Ind. Eng. Chem. Res.

2005, 44, 6963-6972 6963

Molecular Dynamics Study of the Lennard-Jones Fluid Viscosity:

Application to Real Fluids
Guillaume Galliéro,* Christian Boned, and Antoine Baylaucq
Laboratoire des Fluides Complexes (UMR-5150), Université de Pau et des Pays de l’Adour,
Centre Universitaire de Recherche Scientifique, BP 1155, F-64013 Pau Cedex, France

A predictive scheme of viscosity for pure fluids and mixtures of simple molecules is presented.
First, using molecular dynamics data from the literature and also from our own study, a
representative correlation of the viscosity of a Lennard-Jones fluid is developed for a wide range
of thermodynamic states. Second, a corresponding states scheme is proposed which allows the
transposition of the previous results to real fluids. For some simple molecules, this scheme induces
deviations lower than 5% in conditions covering gas, liquid, and supercritical states. For larger
molecules, the results are poorer but can be strongly improved by fitting the atomic diameter.
Then, it is shown for simple binary and multicomponent mixtures that, by using merely a van
der Waals one-fluid approximation and the Lorentz-Berthelot rules, results are as good as for
pure fluids. Finally, the limitations of such a scheme are shown when applied on the methane
+ toluene asymmetric mixture.

1. Introduction proper definition of mixing/combining rules is still an

Viscosity is an important property in fluid mechanics,
in chemical engineering, and, in particular, in the
petroleum industry. It is of great interest in various
research areas, both fundamental and applied. The
theoretical understanding of the viscosity behavior is,
therefore, essential. One of the most significant prob-
lems is the case of the mixtures: in such fluids, the
representation of the temperature-pressure-composi-
tion variations of the viscosity is still widely open,
despite many different approaches proposed in the
literature. It should also be mentioned that one of the
difficulties in developing a model is to correctly describe
the transition between the low-density state (where the
zero-density gas viscosity is very well-described by
kinetic theories involving the collision integrals) and the
high-density state. In recent years, a large amount of
physically based correlations to predict this transport
property have been developed.1-7 Several comparisons
of the efficiency of some of these correlations have been
recently published in the literature.7-10 Even if some
of these models are able to deliver excellent prediction
in some cases, they all suffer from weaknesses in other
cases or need some refitting procedure, which is not
consistent with a predictive scheme. Moreover, when
dealing with mixtures, the number of parameters
needed and the complexity often make them difficult
to be used for engineering purposes.
Nowadays, molecular dynamics (MD) tends to become
an alternative to experiments in order to provide
transport properties. However, because of the complex-
ity of the considered systems and of the force field
simulated (hence, the time needed for the calculation),
MD is not yet able to provide reliable values in all
circumstances,11-13 despite some obvious success.14-16
This is particularly true when dealing with mixtures
where, as for classical macroscopic correlations, the
* To whom correspondence should be addressed. Tel.: +33
5 59 40 76 46. Fax: +33 5 59 40 76 95. E-mail: guillaume.galliero
@univ-pau.fr.
10.1021/ie050154t CCC: $30.25 © 2005 American Chemical Society
Published on Web 07/08/2005
open problem.17-19
In this work, a new, simple, predictive viscosity
correlation based on MD results on a 12-6 Lennard-
Jones (LJ) fluid is presented. This correlation, combined
with a corresponding states scheme, is particularly
efficient on simple mixtures for a large variety of
thermodynamic states. The basis of this scheme, the LJ
potential, is known to be simpler in its form than most
real intermolecular interactions, especially concerning
the repulsive part. It nevertheless takes into account
much of the essential physics of simple fluids. In
addition, apart from the relatively quick MD computa-
tions of the LJ fluid due to its simple shape, one
advantage of such a potential (with only two charac-
teristic parameters) over more complex ones20 is em-
phasized in mixtures, because a two-combining-rules
model is simpler to deal with than a three-or-more-
combining-rules model.
So, in this work, it is assumed that a real fluid
essentially behaves as an LJ one. In other words, the
real fluid is represented by an LJ fluid having effective
intermolecular potential parameters consistent with the
experimental critical coordinates. Besides, correlations
based on this simple fluid description have shown to be
a valuable estimation tool for phase equilibria21 or even
mass diffusion processes.22-23 Concerning viscosities, to
our knowledge, only one previous work similar to this
one has been published.24 Nevertheless, this work was
restricted to pure compounds. Furthermore, partly due
to the bad statistics of the MD simulations used25 to
construct the correlation, some results for pure fluids
were not that convincing.24
In this present study, to adjust the correlation on LJ
fluid viscosity, new boundary driven nonequilibrium mo-
lecular dynamics simulations (80 values) have been per-
formed and a set of reliable values of equilibrium mo-
lecular dynamics (258 values) coming from the litera-
ture26 have been used. This database is then composed of
338 points covering gas, liquid, and supercritical states.
