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Review
Recent Advances and Applications of Statistical Associating Fluid Theory
Sugata P. Tan, Hertanto Adidharma, and Maciej Radosz
Ind. Eng. Chem. Res., 2008, 47 (21), 8063-8082• DOI: 10.1021/ie8008764 • Publication Date (Web): 30 September 2008
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 Ind. Eng. Chem. Res. 2008, 47, 8063–8082 8063

REVIEWS

Recent Advances and Applications of Statistical Associating Fluid Theory

Sugata P. Tan,* Hertanto Adidharma, and Maciej Radosz
Soft Material Laboratory, Department of Chemical and Petroleum Engineering, UniVersity of Wyoming,
Laramie, Wyoming 82071

This review presents recent advances and applications of statistical associating fluid theory (SAFT), which
has been extended in the past few years, conceptually and practically, to improve its performance and to
represent thermodynamic properties of complex systems, such as associating polymers, polydispersed polymers,
aqueous electrolytes, dipolar and quadrupolar systems, ionic liquids, near-critical systems, interfacial
phenomena, crystallizable copolymers, gas hydrates, liquid crystals, biomaterials, and oil reservoir fluids, as
well as dynamic properties such as viscosity.

1. Introduction on the right-hand side of eq 1. However, in SAFT-HR, the chain

It was here in this journal almost two decades ago that the
initial concept and practical applications of statistical associating
fluid theory (SAFT) were presented.1-3 These papers are among
the 12 most-cited articles4 since 1975 of this journal. The
engineering version of SAFT applicable to real fluids and fluid
mixtures, referred to as SAFT-HR (Huang-Radosz), was
proposed in two of those papers.2,3 The name of SAFT itself
was first introduced some time before,5 and the first equation
of state (EOS) example illustrating SAFT is now referred to as
SAFT-0.1 The number of papers reporting SAFT improvements
and applications since 1992 is presented in Figure 1.
There are extensive reviews of SAFT-related research in the
literature.6-8 Therefore, the goal of this review is to focus on
conceptual and computational improvements and practical
applications to complex systems developed in the past few years
since those reviews were published, unless earlier references
are needed for the discussion.
2. Conceptual Progress
2.1. Linear Chains of Identical Segments: How to Pick
a Reference. The SAFT residual Helmholtz energy, ÃR, is
usually defined as a series of terms approximating different free
energies resulting from molecular interactions, which can be
grouped as reference terms and perturbation terms, for example,
for SAFT-HR
term is approximated with a chain model of hard spheres (rather
than an exact chain model of argon-like spheres).
An alternative grouping of terms was proposed by Gross and
Sadowski9 in their perturbed-chain version of SAFT (PC-SAFT),
where, instead of the dispersion term, the chain term becomes
part of the reference group:
à R ) (à hs + à chain) + à disp + à assoc + ... (2)
As a result, the PC-SAFT reference reflects a chain of hard
spheres, while the dispersion term becomes a perturbation term,
which reflects interactions between hard chains, not between
segments. The PC-SAFT dispersion term is obtained from a
fitting to experimental data for n-alkane series9 after an
intermediate step assuming a Lennard-Jones perturbing potential
in calculating two integral expressions that were previously
derived for square-well chains.10 Chiew’s11 average interchain
segment-segment radial distribution function (RDF) is used
in the integrals.
These concepts of EOS reference are illustrated in the upper
part of Figure 2, interacting argon-like spheres for SAFT-HR
(a) and chains of hard spheres for PC-SAFT (b). The lower
part of Figure 2 illustrates the final interacting chains.

à R ) (à hs + à disp) + à chain + à assoc + ... (1)

The superscripts on the right-hand side refer to hard-sphere,
dispersion, chain, and association terms, respectively. The terms
in parentheses in eq 1 allude to a spherical-segment reference,
of which the properties are approximated by a repulsive hard-
sphere term and an attractive dispersion term. In SAFT-HR the
dispersion term2 is approximated using an inverted square-well
potential energy fitted to argon. In other words, the SAFT-HR
reference is an argon-like sphere, which becomes a building
block (segment) of a covalently bonded linear chain. When the
segments form a chain, the energy given up by the chain
formation is accounted for by the chain term, i.e., the third term

* To whom correspondence should be addressed. Tel: 307-766-6772.

E-mail: sptan@uwyo.edu. Figure 1. The progress in SAFT work (1992-2007).

10.1021/ie8008764 CCC: $40.75  2008 American Chemical Society

Published on Web 09/30/2008
8064 Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008
Figure 2. Reference (upper) used for chain molecules (lower) in (a) SAFT-
HR and (b) PC-SAFT. Open circles are hard spheres and filled circles are
spheres with dispersion interactions.
Figure 3. (a) Two monomers (M) form a bond to become neighbors (N) in
a chain, e.g., in SAFT-HR. (b) Four monomers (M) form two dimers (D)
that in turn form a bond and become neighbors (N) and next-neighbors (n)
in a chain, e.g., in PC-SAFT-D.
Regardless of the EOS reference in use, the SAFT chain term
is rooted in Wertheim’s12 idea of the covalent bond as that
between two associating hard spheres in the limit of total
association. All covalent bonds in a chain are treated as dimer
bonds. When compared to simulation data, such a chain term
becomes less accurate for chains with more than eight segments,
particularly in the high-density region.13 This is due to Wer-
theim’s first-order perturbation (TPT1) approximation of the
association, in which all properties can be derived from the
properties of monomers (free segments) alone. This provides a
clue how to make the chain term more accurate for longer
chains.
SAFTEOSbasedondimerreferencehavebeeninvestigated.14-16
The dimer reference incorporates the structural information on
the dimer fluid; thus, it takes into account not only the
neighboring segments in forming the bonds but also the next-
neighbor effects. This dimer approach is shown in Figure 3b,
where the chain is formed through an intermediate step of
forming dispheres, compared to the monomer approach of
SAFT-HR in Figure 3a.
Recently, such a chain-of-dimers approach in PC-SAFT-D
(D for dimer)17 was demonstrated to work better for long-chain
molecules, such as polymers, than a chain-of-monomers in PC-
SAFT. This dimer version utilizes the hard-disphere RDF (ghd),
in addition to the hard-sphere RDF (ghs), to calculate the chain
term as follows:
∑ x ( 2 - 1) ln g
mi mi
à chain ) - ∑x 2i ii (σii) -
ln ghs i
hd
ii (σii)
i i
where mi is the number of segments in molecule i (mi g 2).
Figure 4. (a) Homosegmented chain and (b) heterosegmented chain.
The chain formation is assumed to occur in two steps. The first
step is the formation of dimers from monomers, as in TPT1
(the first term of eq 3). The second step is the formation of
chains from dimers. The cumulative effect of bonding in the
second step is estimated by multiplying the contribution due
to forming one tetramer from dimers by the number of bonds
required to form a chain of dimers (the second term of eq
3). Both RDFs are calculated at a contact distance of hard
spheres σ.
The expression in eq 3 is applicable to a homosegmented
chain, that is, a chain of identical segments. This expression
could in principle be generalized to heterosegmented molecules,
that is, molecules composed of different segments, through an
RDF originally developed15 for mixtures of hard dispheres:
1 + 2ζ2(σiσj/σij) + 26.4503ζ26.17(σiσj/σij)6.17
ij (σij) )
ghd (4)
2(1 - ζ3)2
with σij ) (σii + σjj)/2, and ζ2 and ζ3, defined as usual.
In approaches presented in this section, therefore, all mol-
ecules, small and large, as large as polymeric chains, are
approximated as effective homopolymer chains, that is, linear
SAFT-HR or PC-SAFT chains composed of identical segments,
similar to all conventional polymer equations of state. Such
effective-homopolymer models can realistically represent real
nonlinear heterosegmented molecules, such as copolymers, by
fitting the segment parameters to specific real molecules. As a
result, however, the segment parameters become molecule-
specific. The challenge, therefore, is how to account explicitly
for linear and nonlinear molecules composed of different
segments, which is addressed in the next section.
2.2. Heterosegmented and Branchy Chains: How to
Account for Complex Shapes, toward Universal Segment
Parameters. Since SAFT parameters are inherently segment-
specific, rather than molecule-specific, it is tempting to make
such segments and their parameters transferable from molecule
to molecule, perhaps even universal, toward a user-friendly
SAFT that does not require fitting new parameters for new
molecules, somewhat reminiscent of group-contribution ap-
proaches. This goal calls for relaxing the effective-homopolymer
(homosegmented) SAFT model, toward an explicit copolymer
(heterosegmented) SAFT model, hetero-SAFT for short, which
is applicable to small heterosegmented molecules as well. An
example of a small homosegmented molecule and a small
heterosegmented molecule is illustrated in Figure 4.
Such a heterosegmented SAFT concept has been proposed
and demonstrated for real fluids by Banaszak et al.18 by
extending SAFT-HR to linear and nonlinear molecules com-
posed of different segments. Adidharma and Radosz integrated
this concept into a square-well version of SAFT referred to as
SAFT1.19 SAFT1 turns out to be effective for systems contain-
ing branched polymers and branched random copolymers20-22
as well as diblock copolymers.23 Similar approaches have also
been implemented with PC-SAFT24,25 and SAFT-VR (variable
range).26,27 For example, hetero-SAFT-VR has been demon-
(3) strated to work for perfluoroalkanes and perfluoroalkylalkane
diblock surfactants.28-31 An evaluation of homo- and copolymer
SAFT models is available in ref 32. In all these approaches,

