activity coefficient model

UNIQUAC

Activity coefficient model

3.4.2.4.B

183

VTPR

Volume Translated Peng Robinson

3.4.3.4.E

212

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Ed. Sandler, S. I.; Marcel Dekker, Inc., 1994.
[2] Kiran, E. and Levelt Sengers, J. M. H. Supercritical Fluids; Fundamentals for Applications;
Kluwer Academic Publishers, 1994.
[3] Sadus, R. J. High Pressure Phase Behaviour of Multicomponent Fluid Mixtures; Elsevier
Science Publisher: Amsterdam, 1992.
[4] Poling, B. E., Prausnitz, J. M. and OConnell, J. P. The Properties of Gases and Liquids 5th
Ed.; McGraw-Hill: New York, 2000.
[5] Reid, R. C., Prausnitz, J. M. and Sherwood, T. K. The Properties of Gases and Liquids;
McGraw-Hill Book Company: New York, 1977.
[6] Reid, R. C., Prausnitz, J. M. and Poling, B. E. The Properties of Gases and Liquids 4th
Ed. McGraw-Hill Book Company: New York, 1987.
[7] Domb, C. Phase Transitions and Critical Phenomena, Academic Press, 2000.
[8] Anisimov, M. A. and Sengers, J. V. Critical Region in Equations of State for Fluids and Fluid
Mixtures; Ed. Sengers, J. V., Kayser, R. F., Peters, C. J. and White, H. J. Jr; Experimental Thermodynamics; Elsevier: Amsterdam, 2000.
[9] Maxwell, J. B. Data Book on Hydrocarbons; Van Nostrand Company, Inc: London
New York Toronto, 1950.
[10] API Technical Data Book Petroleum Refining, 3rd Ed. 6; American Petroleum Institute:
Washington, D.C., 1976.
[11] Wuithier, P. Le Ptrole: Raffinage et Gnie Chimique (Tome 1) Ed. Technip: Paris, 1972.