Then, for real fluids, in the framework of the corre-
sponding states law,27 the molecular parameters are
6964 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005
simply deduced from the real critical temperature and
volume of the studied fluid (instead of the critical
temperature and pressure as for Zabaloy et al.24). Using
this correlation, a comparison of the results on viscosity
of some simple pure fluids (CH4, C2H6, C3H8, Ar, N2,
O2, and CO2) is achieved for a wide variety of thermo-
dynamic states (from gas to liquid and in the super-
critical state). Additionally, the limitations of such a
scheme when used on two more complex molecules,
toluene and n-decane, is discussed.
Finally, this correlation has been tested on mixtures,
in the framework of the van der Waals one-fluid
approximation,28 using the Lorentz-Berthelot combin-
ing rules. Tests have been performed on various simple
binary mixtures, two natural gases, and the methane
+ toluene asymmetric mixture.
2. Molecular Dynamics Simulation Background
2.1. Molecular Dynamic Potential. To model the
fluid particle interactions, we have used the classical
Lennard-Jones 12-6 which is, for a molecule i interact-
ing with a molecule j,
(( ) ( ) )
12 6
σij σij
Uij ) 4ij - (1)
r r
where ij is the potential strength, σij is the “atomic
diameter”, and r is the intermolecular separation length.
In the spherical approximation used, this expression
models the interaction between molecule i and molecule
j. For pure compounds, i ) j. For mixtures, it is possible
to define the cross-atomic-diameter and the cross-
potential-strength, thanks to a set of combining rules
defined in the following section.
2.2. Case of the Mixtures. When dealing with
mixtures, the crossmolecular parameters between un-
like particles appearing in eq 1 have to be defined using
a set of combining rules. As for mass diffusion,19,23
thermal diffusion,29 or thermodynamic properties,17,21
it is assumed that these combining rules play an
important role when dealing with viscosities of mix-
tures, even if some clues seem to indicate that their
influence remains limited compared to what occurs for
pressure.30 Even for a simple two-parameter potential,
as for the LJ one, there is a large number of possibili-
ties31 to define the crossmolecular parameters such as
ij or σij. Among them, combining rules involving inter-
action parameters, such as the kij parameter for cubic
equations of state,27 seem to be able to provide good
results for thermodynamic and dynamic properties.18,21
Nevertheless, they imply additional parameters for each
mixture, and so the predictive character is lost. There-
fore, we have chosen to use the classical Lorentz-
Berthelot (LB) combining rules:
( )
σi + σ j
σij ) (2)
2
ij ) (ij)1/2 (3)
2.3. Microscopic Law of the Corresponding States
and One-Fluid Approximation of the Mixture.
2.3.1. Microscopic Law of the Corresponding States.
The law of the corresponding states postulates that,
with an adequate rescaling procedure, different fluids,
at the same reduced conditions, have superposing
thermodynamic phase diagrams. Furthermore, a similar
rescaling procedure is possible for transport properties
and, in particular, for viscosity.32 We have used the
microscopic formulation of the corresponding states law,
which means a rescaling procedure using the molecular
parameters of the LJ potential, σ and .33 In this scheme,
the reduced LJ temperature and density are, respec-
tively,
kBT
T* ) (4)
x
Nσx3
F* ) (5)
V
where kB is the Boltzman constant, T is the tempera-
ture, N is the number of particles, V is the volume of
the simulation box, and σx and x are the characteristic
LJ potential parameters of the studied fluid. The
reduced pressure, which is a unique function of T* and
F* for a given potential, is
Pσx3
P*(T*,F*) )
(6)
x
where P is the pressure of the system. In this scheme,
the reduced viscosity, which is a unique function for a
given potential form, is32
σx2
η*(T*,F*) ) η (7)
xmxx
where mx is the characteristic molecular weight of the
fluid and η is the dynamic viscosity. Notice that, when
expressing a dynamic property in this set of reduced
variables, the thermodynamic state and the molecular
parameters contributions are uncoupled.27
2.3.2. One-Fluid Approximation of the Mixture.
In pure fluids, σx, x, and mx, appearing in eq 7, are equal
to those of the involved species. But in mixtures, these
parameters must be defined thanks to a one-fluid
approximation which lumps the compounds into a single
pseudocomponent “equivalent” to the mixture. To achieve
such a goal, we have used the van der Waals one-fluid
approximation (vdW1) which provides reasonable re-
sults,34
mx ) ∑i ximi (8)
σx3 ) ∑i ∑j xixjσij3 (9)
∑i ∑j xixjijσij3
xσx3 ) (10)
where the xi are the molar fractions and where ij and
σij are calculated using eqs 2-3.