Figure 5. United atom representation of propane molecule with two different
functional groups (open circle for methylene -CH2- and filled circle for
methyl -CH3): (a) tangent and (b) fused.
Figure 6. Molecular structure: (a) PEO and (b) PEG. Diamonds and triangles
are associating sites of different type.38
segments may or may not approximate monomer or functional
groups, but they are not forced to be identical with them.
When segments are forced to be identical with functional
groups, one aims at a group-contribution (GC) version of SAFT.
In a version proposed by Tamouza et al.,33 known as GC-SAFT,
the parameters of different functional groups are averaged out
to give the segment parameters for the molecule, which basically
means that GC-SAFT is a homosegmented model with the
parameters averaged from the heterosegmented model. GC-
SAFT utilizes SAFT-01 and SAFT-VR34 as the working EOS,
but similar GC approaches were proposed with PC-SAFT for
hydrofluoroethers35 and with simplified PC-SAFT for poly-
mers36 using slightly different parameter averaging methods.
Jackson’s group proposed a more rigorous GC approach
building on hetero-SAFT-VR,26 which resulted in SAFT-γ.37
Instead of a TPT1 chain of identical tangent spheres, the SAFT-γ
chain consists of fused hetero united-atom groups, which allows
for including bond bending and torsional energies. An example
illustrating tangent and fused hetero groups for propane is shown
in Figure 5.
To accommodate such a fused hetero model, a new parameter
is introduced, i.e. the shape factor, Sk, that corresponds to the
fraction of the spherical united-atom group that contributes to
the properties of the molecule. The classical SAFT segment
number parameter mi is consequently no longer needed. Instead,
a molecule i is said to have a total number of groups
NS
γi ) ∑ν k,iSk (5)
k)1
where νk,i is the number of united-atom groups of type k in
molecule i. The summation is over the number of segment types
NS existing in the molecule. Tamouza’s GC-SAFT33 has the
chain length parameter, essentially the same as the segment
number parameter mi, which is similar to eq 5, but now Sk is a
fitted parameter describing the contribution of group k to the
chain length; in this case mi ) γi.
In SAFT-γ, the cross group energy parameters are needed in
the same spirit as SAFT binary interaction parameters, kij, except
they apply to all pairs of different functional groups, even when
these two groups belong to the same molecule. This issue is a
challenge that will have to be addressed in further development.
As usual with group-contribution approaches, each new group
added to the database requires a fitting based on the parameters
of the previous groups in the database, not only to obtain its
set of “self” parameters but also the cross energy parameters
with every other group in the database. Such an incremental fit
may and likely will require a global parameter readjustment
for all groups in the database, which can deteriorate the
performance of the EOS.
Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008 8065
3. Computational Algorithm Progress
3.1. Associating Segments and Chains. One of the major
advantages of SAFT is that it explicitly accounts for association
due to donor-acceptor bonding, such as hydrogen bonding
among groups and segments in the spirit of Wertheim’s seminal
TPT1, without invoking the concept of chemical equilibria. One
of the challenges in this area that has been addressed turns out
to be computational, as discussed in this section.
The calculation of the association Helmholtz energy term in
SAFT, i.e., the fourth term on the right-hand side of eqs 1 and
2, requires the mole fractions of associating but nonbonded
molecules. A common method of calculating the mole fraction
of component i with nonbonded sites of type j is from the so-
called mass-action equation:
1
Xij ) n s
i ) 1, ..., n; j ) 1, ..., s (6)
1+F ∑x ∑ k SlkXkl∆ljki
k)1 l)1,l*j
where F is the number density, xk is the mole fraction of
component k, Slk is the number of sites l in component k, and
∆ljki is the bond strength between site type l in component k and
site type j in component i. The upper bounds of the summations
are the number of components n and the number of types of
the associating sites s.
Equation 6 can be solved analytically for specific bonding
types tabulated in the original SAFT-HR paper.2 Though
specialized analytical versions of eq 6 and its derivatives offer
faster computation, their form is bonding-type-dependent, which
makes the coding system-specific. This means that each time
one changes a set of associating sites, for example, in going
from system to system or from one association model to another,
one must change the equations and hence the code. This inhibits
creative applications and hypotheses, for example, testing
different sets of bonding sites, which is often tempting, or
including a different set of associating components, which is
often needed, or both, because of the time-consuming effort of
rederiving and recoding the specific versions of eq 6 and its
derivatives.
This is also true for long-chain molecules with multiple
associating sites, such as PEG (polyethylene glycol) and PEO
(polyethylene oxide) shown in Figure 6.38 Each repeating unit
contains an oxygen atom carrying an electron lone pair; thus,
the two associating sites can be assumed to be of the same type
as that in the oxygen atom of water molecule or of some other
type, and the question is which of these types is the most
appropriate for PEG and PEO.
It was issues like this that motivated developing a generalized
procedure38 for solving eq 6 and its mth-order derivatives that
are needed for calculating thermodynamic properties:
[Λpq] [ ∂m
∂ξ1 ∂ ξ2 ... ∂ξm i ]
[X j] ) [Ψξp1ξ2...ξm] (7)
The matrix [Λpq] has an order of (s × n) × (s × n) with
p ) n(j - 1) + i i ) 1, ... , n; j ) 1, ... , s
(8)
q ) n(l - 1) + k k ) 1, ... , n; l ) 1, ... , s
The variable ξm can be density, temperature, or mole fractions,
one at a time, while the other variables remain constant in the
partial derivatives. If ξm is the mole fraction of component i
(xi) in the mixture, the mole fractions of the other components,
xk with k * i, remain constant as well as the temperature and
density.
8066 Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008

The elements of the matrix [Λpq] are the same for all
derivatives, regardless what the variables ξm are.

Λpq ) { FxkSkl∆ljki(Xij)2 , l * j
δki , l)j
(9)

where the Kronecker delta δki is 1 for k ) i, and 0 otherwise.

However, the elements of the matrix [Ψ] on the right-hand
side of eq 7, the order of which is (s × n) × 1, depend on the
variables ξm. The formulas of the elements of this matrix are
available in the literature for the first derivatives,38 second
derivatives,38 and third-order derivatives.39,40
The effectiveness of this algorithm is illustrated for aqueous
solutions of PEG, which are well-known for their closed-loop
temperature-composition (T-X) phase diagrams, with a limited
miscibility region at intermediate temperatures. Figure 7 shows
a SAFT1-calculated41 T-X phase diagram of such a system,
along with the experimental data42 for three molecular weights
of PEG, assuming only two types of associating sites in the
mixtures. The proposed generalized algorithm allows one to try Figure 7. Closed-loop immiscibility in aqueous PEG solutions.41
other assumptions for the association scheme without changing
the computation coding. 3.2. Polydispersity. One of the generic challenges in ther-
Recent applications of this generalized method illustrate a modynamics is how to account for nonuniform components,
need for a flexible algorithm that can be applied to a large such as polymers and oil fractions, that have the same or nearly
number of association cases43 and a need for high-order the same chemical structure but a continuously distributed
derivatives of Helmholtz energy such as in cross-over SAFT molecular weight or, less commonly, have nearly the same
for near critical systems.39,40 molecular weight but a continuously distributed chemical
This generalized method is also useful, for example, for structure. A common example of the former is polymer
modeling associating systems that allow bonding between sites polydispersity. An example of the latter is a compositional
of the same type, not just donor-acceptor bonding described distribution of a nearly monodisperse copolymer fraction, which
above, such as the hydrophobic association among protein may, for example, result in crystallizability distribution. How-
molecules. In this case, we first remove the l * j restriction ever, the treatment of compositional distribution has not been
from the mass-action equation (eq 6) and its derivatives. Second, developed as rigorously as that of polydispersity, which is
we replace eq 9 for the elements of matrix [Λpq] by discussed in this section.
A common approach to molecular nonuniformity of oil or
Λpq ) FxkSkl∆ljki(Xij)2 + δpq (10) polymer fractions is to lump similar molecules into discrete
where the Kronecker delta δpq is 1 for p ) q, and 0 otherwise.38 components referred to as pseudocomponents; for example,
A different approach in formulating molecular association pseudocomponents having different molecular weights are used
was proposed by introducing a mathematical Q-function at a in PC-SAFT46,47 applications to polymer fractions. The chal-
specified temperature, volume, and composition44,45 (in dimen- lenge is how to characterize and lump individual components
sionless form) (how to define pseudocomponents) because the larger the
number of pseudocomponents, the more accurate the representa-
n
tion, but the greater the number of equations to solve, the longer
Q(X) ) ∑ x ∑ S (ln X
i i
j
i - Xi + 1) -
j j
the computing times.
i j
In order to start addressing this problem, let us observe in
n n
F
2 ∑∑xx ∑∑S X S X ∆
i k
j j l l
i i k k
lj
ki (11)
most SAFT-based EOS that, for large molecules such as
polymers, the number of segments m is directly proportional to
i k j l
the molecular weight M (B is a constant):
where the maximum of Q is located exactly at the fraction of
nonbonded molecules as described by the mass action equation m ) BM (13)
48
(eq 6). The maximum value of Q is equal to the association Using this proportionality, Jog and Chapman found that,
term of the residual Helmholtz energy.44 for a polydisperse polymer component, the residual Helmholtz
Consequently, the first derivatives of the association term can energy terms and the corresponding compressibility factors can
be calculated in a simple way, for example that with respect to be expressed as functions of number-averaged molecular weight
a variable, ξ: (Mn) of the polymer and the overall polymer mole fraction xp
that is defined as
∂à assoc ∂Q
∂ξ
)
∂ξ ( ) Xij
(12)
xp )
n

where the partial derivative on the right-hand side is calculated
at constant Xij and constant variables other than ξ, so that the
first derivatives of Xij is never needed. This fact substantially
speeds up the computation of many thermodynamics properties
that apply the first derivatives of Helmholtz energy such as
pressure and chemical potential.
∑x i (14)
i)1
where n is the number of pseudocomponents used to represent
the molecular weight distribution. They assumed that the
polymer pseudocomponents have exactly the same segments
and hence the same SAFT parameters; thus, the binary interac-
tion parameters (kij) between them can be set equal to zero.

The interaction parameters between any pseudocomponent and
the solvent segments are taken to be identical.
In this approach, the residual chemical potential of a
pseudocomponent i in phase R, which can be directly obtained
from the residual Helmholtz energy, and the logarithm of the
partition coefficient of pseudocomponent i between phase R and
phase β, which can be obtained from the equality of chemical
potential of pseudocomponent i in both phases, are linear
functions of the molecular weight Mi:
RR R R RR R R (right), where εw is the water dielectric constant and the small shaded circles
i ) µA (xP , Mn ) + Mi µB (xP , Mn )
µRR
xRi
ln Ki ) ln ) KA(xPR, MnR, xPβ, Mnβ) + MiKB(xPR, MnR, xPβ, Mnβ)
xβi
In a cloud-point calculation, the composition in one of the
phases is known, i.e., the same as that of the feed, xiR ) ziR.
According to eq 15b, the composition in the other phase, xiβ,
can be calculated if KA and KB on the right-hand side are known.
Therefore, KA and KB are the variables to solve for in addition
to the densities of the phases, FR and Fβ. There are four equations
to solve in the phase equilibrium, two of which come from the
expressions of KA and KB in terms of chemical potentials, while
the other two are the equality of pressure and the equality of
chemical potential of the solvent in both phases.
Note that KA and KB, also µA and µB, are the same for all
pseudocomponents. Therefore, additional pseudocomponents
will not increase the number of phase-equilibrium equations,
which is a significant computational advantage for polydisperse
polymer systems. Behme et al.49 later proposed a more general
algorithm, called POLYMIX, that can be used in any segment-
based EOS, including those other than SAFT. This general
algorithm was used with PC-SAFT for polydispersed associating
copolymer solutions.50
Later, the expressions in Jog and Chapman’s approach are
recast in terms of density moments to compare with another
version that uses continuous distributions,51 as well as with a
third approach known as the moment method,52 where the
number of equations to be solved is also independent of the
number of pseudocomponents.
4. Applications in Electrically Charged Systems
4.1. Aqueous Electrolytes: From Single-Salt Solutions
to Brine. Aqueous electrolytes are important in numerous life
and energy systems, such as protein solutions and separations,
drug- and gene-delivery systems, water- and CO2-driven oil
recovery, and CO2 storage in saline aquifers, just to mention a
few examples, where a realistic approximation of electrostatic
interactions due to the presence of ions is needed to predict
their impact on the macroscopic and microscopic solution
properties. SAFT approximations are attractive because they
allow for estimating the solution density, and hence the pressure
effects, in contrast to common activity-coefficient solution
models.
Most of SAFT work on electrolytes utilizes the mean
spherical approximation (MSA), which accounts for the long-
range Coulombic ion-ion interactions. In the primitive model
(PM)53 of MSA, the solvent is assumed to be uniform and
represented by the medium dielectric constant. If the ions are
further assumed to have equal diameters, the approximation is
referred to as the restricted primitive model (RPM).54 MSA ideas
are illustrated in Figure 8 for RPM, PM, and a nonprimitive
model that has a molecularly realistic representation of water.
Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008 8067
Figure 8. MSA of aqueous electrolytes: restricted primitive model (left),
primitive model (middle), and molecularly realistic (nonprimitive) model
(15a)
are water molecules.
Examples of SAFT models that have been applied with RPM
are SAFT-VRE,55,56 SAFT1-RPM,57,58 and SAFT2,59,60 where
(15b) an extra perturbation term is added to eq 1 to account for the
impact of ionic interactions on the residual Helmholtz energy,
which is
3x2 + 6x + 2 - 2(1 + 2x)3⁄2
Ãion ) - (16)
12πFd3
where F is the solution number density, d is the hydrated
diameter, and x is a dimensionless quantity defined by
x ) κd (17)
where κ is the Debye inverse screening length given by
κ2 ) R02 ∑Fz j j
2
(18)
j
and
4πe2
R02 ) (19)
εwkT
In eq 19, εw is the dielectric constant of water, F j is the
number density of ion j, zj is the valence of the charged ion j,
e is the charge of an electron ()-4.803 × 10-10 esu), k is the
Boltzmann constant, and the summation is over all ions in the
mixture.
The implementation of the ionic term expressed by eq 16
can vary from one SAFT model to another. For example, the
type and number of EOS parameters may vary, and they can
be defined with respect to individual ions or with respect to
salts (ion pairs). In the individual-ion approach, the ion-specific
parameters are universal and hence transferable from salt to salt
containing the same ion. Such an approach, therefore, can reduce
the number of parameters needed to represent electrolytes. In
the salt approach, the salt-specific parameters are derived from
experimental data and hence unique to that salt.
SAFT257,58 is an example that combines the individual-ion
and salt approaches. While it has universal parameters for each
individual ion, the hydrated diameter in eq 16 is derived from
the salt properties and hence is salt-specific. However, a version
of SAFT2 with individual-ion parameters only is also available.61,62
In SAFT-VRE,55,56 the hydrated diameter is simply replaced
by the molar average of Pauling diameters of the ions in a
solvent-free basis, so that the EOS has individual-ion parameters
only.
Actually, in addition to the long-range ionic interactions
represented by eq 16, other weaker interactions56 may be
considered, for example, the ion pairing around the critical
temperature of water due to the decrease of the water dielectric
constant and the association between water and the ions that is
responsible for their hydration.
Replacing RPM by PM, i.e., allowing ions to have different
diameters, does not improve the EOS performance.41 Liu et al.63
8068 Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008
applies the nonprimitive model to be coupled with SAFT-0, in
which a low-density expansion of nonprimitive MSA is used
to account for interactions among ions and solvent dipoles.
These interactions call for adding a new electrostatic term to
eq 1 as follows:
à elec ) à ion + Ã∞sol + à dd (20)
The ionic term used on the right-hand side of eq 20 is an
RPM term, eq 16, but with effective average ion diameter d )
σ, a salt-specific parameter correlated from experimental data.
The next term is a solvation free energy at infinite dilution,
which accounts for the hydration, given by
-κ2 εw(λ) - 1
̰sol ) (21a)
4πF σ + σw/λ
where λ satisfies
( )
1 12πFxwµw2
(λ + 2)2λ2 1 - ) (21b)
εw(λ) kT
The subscript w in eqs 21a and 21b refers to water molecules.
The dielectric constant of water is defined as
λ2
εw(λ) ) (1 + λ)4 (22)
16
which implicitly indicates that εw is density- and concentration-
dependent, as it should. As a result, nonprimitive MSA does
not require empirical expressions for the dielectric constant, in
contrast to SAFT2 and SAFT-VRE coupled with primitive
models that require either an empirical expression for εw in
temperature or experimental values at various temperatures,
respectively.
The last term in eq 20 results from the dipole-dipole
interaction (discussed in the next section) in pure water. In
addition to this dipole-dipole interaction, Liu et al.63 also
applied the association due to hydrogen bonding between the
ions and water; in this case, monovalent ions are allowed to
have between 7 and 12 associating sites.
In all electrolyte SAFT models discussed so far, ions and
water molecules are spherical particles, so the chain term in eq
1 is set equal to zero. Furthermore, since the ions are assumed
to be hard spheres, there is no dispersive interactions between
them, though in recent versions of SAFT261,62 these interactions
are also included.
In the limit of treating the ions as point charges, the primitive
models reduce to the Debye-Hückle (DH) approximation, and
the solvation free energy in eq 21a reduces to Born’s hydration
model. For example, ePC-SAFT64 uses the DH approximation
to represent the ionic long-range interactions
κR02
à ion
)-
12πF ∑Fz j j
2
χj (23a)
j
where
3 3 1 homosegmented, so that all segments for a given molecule are
χj ) (
κ3σj3 2
+ ln(1 + κσj) - 2(1 + κσj) + (1 + κσj)2
2 )
(23b)
In the DH limit of σj f 0, χj in eq 23a reduces to unity.
However, ePC-SAFT is applied using eqs 23a and 23b still with
χj as a correction that accounts for the finite ion diameters σj.
Behzadi et al.65 couple PM MSA with Yukawa SAFT-VR
to represent both aqueous and nonaqueous (alcohol) electrolyte
solutions. More recently, Zhao et al.66 proposed a “semi-
nonprimitive” model coupled with their SAFT-VR+D, which
is still in an early stage of testing against Monte Carlo
simulations, to account for ion-dipole interactions, in addition
to the dipole-dipole and ion-ion interactions; no dielectric
constant is needed as an input in their model. Also, Liu et al.
proposed FMSA (first-order primitive MSA)67 with a short-range
Sutherland potential mapped with a two-Yukawa potential, as
well as ion-ion dispersion interaction and association between
water and ions (4 to 16 associating sites on the ions).
Table 1 provides a summary of SAFT-based EOS for
electrolytes discussed in this section. All these EOS approximate
ions as single spheres and explicitly account for long-range ionic
interactions as well as association of water molecules due to
hydrogen bonding. In order to illustrate examples of practical
applications, such SAFT electrolyte models have been demon-
strated to represent the properties of seawater (brine),60 the
salting-out effects in water + alkane solutions,68 and the
solubility of CO2 in NaCl-containing water solutions.69
4.2. Polarity: Systems with Dipoles and Quadrupoles.
Polar molecules, such as water, alcohols, ketones, and carbon
dioxide, have either a permanent dipole or quadrupole or both
or higher-order polarity. Since such polar interactions are
directional, it has been tempting to apply association theories
to approximate, at least qualitatively, the dipolar70 and
quadrupolar39,69 effects. A more rigorous approach to account
for multipolar contributions in SAFT framework was initiated
by Walsh et al.,71 followed by Müller and Gubbins72 for the
first SAFT water model, using a multipolar interaction term in
the form of a Padé approximant73
A2
à mp ) (24a)
1 - A3/A2
where A2 is the second-order term, related to two-body interac-
tions, and A3 is the third-order term, related to three-body
interactions, in the Helmholtz energy perturbation expansion.
In an application for dipolar chains, which was proposed by
Jog and Chapman,74,75 the dipole-dipole interaction term is
Add
2
à dd ) (24b)
1 - Add dd
3 /A2
The second- and third-order terms are calculated explicitly
by extending the expression of Gubbins and Twu76
2π F µi2µj2
2 )-
Add
9 (kT)2 ∑∑xxmmx i j i j pixpj
dij3
I2,ij (25a)
i j
µi2µj2µk2
5π2 F2
3 )
Add
162 (kT)3 ∑∑∑ xixjxkmimjmkxpixpjxpk I
dijdjkdik 3,ijk
i j k
(25b)
where the fraction of dipolar segments in molecule i, xpi, is
introduced as a fitted parameter. As usual, mi is the number of
segment i, xi is the mole fraction of molecule i, and dij is the
cross diameter of segments i and j. Here, the molecules are
identical.
There are two integrals in eqs 25a and 25b, I2,ij and I3,ijk,
which are integrated over the pair and triplet correlation
functions for the reference fluid, respectively. They can be
expressed analytically as:74,75
1 - 0.3618(Fd̄3) - 0.3205(Fd̄3)2 + 0.1078(Fd̄3)3
I2,ij )
[1 - 0.5236(Fd̄3)]2
(26a)
Table 1. Summary of SAFT-Based EOS for Electrolytes
ref electrolyte EOS parent EOS model for ionic term other interaction accounted for fitted parameters ions properties discussed
+ + + - - -
55 SAFT-VRE SAFT-VR RPM MSA 1 (water-ion) Na , K , Li , Cl , Br , I vapor pressure
(up to 100 °C), density
(up to 70 °C), one two-salt
solution (density only)
56 SAFT-VRE SAFT-VR RPM MSA; DH various parametric study Na+, Cl- vapor pressure
interactions tested (0 °C-100 °C),
density (25 °C), mean activity
coefficient (γ()
57, 58 SAFT1-RPM SAFT1 RPM MSA 1 (ion), 2 (water-ion), Na+, K+, Li+, Cl-, Br-, I- vapor pressure,
1 (salt), 1 (mixed salts) density, γ(, osmotic
coefficient (φ), solubility,
eight two-salt solutions
59, 60 SAFT2 SAFT2 RPM MSA 1 (ion), 2 (water-ion), 1 (salt) Na+, K+, Li+, Ca2+, Mg2+, vapor pressure,
Cl-, Br-, I-, NO3-, density, γ(,
SO42-, HCO3- φ, 31 two-salt solutions,
brine modeled as
five mixed-salts solution
61, 62 ion-based SAFT2 SAFT2 RPM MSA ion dispersion 1 (ion), 3 (water-ion), Na+, K+, Li+, Ca2+, Mg2+, density, γ(,
1 (cation-cation, in mixed salts) Cl-, Br-, I-, NO3-, φ (up to 200 °C and 1000 bar),
SO42-, HCO3-, CO32- 27 two-salt solutions, three
three-salt solutions, one four-salt
solution, brine (up to 200 °C)
63 no specified name SAFT-0 nonprimitive dipole-dipole, 1 (ion), 1 (water-cation), 1 (salt) Na+, K+, Li+, Rb+, Cs+, density, γ(, φ,
MSA ion association,water-ion Cl-, Br-, I- water activity
association, solvation
64 ePC-SAFT PC-SAFT DH 1 (ion), 1 (water-ion) Na+, K+, Li+, Cl-, vapor pressure
Br-, I-, SO42- (up to 70 °C), density
(20 and 40 °C), two
two-salt solutions
65 no specified name SAFT-VR PM MSA 2 (water-ion);for Na+, K+, Li+, Ca2+, Cl-, solvents: water
(Yukawa potential) nonaqueous solutions, 4 (water-ion) Br-, I-, NO3-, OH- and six alcohols;
vapor pressure,
density (up to 100 °C)
66 SAFT-VR+DE SAFT-VR+D semi-nonprimitive dipole-dipole; parametric study comparison with
MSA ion-dipole computer simulation
67 no specified name FMSA-SAFT PM MSA ion dispersion 2 (ion), 2 (water-ion) Na+, K+, Li+, Ca2+, Mg2+, density, γ(, φ, water
Cl-, Br-, I-, NO3-, SO42- activity, 19
two-salt solutions
Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008 8069
8070 Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008