2.4. Determination of the Molecular Parameters.
There are different ways to obtain the molecular pa-
rameters of pure compounds, based on zero-density
transport properties, second virial coefficients for which
analytical forms exist, or even optimization of MD
results on experiments. But depending on the property
and the phase in which the regression is done, values
could differ.35

We propose a simple scheme where the two param-
eters are deduced from the critical temperature and
volume of the studied species in the same way as by
Zabaloy et al.,24 except that the latter use the critical
pressure instead of the critical volume. We use the
critical volume because such a quantity is, in some
sense, more representative of the molecular diameter
than the critical pressure. One may note that such an
assumption connects microscopic to macroscopic corre-
sponding states law. Reduced critical temperature and
density in LJ systems are properties that slightly
depend on the technique used and on the numerical
parameters applied,36,37 mainly the choice of the cutoff
radius (see Section 3.2). Nevertheless, Dunikov et al.38
have shown that LJ fluids having different cutoff radii
are thermodynamically similar, i.e., obey a correspond-
ing states law.
We have chosen to take T/c ) 1.2593, as in Chung’s
method, which is devoted to predict low-density viscos-
ity.33 Concerning the critical density, we have taken F/c
) 0.302, which has been chosen to yield good viscosity
results on methane for a large range of thermodynamic
states, as we will see later. From these values we can
deduce that
k B Tc
) (11)
1.2593
σ ) (0.302Vc)1/3 (12)
where Tc and Vc are, respectively, the critical temper-
ature and volume of the compound, which have been
taken from ref 33. For example, eqs 11 and 12 applied
on methane give  ) 1258.1 (kJ mol-1) and σ ) 3.670
Å, which is consistent with the literature,35 even if the
atomic diameter is slightly lower than that for a set
fitted on thermodynamic properties.39
3. Nonequilibrium Molecular Dynamics
3.1. Algorithm Used. One important point of this
work is to have of a reliable database on the reduced
viscosity η* of LJ fluids on which to construct an
accurate correlation. To compute this transport property
in Lennard-Jones fluids using molecular dynamics, a
large number of techniques are available. They are
based on either equilibrium, synthetic nonequilibrium,
or boundary driven nonequilibrium approaches.40-42
Among them, we have chosen a boundary driven non-
equilibrium molecular dynamics scheme, which is simple
to handle and provides reliable results.43 In this tech-
nique, the simulation box is divided into 32 slabs along
the z direction. Then, the fluid is sheared using a net
exchange of the momentum along the x direction
(perpendicular to z), px, which is performed between the
central part of the simulation box, slabs 16 and 17, and
the edge layers, slabs 1 and 32, to conserve the periodic
boundary conditions. To do so, we look for the two
particles in slabs 1 and 32 with the largest -x compo-
nents of the momentum and for the two particles in
slabs 16 and 17 with the largest +x components of the
momentum. Then, we exchange x components of the
velocity between the particles involved. This procedure
keeps constant the overall energy and momentum and
corresponds to a redistribution in the simulation box of
a certain amount of momentum,44 noted ∆ptot. This
exchange is done every A time step (exchange fre-
Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6965
quency), to avoid too large shear. Applying this scheme,
the transverse linear momentum flux induced is
∆ptot
Jz(px) ) (13)
2AtLxLy
where t is the time step and Lx and Ly are the lengths
of the simulation box in the x and y directions, respec-
tively. After a transient stage, the system tends toward
a stationary state, and the viscosity of the system is
simply deduced from Newton’s law and eq 13
∂vx
Jz(px) ) -η (14)
∂z
where ∂vx/∂z is the shear rate. At the stationary state
in the linear response regime, the shear rate reduces
to ∆vx/∆z and is evaluated thanks to the local velocity
computed in each slab. The slabs where the exchanges
are performed have been discarded to measure the shear
rate.