1 + 0.62378(Fd̄3) - 0.11658(Fd̄3)2
I3,ijk )
1 - 0.59056(Fd̄3) + 0.20059(Fd̄3)2
with
d̄3 ) ∑xmd i i i
3
In eqs 25a and 25b, the dipole moment, µi, may take the
experimental value, or be estimated; for example, an average
of µ ) 2.7 D is used for the homologous series of ketones.77
Using the dipole-dipole term (eq 24b) in SAFT-HR and PC-
SAFT makes them more predictive for mixtures, thus giving
smaller binary parameters kij.77 Polar PC-SAFT has been used
in many dipolar systems such as ethers and esters78 and polar
copolymers.79,80 This version has also been demonstrated80 to
work with an alternative polar term originally developed by
Fischer and co-workers,81 which is an empirical expression fitted
to simulation data.
An alternative approach to modeling polar systems is PCP-
SAFT82 (perturbed-chain polar SAFT), proposed by Gross and
Later, Kleiner and Gross added a small correction due to the
(26b) polarizability, which resulted in PCIP-SAFT,84 where IP stands
for induced-polar. Also, Economou and co-workers proposed
an alternative PCP-SAFT85 using Nezbeda’s water approxima-
tion for the second- and third-order perturbation terms A2 and
(27) A3. The difference between the two PCP-SAFT versions, Gross
and Vrabec’s PCP-SAFT82 and Economou’s PCP-SAFT,85 is
how they treat associating molecules that have dipole moments,
such as water and alcohols. The former PCP-SAFT82 ignores
polarity, as the addition of the polar term did not improve the
representation of pure components and made it worse for the
mixtures.86 The latter PCP-SAFT,85 on the other hand, explicitly
accounts for the polarity contribution because it is found to be
as large as the dispersion contribution to the Helmholtz energy.85
A different approach, referred to as SAFT-VR+D,87,88 is
proposed for SAFT-VR with dipolar square-well spheres as the
reference. The dipole-dipole excess free energy is calculated
from Wertheim’s solution89 of the Ornstein-Zernike equation
for dipolar hard spheres with an MSA closure

[ ]
Vrabec, which also starts from eq 24b, but with some constants 8 (1 + κη)2 (2 - κη)2
in eqs 25a and 25b absorbed: Ã dd ) - (κη)2 + (32)
η (1 - 2κη)4 8(1 + κη)4
npinpj µi2µj2
2 )-
Add
πF
(kT)2
∑∑ xixj
mimj d 3 2,ij
I (28a)
where η is the reduced density and κ is a scaling parameter
determined from
i j ij

4π2 F2 npinpjnpk µi2µj2µk2 4π µ2 (1 + 2κη)2 (1 - 2κη)2

3 )-
Add
3 (kT)3 ∑∑∑ xixjxk I
mimjmk dijdjkdik 3,ijk
F )
3 kT (1 - κη)4
-
(1 + κη)4
(33)
i j k
(28b) In this approach, RDF for dipolar square-well monomers is
consequently used in estimating the chain term. Some results
where the previously regressed parameters xpi in eqs 25a and for pure compounds were shown in agreement with those from
25b are now defined as the ratio of the number of segments Monte Carlo simulation.87,88
with dipolar moments to the total number of segments per For the special case of a dipolar molecule that does not self-
molecule, xpi ) npi/mi, thus eliminating the need for an additional associate, for example, acetone, but can cross-associate, for
fitted parameter. For nonpolymeric species, npi ) 1.82 example, with water that self-associates as well, Kleiner and
The integrals I2,ij and I3,ijk are now expressed as power Sadowski86 proposed to set (1) the association energy of the
functions non-self-associating component equal to zero to make the cross-

∑ (a )
4
εij n association energy one-half of the association energy of the self-
I2,ij ) n,ij + bn,ij η (29a) associating component upon the arithmetic average mixing rule
n)0
kT used in PC-SAFT and (2) the association volume parameter of
4 this component equal to that of the self-associating component.
I3,ijk ) ∑c n,ijkη
n
(29b) Such assumptions allow for cross-association that depends on
the properties of the self-associating component alone.
n)0
A similar approach can be used for molecules with quadrupole
where the reduced density η is defined as usual in SAFT and
moments, for example, by extending PCP-SAFT82 to account
the coefficients a, b, and c depend on the chain length:
for quadrupole-quadrupole (qq)90 and dipole-quadrupole
mij - 1 mij - 1 mij - 2 (dq)91 interactions using the same Padé-approximant formality
an,ij ) a0n + a + a (30a) as that for the dipole-dipole case:
mij 1n mij mij 2n
mij - 1 mij - 1 mij - 2 Aqq
2
bn,ij ) b0n + b + b (30b) Ã qq ) (34a)
mij 1n mij mij 2n 1 - Aqq qq
3 /A2

mijk - 1 mijk - 1 mijk - 2 Adq

cn,ijk ) c0n + c + c (30c) Ã dq )
2
(34b)
mijk 1n mijk mijk 2n
1 - Adq dq
3 /A2
Here the nine constants were adjusted to simulation data83
and tabulated in ref 82. The number of segments per chain is where the second- and third-order perturbation terms also take
estimated as follows similar forms:
9π F nqinqj Qi2Qj2
mij ) √mimj (31a) 2 )-
Aqq
16 (kT)2 ∑∑xx mm i j
i j dij7
qq
I2,ij (35a)
i j
mijk ) √mimjmk
3
(31b)
9π2 F2 nqinqjnqk Qi2Qj2Qk2 qq
where mi in eqs 31a and 31b must be less than or equal to 2. If 3 )
Aqq
16 (kT)3 ∑∑∑ xixjxk I
mimjmk d 3d 3d 3 3,ijk
mi > 2, then mi ) 2 in eqs 31a and 31b alone; it is still equal i j k ij ik jk
to its original value in eqs 28a and 28b. (35b)
 Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008 8071

2 )-
Adq
9π F
∑∑xx mm i j
npinqj µi Qj 2 2
Idq
2,ij (36a) T̃ ) kT
∑∑xxmmσ i j i j ij
3

(41)
∑∑xxmmσ u
4 (kT)2 i j i j dij 5
3
i j i j ij ij

3 )
Adq
∑ ∑ ∑ x x x m m m √µ̃ µ̃ Q̃
3

2 npjµj dj + RnqjQj /dj di npiµi nqkQk dq

2 2 2 2
Λ)
i j k i j k i j k
πF
(kT)3
∑∑∑xxx i j k
mimjmk
I
dk d 2d 2d 2 3,ijk (∑ x m ) i i
3
(42a)
i j k ij ik jk
(36b)
∑ ∑ ∑ x x x m m m √µ̃ Q̃ Q̃
3
i j k i j k i j k
For nonpolymeric compounds, such as CO2, the number of Γ) (42b)
quadruple moment nq ) 1. In eq 36b, the empirical constant R (∑ x m ) i i
3

) 1.19374. The correlation integrals in eqs 35a, 35b, 36a, and

36b all can be written as in eqs 29a and 29b. The constants are If Ψ represents the dipole moment µ or quadrupole moment
tabulated in the literature.90,91 Q or polarizability R, then
In summary, a complete polar contribution to the Helmholtz
energy is the sum of eq 24a and eqs 34a and 34b:
ψ̃ )
∑ ∑ x x m m √ψ̃ ψ̃
i j i j i j
(43a)
à ) à + à + Ã
polar dd qq
(37) dq (∑ x m ) i i
2

These three Helmholtz energy terms (referred to as multipolar

∑ ∑ ∑ x x x m m m √ψ̃ ψ̃ ψ̃
3

term) have also been coupled with GC-SAFT33 to describe ψ̃' )

i j k i j k i j k
(43b)
1-alkanols, alkyl benzenes, heavy esters, and their mixtures,92,93
using the rigorous form of the third-order perturbation term A3
(∑ x m ) i i
3

according to Gubbins and Twu.76 With a quadrupolar interaction The pure substance properties in dimensionless form are
alone, this method was applied to polycyclic aromatic hydro-
carbons and their mixtures.94 For the special case of a dipolar µi/mi
µ̃i ) 85.12 (44a)
molecule that does not self-associate but can cross-associate with
associating molecules, such as in ester + alcohol systems, polar
√σ3i ui/k
GC-SAFT applies one cross-association site with association Qi/mi
parameters equal to those of the hydroxyl group in the alcohol Q̃i ) 85.12 (44b)
molecules.93 √σ5i ui/k
In a different approach to accounting for polarity, the second- Ri
and third-order terms proposed by Larsen et al.95 are coupled R̃i ) (44c)
with SAFT-VR to predict the phase behavior of quadrupolar miσ3i
nitrogen in n-alkanes.96 Larsen’s95 formulation is also used in Table 2 provides a summary of SAFT-based EOS for polar
truncated PC-SAFT (tPC-SAFT),97-99 namely, the terms on the systems discussed in this section. Most of the polar terms are
right-hand side of eq 37 are approximated with Larsen’s zeroth- formulated in the form of a Padé approximant, though details
order pair- and triplet-correlation integrals. An induced-polar of the second- and third-order perturbations may differ from
term is also introduced in tPC-SAFT in the form of a Padé one version to another.
approximant 4.3. Ionic Liquids. The first SAFT-based model for ionic
liquids (IL), tPC-SAFT without the induced-polar term,103,104
à polar + à ind )

( )
was demonstrated to account for gas solubility in IL. The IL
Apolar Aind molecules were assumed to have the same dipole moment, µ )
∑xm i i
2

1 - [A3,2 + A3,3 ]/A2

polar polar polar
+
2

1 - A3 /A2
ind ind
(38) 1.70 D, but no ionic long-range interactions between cations
i
and anions. However, cross-association was allowed between
where IL and CO2, though the pure components do not self-associate.
At first,103 in working with CO2, the pure-IL parameters were
Apolar
2 )-
η
T̃2K3 3 [
4 4 12 µ̃2Q̃ 2 12 Q̃ 4
µ̃ +
5 K2
+
5 K4 ] (39a)
estimated on the basis of experimental thermodynamic physical
data (density, enthalpy, entropy of dissolution of CO2) and
physicochemical data (size, polarizability, number of electrons)

3,2 )
Apolar
η
T̃ K 5
3 8 [
6 4 2 144 µ̃2Q̃ 4
µ̃ Q̃ +
175 K2
+
72 Q̃ 6
245 K4 ] (39b)
that are available in the literature, but later,104 in working with
other gases, the parameters were fitted to the IL density subject
to reproducing the vapor pressure within the order of magnitude

3,3 )
Apolar
η2
T̃3K3 9
µ̃[
10 ′6 159 Λ6
+ +
689 Γ6 243 Q̃ ′6
+
125 K2 1000 K4 800 K6 ] of the experimental values. In order to reproduce the gas
solubility in IL, temperature-dependent binary parameters were
needed.
(39c) Andreu and Vega105 modeled IL as a simple associating
8η molecule to obtain the IL parameters for their soft-SAFT in
2 )-
Aind µ̃2R̃ (40a) representing the solubility of CO2 in IL. In that work, CO2 is a
T̃K3 quadrupolar component that cross-associates with IL.
10η2 Wang et al.,106 using a SAFT-like EOS known as SWCF,
3 )-
µ̃4R̃′
Aind (40b) proposed a “diblock” square-well chain IL model, where one
T̃ 2K3 block is an alkyl chain and the other block is the imidazolium
K is a dimensionless quantity adjustable to experimental data. ring plus the anion, so that there are two types of segments,
The other dimensionless variables in the equations above are each of which is the constituent of each block. The parameters
Table 2. Summary of SAFT-Based EOS for Polar Systems
additional pure component
ref polar EOS parent EOS model for polar term polar interactions accounted for examples of real systems
parameters
63 no specified name SAFT-0 Stell et al.73 dipole-dipole as one of
the terms in
dealing with
aqueous electrolytes
75 polar SAFT SAFT-HR Gubbins and Twu76 dipole-dipole 1 (xpi) acetone in
some n-alkanes
77 polar SAFT SAFT-HR Gubbins and Twu76 dipole-dipole 1 (xpi) ketones and their
polar PC-SAFT PC-SAFT binary mixtures in alkanes

78 polar PC-SAFT PC-SAFT Gubbins and Twu,76 and dipole-dipole 1 (xpi) ethers, polyethers,
Saager and Fischer81 epoxies, cyclic ethers,
esters, ketones; binary
mixtures in alkanes
8072 Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008

82 PCP-SAFT PC-SAFT Stoll et al.83 dipole-dipole none ketones, aldehydes,

esters, ethers, DMSO,
HCl, CH3Cl,
C2H5Cl; binaries in n-alkanes
and toluene
84 PCIP-SAFT PC-SAFT Stoll et al.83 and dipole-dipole; induced none ketones, aldehydes,
Gray et al.100 (induced) (polarizability) esters, ethers, DMSO,
nitriles, DMF, halogenated,
CH3NO2, C2H5 NO2;
binary mixtures
85 PSAFT PC-PSAFT SAFT-HR Nezbeda and Pavlilcek101 dipole-dipole 1 (K, or σd alcohols, ketones,
PC-SAFT in K ) σd/σ) ethylene glycol, acetic
acid, H2O, H2S, chloroform,
ammonia; binary mixtures; two
ternary mixtures
87, 88 SAFT-VR+D SAFT-VR Wertheim89 dipole-dipole (comparison with simulation)

90 PCP-SAFT PC-SAFT two-center LJ and quadrupole-quadrupole none CO2, CS2, ethylene,

data from Stoll et al.102 acetylene, N2, Cl2, benzene;
binary mixtures
91 2CLJDQ 2CLJ (2 center simulation data91 dipole-dipole, none five binary
Lennard-Jones) (for dipole- quadrupole-quadrupole, mixtures
quadrupole) dipole-quadrupole
92, 93 polar GC-SAFT GC-SAFT Gubbins and Twu76 dipole-dipole, 1 (xpi), 2 alcohols, alkyl benzenes,
quadrupole-quadrupole, for esters xylenes, esters,
dipole-quadrupole alkyl esters;
binary mixtures
96 quadrupolar SAFT-VR SAFT-VR Larsen et al.95 quadrupole-quadrupole none nitrogen in n-alkanes

97-99 tPC-SAFT PC-SAFT Larsen et al.95 dipole-dipole, 1 (Vp) N2, CO2, O2, naphthalene,
quadrupole-quadrupole, H2O, benzene, acetonitrile,
dipole-quadrupole, induction alcohols, etc.; binary mixtures; seven
ternary mixtures