3.2. Numerical Details of the Code. The code used
is a homemade one in FORTRAN 90 which uses the
Verlet velocity algorithm to integrate the equation of
motion. The usual periodic boundary conditions and
minimum image convention were applied. To keep the
temperature constant during the simulation, we have
used a Berendsen thermostat.45 To avoid finite size
effects and to obtain a good accuracy on the value
obtained, we have performed simulations on a 1500-
particle system having a 2.5σ cutoff radius during 107
nonequilibrium time steps. The reduced time step has
been taken to be 0.002. The A exchange frequency has
been taken to be 300 to avoid any disturbances.43
The simulations have been performed on SGI Origin
3000 supercomputers in the Centre Informatique Na-
tional de l’Enseignement Supérieur (CINES; Montpel-
lier, France) and in the pôle de Simulation et Modéli-
sation en Aquitaine (SIMOA; Bordeaux, France). Using
these numerical parameters, the statistical errors pro-
duced are around (3%, except in the dense liquid phase,
where errors may reach 5%.
3.3. Validation of the Code. We first tested the
ability of our own code to provide consistent results by
comparing with results coming from a reliable study
using equilibrium molecular dynamics on Lennard-
Jones 12-6 particles.26 To achieve such a goal, we have
performed simulations at T* ) 1.5 and T* ) 4 for F*
going from 0.3 to 1 with a step of 0.1. To estimate the
reliability of the Nc results, we have estimated the bias,
( )
Nc /
1 ηthis
∑100 1 -
work
bias ) (15)
Nc i)1 η/Meier
the average absolute deviation (AAD),
/
1
Nc
| ηthis work |
∑
AAD ) 100 || 1 - |
| (16)
Nc i)1 | ηMeier |
/
and the maximal deviation (∆max),
( )
| / |
ηthis
|
∆max ) max 100 | 1 - /
work |
(17)
|
| ηMeier |
which are all expressed in percentages. For these 16
points, we have AAD ) 1.23%, ∆max ) 2.75%, and bias
6966 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005
Figure 1. Thermodynamic state points where viscosity has been
computed. Full circles correspond to our simulations and open
squares correspond to those of Meier.26
) -0.22%, which remains reasonable compared to the
inherent statistical errors of molecular dynamics. It is
worth noticing that the results are in a good agreement,
despite the fact that the two techniques are different
(equilibrium and nonequilibrium methods) and that
some parameters differ (size of the system, cutoff radius,
and simulation duration).
3.4. New LJ Viscosity Data. To complete Meier’s
data set, which is one of the most precise in the
literature, we have performed calculations for 80 more
values. The choices made for the duration and for the
system size (see Section 3.2) allow us to get statistical
error bars as small as those of Meier. Figure 1 indicates
the distribution of these 80 new data points in the
reduced thermodynamic space of these simulations, as
well as that of the 258 data points of Meier. Our
simulations have been performed for thermodynamic
conditions going from 0.22 to 1 for F* and from 0.6 to
2.5 for T*. Because liquid phase simulations induce
generally larger statistical errors and larger values of
viscosity, we have concentrated the majority of our
simulations in this dense, low-temperature state (see
Figure 1) to get a consistent set of values in this
particular state. The whole database composed of our
simulations and those of Meier cover conditions going
from 0.1 to 1.275 for F* and from 0.6 to 6 for T*, as
shown in Figure 1. New LJ viscosity values obtained
by us are provided in Appendix A with the correspond-
ing LJ thermodynamic conditions.
4. Viscosity Correlation
4.1. Reduced Viscosity Expression. As proposed
many times in the literature,4-6 we have assumed that
the reduced viscosity defined by eq 7 can be expressed
as a sum of a Chapman-Enskog low-density contribu-
tion, η/0, and a residual viscosity, ∆η*:
η*(T*,F*) ) η*0(T*) + ∆η*(T*,F*) (18)
For η/0, we use the first-order approximation of the
Chapman-Enskog approach applied to the Lennard-
Jones potential,33 which, in reduced units, is
(T*)1/2
η/0 ) 0.17629 A (19)
Ωv c
where Ωv is the collision integral, which is a function
of T*, that can be estimated using the correlation by
Neufeld et al..33 This correlation is applicable from 0.3
< T* < 100. The coefficient Ac ) 1 for the LJ fluid. For
real fluids, this parameter has been adjusted on meth-
ane results, then taking a value of 0.95 (see Section 5.1).