of the alkyl block are estimated from those of hydrocarbons. If
there are two alkyl chains, the shorter alkyl chain is included
in the imidazolium-anion block, the parameters of which are
obtained from the PVT data of IL. This approach assumes no
cross association between IL and a self-associating solvent, and
it requires three binary parameters, i.e., one between segments
of different blocks and two between solvent segments and two
different block segments. This approach was demonstrated for
IL-solvent vapor-liquid equilibria.
5. Applications in Special Regions
5.1. Near-Critical Region: Classical-to-Nonclassical
Crossover. SAFT is a mean-field theory, in which a molecule
is assumed to occupy a region with uniform bulk properties,
such as density and composition, where the contribution of
density fluctuations to the Helmholtz energy density is neglected.
Such mean-field theories are not accurate near the critical point;
the coexistence curve that resulted from mean-field theory is
quadratic.
An early attempt to make SAFT more accurate in the vicinity
of the critical point is through a crossover theory based on the
renormalized Landau expansion by Kiselev,107 where a cross-
over function is introduced to reproduce the asymptotic scaling
laws in the immediate neighborhood of the critical point but
can reduce back to a classical Helmholtz energy away from the
critical point. SAFT-HR39,108-111 and, later, SAFT-VR112-115
were demonstrated to work with such a crossover theory, and
their SAFT versions are marked with X, indicating that a
crossover approach has been incorporated, for example, SAFT-
HRX and SAFT-VRX.
In the crossover theory, the dimensionless Helmholtz energy
is written as
Ã(T, V) ) Ã(T, V0C) - ∆VP̃0(T) + ∆Ã(τ, φ̄) (45)
The first terms on the right-hand side of eq 45 is the
background contribution, i.e., the Helmholtz energy along the
classical critical isochore V ) V0C, the second term is the work
done from V0C to V at pressure P0C (P̃0(T) ) P0CV0C/RT), and
the last term is the critical part of the Helmholtz energy
∆Ã(τ, φ̄) ) à R(τ, φ̄) - à R(τ, 0) - ln(1 + φ̄) + φ̄P̃0(τ) (46)
where the renormalized variables are given as follows:
τ ) τY-R⁄2∆1 + (1 + τ)∆TCY2(2-R)/3∆1 (47a)
φ̄)φY(γ-2β)/4∆1 + (1 + φ)∆VCY(2-R)/2∆1 (47b)
The universal nonclassical critical exponents used in eqs 47a
and 47b are R ) 0.11, β ) 0.325, γ ) 1.24, and ∆1 ) 0.51.
The deviation from the critical point is represented by τ ) (T
- TC)/TC and φ ) (V - VC)/VC, and the shift of critical point
relative to the classical values is represented by ∆TC ) (TC -
T0C)/T0C and ∆VC ) (VC - V0C)/V0C. For pure components, the
classical critical values P0C, T0C, and V0C are related through
the criticality conditions as follows:39,116
( )
∂2P
( ∂P
∂F )
x,T0C
)
∂F2 x,T0C
)0 (48)
while the real critical values PC, TC, and VC are determined from
the critical-point conditions in terms of the partial derivatives
of the chemical potential with respect to mole fractions, for
example, for a binary116,117
Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008 8073
( )
∂µ2
∂x2 TC,PC
)
( )
∂2µ2
∂x22 TC,PC
)0 (49)
The crossover function Y in eq 47b, which approaches 1 as
the system goes away from the critical point, adds a parameter
to the SAFT-HRX pure-component parameters, namely the
Ginzburg number (Gi).39 For mixtures, SAFT-VRX, using a
different crossover function, has three adjustable crossover
parameters for each component, including Gi.114,115
A generic procedure for deriving a crossover EOS is to
differentiate eq 45 with respect to the molar volume
( ) ( )
∂à RT ∂∆Ã
P(V, T, x) ) -RT ) P(V0C, T, x) - (50)
∂V x,T VC ∂φ x,T
where the critical part ƈ is calculated through eq 46. The
residual Helmholtz energies and pressure in eq 46, as well as
the pressure on the right-hand side of eq 50, are given by SAFT.
Another example of a crossover approach, based on a set of
recursive equations of global renormalization-group theory
(RGT), is applied with soft-SAFT that has LJ spheres as
reference.118-120 In a recursive manner, the Helmholtz energy
per unit volume of a system at density F is defined as
∞
a) ∑ a (F) )
{
n
n)1
kT Ωsn(F) 1
∞ an-1(F) - ln , 0 e F e Fmax
∑
3n 3 l 2
2 L Ωn(F) (51)
n)1 1
an-1(F), F e F e Fmax
2 max
where the maximum molecular density, Fmax, depends on the
EOS used; for example, it is (mNAσ3)-1 for soft-SAFT. The
logarithm expression is the ratio of density fluctuation for short-
range attraction to that for long-range attraction; the attractions
are both in the form of integral in density. As the density ranges
suggest, the long-wavelength fluctuations are relevant only at
densities below half of the maximum density upon approaching
the critical region.
In eq 51, L is the cutoff length, below which the mean-field
theories, such as SAFT, can accurately describe the fluid system;
L is one of the adjustable crossover parameters. The other
parameter, inside Ωns (F), is called the average gradient of the
wavelength function φ. The series in eq 51 starts with a0, a
zero-order term, which is calculated using SAFT at the
molecular density F. Therefore, the overall accuracy depends
on the SAFT accuracy away from the critical point. Iterations
typically converge after five cycles, though more iterations are
usually needed to get accurate critical exponents.118
Independently, Mi et al.121,122 proposed the same RGT
coupled with SAFT-0 and dipole-dipole interactions. Their
recursive expression, however, involves slightly different forms
of the density fluctuation integrals (than those in crossover soft-
SAFT). There is no need for an adjustable pure-component
parameter, but two binary interaction parameters are needed,
as with crossover soft-SAFT.
It is worth mentioning a phenomenological approach that
happens to work for pure components, referred to as SAFT-CP
(critical point).123-125 There are two assumptions: (1) molecules
consist of nonspherical segments and (2) the dispersion energy
term is so far overestimated due to the fact that the chain
formation reduces the space available for dispersive interaction.
The first assumption is implemented using Boublik’s hard-
convex body126 to replace the hard-sphere term in SAFT
8074 Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008

where the superscripts refer to ideal gas, short-range, and long-

range terms, respectively. In the application of SAFT to
inhomogeneous systems, the short-range part accounts for all
short-range interactions, such as hard-sphere, chain, and as-
sociation, while the long-range part accounts for all longer-range
interactions, such as dispersion and ionic interactions. The ideal
gas part of the Helmholtz energy functional is given by

Aig[F(r)] ) kT ∫ F(r)[ln{Λ F(r)} - 1] dr

3
(56)

where Λ is the de Broglie wavelength.

Figure 9. Typical density profile in a planar interfacial region. The short-range part of the Helmholtz energy functional can
be derived from local density approximation (LDA) or weighted

Ãhcb ) m [ R2
(1 - η)2
-
R2 - 3R
1-η
- (1 - R)2 ln(1 - η) - 3R ] density approximation (WDA). In the former, local density F(r)
is used, while in the latter, a weighted (smoothed) density Fj(r)
is used
(52)
where R is the nonspherical parameter and η is the reduced ASR[F(r)] ) ∫f SR
[F(r)] dr (57a)
density. The corresponding hard-convex-body RDF is used in
the chain term. The second assumption requires a dispersion
energy term correction that is proportional to the ratio of the
ASR[F(r)] ) ∫f SR
[F(r)] dr (57b)

chain term to the hard-convex-body term as follows: with

(
à ′disp ) 1 + 1.75
à ′chain
à hcb
à disp ) (53) F(r) ) ∫ F(r′) ω[|r - r′|;F(r)] dr′
where ω is the weighting function and fSR is the short-range
(57c)

The dispersion and chain terms used here are those of SAFT- part of Helmholtz energy density, which reduces to that for a
HR, but the prime sign in the chain term in eq 53 means that homogeneous fluid if the local or weighted density is replaced
this term is estimated using the hard-convex-body RDF instead with the bulk density. In the latest development of WDA, the
of the hard-sphere RDF. This approach is accurate for pure so-called fundamental measure theory (FMT),130 the Helmholtz
components, but requires more work to extend it to mixtures, energy density in eq 57b is a functional of several weighted
even those as simple as binary mixtures of small n-alkanes.127 densities with density-independent weighting functions, which
While criticality represents a special challenge in a relatively considerably reduces the computational effort. LDA is usually
small phase-diagram region in pressure, temperature, and sufficient for vapor-liquid interfaces. WDA is more accurate
composition coordinates, inhomogeneous systems, such as the for oscillatory profiles around fluid-solid interfaces.
small length scale interfacial “regions”, also call for special The long-range part of the Helmholtz energy functional can
theories to work with SAFT, which by itself works well for be obtained from
bulk phases, but cannot represent the crucial details around the
interface.
5.2. Interfacial Region: Inhomogeneous Systems. Inter-
ALR[F(r)] )
1
2 ∫ ∫ F(r) F(r′) g ref
(r, r′) u(|r - r′|) dr′ dr
faces are thin but finite boundaries that provide a spatial (58)
transition of properties, such as composition and density, over
a short length scale upon crossing from one bulk phase to where gref is the segment-segment RDF of the inhomogeneous
another. If we take density, for example, to characterize this reference fluid and u is the long-range interaction potential.
transition, the free energy becomes a functional of the spatially DFT with LDA has been applied with SAFT-HS (hard
varying density. A one-dimensional example of an equilibrium sphere)131,132 and SAFT-VR133,134 for vapor-liquid interfacial
density profile in the interfacial region that minimizes the system tension of pure components, such as water, alkan-1-ols, and
grand potential is shown in Figure 9. The shaded region where refrigerants. In vapor-liquid equilibrium, the external potential
the density varies with position is a rough measure of the Ψ in eq 54 is zero, so the equilibrium density profile can be
thickness characterizing the interface. calculated through minimizing eq 54
Among other theories describing inhomogeneous systems, δA[F(r)]
density functional theory (DFT) has been demonstrated to be -µ)0 (59)
δF(r)
compatible with SAFT for associating fluids interacting with a
hard wall.128,129 In DFT, the grand potential functional at Once the density profile F0(r) is obtained by iteratively solving
temperature T, chemical potential µ in an open system with eq 59, the interfacial tension can be calculated through a
volume V, is to be minimized in the equilibrium. For a pure thermodynamic relation:
component, the grand potential functional is dΩ[F0(r)] - p dV
γ) (60)
Ω[F(r)] ) A[F(r)] + ∫ F(r){ψ(r) - µ} dr (54) dS
where S is the interfacial area and p is the bulk pressure.
where A is the Helmholtz free energy functional, Ψ is the Lu et al.,135 who applied DFT with SAFT-0 plus dipolar term,
external potential (such as that of a wall), and F(r) is the density calculated the surface tension of pure polar and associating fluids
profile. In a perturbation-like manner, the Helmholtz energy using eq 60 for a planar interface:
functional is separated into three terms
∫
∞
A[F(r)] ) Aig[F(r)] + ASR[F(r)] + ALR[F(r)] (55) γ) -∞
(p - p[F(z)]) dz (61)

A DFT-WDA applied with SAFT, with LJ dispersive interac-
tion, is the inhomogeneous/interfacial SAFT (iSAFT)136-139 that
has been applied to n-alkanes and polymers. Another version
of inhomogeneous SAFT140 exploits intramolecular potential
formalism and DFT for associating particles of Yu and Wu.141
If the Helmholtz free energy density of inhomogeneous
system is expanded in a Taylor series,
a[F(r)] ) a0[F(r)] + κ[F(r), T]{∇F(r)}2 +
κ′[F(r), T]{∇2F(r)}+ ... (62)
where the a0 term on the right-hand side is the Helmholtz energy
density of the homogeneous fluid, we have another popular
approach known as density gradient theory (DGT). Including
the two lowest terms in the expansion gives the following
expression for the Helmholtz energy
A[F(r)] ) ∫ (a [F(r)] + κ[F(r), T]{∇F(r)} ) dr
0
2
where κ, a so-called influence parameter, can be a constant or
a function of temperature for vapor-liquid and liquid-liquid
interfaces,142 which is obtained from fitting experimental data
if applied with SAFT.
The density profile for a planar vapor-liquid interface can
be obtained by inversion of the following expression
∆a[F(z)]
z ) z0 + ∫ FL
FV
κ
dF(z)
where
∆a[F(z)] ) a0[F(z)] - F(z)µ + p
where F(z0) ) (F + F )/2, as in Figure 9, µ is the chemical
L V
potential of the bulk phase, and p is the pressure of the bulk
phase. Once the equilibrium density profile is obtained, the
surface tension can be calculated from
γ)2 ∫ FL
FV
√κ∆a[F(z)] dF(z)
DGT was first used with SAFT-HR for pure components.143
Then, Duque et al.144 used it with soft-SAFT to match their
molecular-dynamics simulation data. Later, Fu and co-workers
used it with SAFT-0145 (for n-alkanes) and PC-SAFT146,147 (for
alcohols and water). While Fu combines DGT with RGT to
approximate both interfacial and critical regions in his
papers,145,146 Kiselev et al.148 combines DGT with SAFT-HRX
to accomplish the same goal (for alcohols). They call their
version global crossover (GC) SAFT-DFT, although probably
GX-SAFT-DFT would have been more consistent with their
previous crossover methods.
Among other approaches, Fu et al.149 used SAFT-0, without
DFT or DGT, to estimate the interfacial pressure of surfactant
solutions as follows
hF2 ∂A
Π ) γ0 - γ ) - ( ∂A∂s )
N,T
) ( )
NA ∂F N,T
where γ0 is the surface tension of pure solvent or the interfacial
tension of the oil-water system and γ is that of surfactant
solution, A is the Helmholtz energy, s is the molar surface area
of the surfactant (s ) NAs0; NA is the Avogadro number and s0
is the average area occupied by one surfactant molecule in the
surface), N is the number of surfactant molecules, and h is the
interface thickness treated as an adjustable parameter. This
approach also works for ionic surfactant solutions if long-range
ionic interactions are added; Fu et al. applied primitive MSA
Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008 8075
with a consequence that two adjustable parameters are needed
to calculate the surface tension.
Among the interfacial models discussed up to this point
that are limited to pure components, some have been extended
to binary mixtures only, but not yet to real mixtures, not to
mention multicomponent real mixtures. In a different way
from the methods discussed above, there is an attempt to
apply simpler theory that needs the EOS only to provide the
number density. At sufficiently low temperatures, Li et al.150
coupled scaled particle theory (SPT) with SAFT to correlate
and predict the surface tension of binary and ternary liquid
mixtures as follows
γiσ2i
γ)
ψ
σ2
∑ xi
ψi
(68)
i
where
(63)
12η 18η2
ψ) + (69)
1 - η (1 - η)2
and σ is estimated from
∑ ∑ x x (1 - l ) ( )( ( ))
σi + σj 3 σi - σj 2
σ3 ) 3
1 + 3η (70)
i j
i j ij
2 σi + σj
where the mixture reduced density is
(64)
π
η) F
6 ∑xmσ i i i
3
(71)
i
(65) By adjusting the binary parameter lij in eq 70 to experimental
data, the calculated surface tensions of most binary mixtures
have an average absolute deviation of less than 1% and a
maximum deviation of 2.5%, except for aqueous mixtures,
where these deviations can be greater.
Other inhomogeneous systems that are of interest are systems
that can form micelles in selective solvents, such as surfactants
(66) and diblock copolymers. A natural approach that can describe
the behavior of these systems is to use SAFT with DFT or DGT.
Yeh et al. used SAFT-DFT to describe the interfacial properties
of water + oil + CiEj (CiEj ) alkyl polyoxyethylene ethers),151
where comprehensive wetting behavior was also discussed as
in their other papers.152-154 However, SAFT by itself, without
DFT or DGT, has been explored to describe such systems with
the benefit of computational simplicity. For example, perfluo-
roalkanes and perfluoroalkylalkane diblock surfactants are
treated as nonassociating molecules,28-31 whereas CiEj are
treated as associating molecules using SAFT-HS155 or molecules
with dipoles using SAFT-0.156 For ionic surfactants, SAFT-0
is used with dipolar interaction and the primitive model of ionic
interaction.157 The system properties studied in the SAFT work
includeVLE,28,29 LLE,29 closed-loopLLE,145 VLLE,28 density,30,31
cmc (critical micellar concentration),156,157 and aggregate forma-
tion.158
(67) For block copolymers, SAFT-HR with association was used
to estimate the critical micellar density of PTAN-PVAC block
copolymer in supercritical CO2,159 and SAFT1 was used to
estimate the onset pressures of micellar-phase transition of
polybutadiene-block-polystyrene (PBD-b-PS) and polyiso-
prene-block-polystyrene (PiP-b-PS) in supercritical propane.23
Figure 10 shows SAFT1 prediction of the micellar phase
boundaries along with the experimental data.23,160 Under-
standing the bulk-phase and micellar-phase behavior of
diblock copolymers may provide a route to the production
of nanoparticles that serve as carriers in drug delivery.
8076 Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008
5.3. Across Solid-fluid Boundary. 5.3.1. Crystallizable
Copolymers. While EOS is an effective method to represent
fluid phases, i.e., liquid and vapor, it is not well established to
represent the solid phase. The common approach to represent
the solid-fluid equilibria is to use thermodynamics cycle starting
from the solid side to the liquid side to get the fugacity of
subcooled liquid phase while assuming the solid phase consists
of pure solute. The final expression for the solubility of a solute
i at temperature and pressure (T, P):
[ ( )
φL0,i ∆HSL
0,i T ∆Cp
xLi ) exp - 1 - SL - (T - TSL
0,i ) +
φ̂ Li RT T RT
]
0,i
∆Cp
R
T
ln SL -
T0,i
∆V(P - Psat)
RT
(72)
where the subscripts 0 refer to pure-component properties, while
the superscripts L and SL stand for liquid and solid-liquid (on
melting curve), respectively; thus, ∆HSL is the enthalpy of fusion
and TSL is the melting temperature. Psat is the saturated-vapor
pressure of the solute. The ratio of fugacity coefficients in the
liquid phase is calculated using an EOS. ∆Cp and ∆V are the
change of isobaric heat capacity and molar volume of the solute
from solid phase to liquid phase. In most cases, the heat capacity
effect is small and hence can be neglected. At low pressures,
the last term in the exponential can also be neglected.
For crystallizable copolymers in solvents, there have been
exclusion and inclusion models, which are shown in Figure 11.
In the exclusion model, the solid polymer is divided into two
distinct domains, i.e., crystalline and amorphous. The crystalline
domain, shown in a box, contains homopolymer units only; the
copolymer units are excluded. The amorphous domain, shown
Figure 10. Micellar phase transition of PBD-b-PS and PiP-b-PS, both in
propane.
Figure 11. Models for crystallizable copolymers:160 (a) exclusion and (b)
inclusion.
as a collection of flexible chains with solid circles (comonomer
units), contains both homopolymer and copolymer units. On
the other hand, in the inclusion model, the solid polymer forms
a single crystalline domain, shown in a box, that contains both
the homopolymer and copolymer units; the comonomer units
are included in the crystalline domain as defects that introduce
a degree of disorder within the crystal. SAFT119 EOS has been
applied to these models of crystallizable copolymers,161,162
where eq 72 must be modified in two aspects. First, the enthalpy
of fusion is now the enthalpy of melting per mole crystal unit
∆Hu, and second, the expression in the exponential of eq 72
has to account for the crystallizability
xLp )
φL0,p
φ̂ pL [ { ( ) }]
exp cu -
∆Hu
RT
T
1 - SL -
T
P∆V
RT
0,p
(73a)
[ { ( ) }]
φL0,p ∆Hu T P∆V
xLp ) exp u - 1 - SL - (73b)
φ̂ pL RT T RT
0,p
where u is the number of crystallizable units in a polymer
molecule and c is a model parameter quantifying the fraction
of the crystallizable units that are actually crystallized, which
is fitted to experimental solid-liquid data. In eqs 73a and 73b,
the heat capacity effect and the saturated pressure Psat of the
copolymer are neglected. For similar systems with semicrys-
talline polyethylene, SAFT-VR is used with Flory theory of
crystallization to calculate the solubility.163
As an additional note, the classical eq 72 was also recently
used with PC-SAFT to deal with solid-complex phases of
organic compounds at atmospheric pressure.164,165
5.3.2. TPT1 Solids. The idea to extend Wertheim’s TPT1
to solid phases has been proposed in an effort to treat solid and
fluid phases within the same framework of a SAFT-like EOS.
Vega and MacDowell, for example, applied TPT1 to the solid
phase of the pearl necklace model.166 Their reference is a hard
sphere, of which the solid-phase compressibility factor is
accurately described by Hall’s EOS167
6
12 - 3β
Zhs )
β
+ ∑ ciβi (74)
i)0
where β ) 4(1 - η/τ), with η being the hard-sphere packing
fraction and τ the fraction at close packing [τ ) (π/6)2]. The
coefficients ci are listed in the literature.166,167 The corresponding
residual Helmholtz energy is available by integrating eq 74
according to the relation
Z hs - 1
∫
η
à hs ) 5.91889 + dη (75)
η
0.5450
from which the close-form analytical solution can be obtained.168
On the basis of this hard-sphere solid EOS and modified
Weeks-Chandler-Andersen (WCA) perturbation theory, an LJ
EOS for a face-centered cubic (fcc) solid has been shown to
work, either with SAFT-HR168 or LJ-WCA169 for the liquid
side, in describing the solid-liquid equilibrium of real fluids,
such as argon, krypton, and methane, as well as nitrogen and
mixtures of argon/methane and argon/krypton.170 With LJ-WCA
for the liquid side, it is demonstrated that both liquid and solid
phases of real compounds can be described using the same
theoretical concept. The LJ solid EOS has also been extended
to chain molecules and used to describe the thermal properties
of solids.170
Later, Blas et al. applied eqs 74 and 75 for solid-liquid-vapor
phase equilibria of flexible chain molecules,171 as well as
solid-fluid equilibria of flexible and linear rigid tangent chain
 Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008 8077

( )
172 hs
molecules, but with a simpler Z based on the cell theory Akj Bkj
for the latter case. Ckj(T) )
exp (83)
T T
Another expression of the Helmholtz energy of hard-sphere
The number of cavities of type k (small k ) 1, large k ) 2)
monomers in solid phase by Young173 is
per water molecule in the lattice, νk in eq 82, and the chemical
6η η τ potential difference ∆µwβ-L0, as well as the fitted constants, Akj
à hs ) 1 - ln
π
+ 15.022 - 3 ln 1 - + 5.124 ln -
τ (
η ) and Bkj in eq 83, are available from the literature.179
τ τ 2 τ 3
20.78 + 9.52
η η
- 1.98
η
(76) () () 6. Other Applications
and has been used to develop solid perturbed-chain EOS174-176 6.1. Liquid Crystals. Thies and co-workers proposed SAFT-
LC (liquid crystal) EOS.180,181 A statistical treatment of nematic
à ) à hsc + à pert (77) mesophase based on a theory by Maier and Saupe (M-S) was
where the first term on the right-hand side is the hard-chain used to calculate the Helmholtz energy due to the change in
term and the second term is the perturbation term. For binary molecular orientation. This new term was added as a perturba-
mixtures, the hard-chain term is176 tion term in eq 1 of the nonassociating SAFT-HR
εij
à hsc ) ∑
2
xi ln(xiFdi3) - 1 + mxà hs -
à orient ) -
1
2 ∑ ∑ x x kT P̄ P̄ - ∑ x ln Z
i j i j i i (84)
i j i
i)1

(mx - 1){ln g hs(dY+) + 0.156} (78) where the orientational partition function is given by

which is the sum of the ideal-gas term, the hard-sphere term

(eq 76), and the chain term, orderly written in eq 78. In eq 78,
F is the solid chain density, mx is the mixture segment length:
Zi ) ∫
0
π⁄2
exp -
(∑ j
xj
εij
)
P̄ P sin θi dθi
kT j i
(85)

with the average order parameter

∑ ∑ x x (m + m )(1 - k
(∑ )
1
mx ) m,ij) (79) εij
1
∫
i j i j
2 i j P̄j ) π⁄2
Pj exp - xi P̄ P sin θj dθj (86)
Zj 0
i
kT i j
and the RDF at contact is given by
This average is obtained from eq 86 by successive substitution

g hs(dY+) )
4(
1 ∂(Ã + Ã )
∂η
hs
The subscript Y refers to values defined by Young.176 The
binary parameter used is km,ij in eq 79.
The perturbation term in eq 77 applies LJ potential174 or Mie’s
potential.175 The latter was applied to solid-liquid equilibria
of pure n-alkanes175 and their binary mixtures.176
5.3.3. Gas Hydrates. Reliable models that can describe the
behavior of gas hydrates with or without the existence of other
molecules are important in many applications, such as flow
assurance, methane hydrate exploration, separations, natural gas
storage and transportation, bioengineering and biotechnology,
desalination, and waste minimization.
The modeling of gas hydrates, however, is not trivial. The
common approach is to use several different models to describe
each of the equilibrium phases. For example, Li et al. proposed
SAFT-0 to work with the statistical model of van der Waals
and Platteeuw for solid hydrate phases.177,178 For hydrate-
forming components including water, the solid-liquid-vapor
phase equilibrium requires the equifugacity equations
f̂iH ) f̂iL ) f̂iV
While the fugacities in vapor and liquid phases are directly
obtained from the EOS, the fugacity of water in hydrate phase
is obtained from
ig
) η)ηY
(80)
using an initial guess of 0.6. Pj describes the orientational order
of molecule j, Pj ) 1/2(3 cos2 θj - 1). The angle θj is the angle
between the axis of molecular symmetry of molecule j and the
director, which is a vector that defines the direction in which
the molecules tend to align themselves.
The energy parameter in eqs 84-86 is calculated from
εij -4.542
) √ViVjTcl,iTcl,j (87)
k
∑
xV i i
i
The clearing temperatures Tcl,i is the temperature at which
the phase transition from the anisotropic to isotropic state takes
place for species i; it is assumed to be a linear function of
molecular weight. Vi is the molar volume of species i under
ambient conditions. For application to carbonaceous pitches,
SAFT-LC also requires binary parameters, between two pitch
pseudocomponents and between a pseudocomponent and solvent.
6.2. Biomaterials. SAFT-HR was used to calculate density,
water activity, sugar solubility, and oxygen solubility for sugars
in water and alcohols182-184 assuming four to six associating
sites in a sugar molecule.
Also, SAFT-HR and PC-SAFT were used to describe amino
(81)
acids. SAFT-HR was set to have between three and four
associating sites to calculate the density of amino acids in water
and the corresponding water activity.185 PC-SAFT was set to
have four associating sites both for amino acids and polypeptides

[ ]
to calculate the solubility in water and alcohols (including the
-∆µwβ-L0 2 n
effect of pH on the solubility),186 vapor pressure, and density
f̂wH ) fwL0 exp
RT
+ ∑
νk ln(1 + Ckjf̂jV) ∑ (82) of aqueous amino acids and polypeptides.187
k)1 j)1
In bioengineering, SAFT was used to determine the extra-
where the fugacity of pure liquid water (fwL0) and the fugacity cellular pH of a saline solution of a test microorganism of
of hydrate-forming gas component j in the exponent (f̂ jV ) Bacillus subtilis under CO2 treatment.188
yjφ̂V
j P) are obtained from the EOS. The Langmuir constants that 6.3. Oil Reservoir Fluids. SAFT is a more predictive and
represent gas-water interactions, Ckj, at 260 K e T e 300 K physically realistic alternative to the conventional cubic EOS
are estimated from an empirical equation: for estimating properties of oil reservoir fluids.189-193 For
8078 Ind. Eng. Chem. Res., Vol. 47, No. 21, 2008
example, SAFT accounts for electrolytes in formation brine;
CO2 pressure; surfactants and polymers in injected fluids;
associating and polar components, especially asphaltenes and
wax, including their polydispersity; and gas hydrates, just to
mention a few typical challenges associated with the rich
molecular diversity of reservoir fluids.
SAFT is particularly useful to characterize, and ultimately
predict, asphaltenes aggregation, which has a 2-fold impact:
asphaltene precipitation, which causes reservoir and pipeline
deposition, and oil viscosity, which determines its transport
outcomes. For example, using six associating sites per asphaltene
molecule, Wu et al. applied SAFT in the framework of
McMillan-Mayer theory to get the chemical potential of
asphaltene and the osmotic pressure of an asphaltene-containing
solution,194 and later to calculate the onset pressure of and the
effect of CO2 injection on the asphaltene precipitation.195 Within
the same framework, SAFT-VR was used with two or three
associating sites to predict the asphaltene precipitation.196 PC-
SAFT was also used to study the asphaltene phase behavior,
but without invoking the association.197-200 Instead, the mo-
lecular size and van der Waals interactions were assumed to
dominate the asphaltene phase behavior in crude oil, rightly or
wrongly, as the association was assumed to be significant only
to form preaggregates prior to the precipitation.
6.4. Viscosity. Beside the phase-equilibria-related applica-
tions illustrated in the previous sections, SAFT has also been
applied to estimating dynamic properties, such as heat conduc-
tivity148 and viscosity. The recent common choice for a viscosity
model has been friction theory (FT),201 which has been coupled
with various EOS including SAFT1202,203 and PC-SAFT.202-204
In FT, the dynamic viscosity is divided into two parts,
η ) η0 + ∆η (88)
where η0 is the viscosity of dilute gas given by Chung et al.205
and ∆η is the dense-state correction term, which vanishes in
the dilute gas limit.
The dense-state correction term is the friction contribution
derived from classical mechanics and the van der Waals theory
of fluids:
∆η ) κr(T)Pr + κa(T)Pa + κaa(T)Pa2 + κrr(T)Pr2 (89)
where Pr is the repulsive pressure and Pa is the attractive
pressure; both pressures come from the EOS coupled with this
theory. In the dilute gas limit, Pr ) Pa ) 0, so that the correction
term ∆η ) 0, as desired. The temperature-dependent coefficients
also depend on the critical temperature and several component-
specific parameters.
When coupled with SAFT1 and PC-SAFT, κaa ) 0;202,203 Pr
and Pa are calculated from the first derivatives of repulsive and
attractive residual Helmholtz energy terms with respect to
density:
Pr ) RTF2 ( )
∂ã hs
∂F
(90a)
( )
∂ã disp ∂ã chain
Pa ) RTF2 + (90b)
∂F ∂F
Equations 90a and 90b are for nonassociating molecules. For
associating molecules, the attractive association term should be
added in eq 90b. In a more recent application with PC-SAFT,
with κaa * 0,204 Pr includes the ideal-gas and chain terms, so
that Pa consists of a dispersion term only. The SAFT-FT model
was applied to n-alkanes and their mixtures202-204 and some
CO2 + n-alkanes mixtures.204
Very recently, a kinetic study on dense fluids of chain
molecules relates the viscosity of pure fluid to molecular
parameters, i.e., the segment diameter and the effective chain
length.206 When applied to n-alkanes, the parameters are found
to agree with those obtained from SAFT-VR. This finding
suggests that, in principle, values of SAFT parameters can be
adopted for the viscosity model. However, whether the model
can predict the viscosity of mixtures still needs to be tested.
7. Conclusion and Future Directions
The original SAFT model has been extended, conceptually
and practically, to be more accurate and predictive for more
and more complex systems and to work with other theories to
provide wider applications. More and more relevant interactions
have been included to obtain more realistic representations. All
in all, the recent progress has made SAFT even more powerful
for scientific and engineering purposes.
Examples of future challenges that are likely to attract more
research attention are SAFT-like solid-phase models, based on
TPT1, conceptually consistent with the current fluid-phase SAFT
models, and SAFT-DFT models of mixtures in confined
geometries, for example, to characterize interfaces and fluids
in porous media. In addition, life-science-related applications,
for example, those related to biomaterials, are also likely to
attract growing attention.
Acknowledgment
This work is funded by Wyoming’s Enhanced Oil Recovery
Institute. The authors also thank Dr. George Jackson, Dr.
Gabrielle Sadowski, Dr. Erich Müller, Dr. Clare McCabe, and
Dr. Pascal Tobaly for their useful comments leading to
refinements in some parts of this review paper.
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ReceiVed for reView June 3, 2008
ReVised manuscript receiVed August 1, 2008
Accepted August 1, 2008
IE8008764