To model the residual viscosity, a new formulation is
proposed. We have divided it into two contributions: one
independent of temperature, corresponding to a classical
mid-density contribution46 composed of two terms, and
one introducing the coupling between temperature and
density effects
b5
∆η* ) b1(eb2F* - 1) + b3(eb4F* - 1) + (eb6F* - 1)
(T*)2
(20)
where the coefficients bi are fitted on molecular dynam-
ics simulations results. One may note that, for this
correlation, we have adjusted only 1 + 6 coefficients,
which is far less than that needed for the correlations
in refs 25 and 24, which need, respectively, 5 + 24 and
5 + 18 coefficients. Despite its simplicity, this new
formulation is able to fit the results with an accuracy
close to the one provided by MD. In addition, it should
be noted that this correlation, eqs 18-20, does not
embody the enhancement of viscosity close to the critical
point,24 which is nevertheless limited to a small area
close to the critical point.
4.2. Correlation Regression of the LJ Fluid. To
regress the 6 numerical coefficients, bi, appearing in eq
20, we have used the database composed of 80 new
points of simulations of our own and 258 points coming
from Meier et al.26,47 and described in section 3.4. The
regression has been performed in order to minimize the
∆max (with the bias constrained to nil). These coefficients
are summarized in Table 1.
Table 1. Coefficients Used in the Viscosity Correlation
(Eq 20)
i 1 2 3 4 5 6
bi 0.062692 4.095577 -8.743269 11.124920 2.542477 14.863984
× 10-6 × 10-6
The AAD between the molecular dynamics values and
those using the correlation is equal to 1.925% and the
∆max ) 5.75%. Compared to the inherent statistical
errors of the molecular dynamics simulations, such a
low AAD can be considered excellent.
The efficiency of this correlation, despite its low
number of coefficients, is strongly improved compared
to the ones given by previous correlations.24,25 Neverthe-
less, it should be noted that the LJ MD database on
which we have adjusted our correlation can be consid-
ered as more accurate than the one used by Rowley and
Painter25 and Zabaloy et al.24 This is mainly because
the simulations were 1 order of magnitude longer and
applied on, at least, five times larger systems. Figure 2
shows that the deviations between the MD values and
the correlated values do not exhibit any particular
systematic trend with density, except that results are
less spread at mid-density. Thus, this viscosity correla-
tion adequately represents the LJ reduced viscosity over
the domain 0 e F* e 1.275 and 0.6 e T* e 6, which
covers gas, liquid, and supercritical phases. Using eqs
11 and 12, this domain of validity can be expressed in
terms of classical reduced thermodynamic properties Fr
) F/Fc and Tr ) T/Tc, which is then 0 e Fr e 4.05 and
0.45 e Tr e 4.53 (where Fc ) critical density and Tc )
critical temperature).
 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6967

Figure 2. Deviations between MD computation results and those Figure 3. Viscosity deviations for methane given by the correla-
given by the correlation, eq 18. Full circles correspond to our tion, eq 18, relative to the values of Friend et al.48
simulations and open squares correspond to those of Meier.26
compounds being deduced using eqs 11 and 12. For the
Table 2. Critical Properties of the Tested Components
and Corresponding Lennard-Jones Molecular tested components, critical properties, drawn from ref
Parameters Deduced from Eqs 11 and 12 33, and corresponding molecular parameters are given
in Table 2.
compound Tc (K) Vc (cm3/mol) M (g/mol) σ (Å)  (J/mol) Table 3 shows the results obtained on these pure
methane 190.56 98.6 16.043 3.670 1258.1 compounds compared to reliable databases covering
ethane 305.32 145.5 30.07 4.179 2015.8 liquid, gas, and supercritical states. All these databases
propane 369.83 200 44.097 4.646 2441.8 are expressed in specific correlations for each compound,
argon 150.86 74.57 39.948 3.344 996
nitrogen 126.2 90.1 28.014 3.562 833.2
which corresponds to the best possible fit of a large
oxygen 154.58 73.37 31.999 3.326 1020.6 variety of experimental results. The values for which
carbon dioxide 304.12 94.07 44.01 3.613 2007.8 comparisons have been achieved are equally distributed
in all thermodynamic states. Because our correlation
5. Numerical Results for Real Fluids on LJ fluids has the restricted validity range given
previously, the test for the real fluids does not always
The scheme for the calculation of the viscosity is the correspond to the whole range accessible through the
following. First, it is necessary to calculate  and σ with corresponding real database and is restricted to the
eqs 11 and 12 and then to evaluate the reduced LJ ranges available for LJ fluids. So in Table 3, the
temperature T* and reduced LJ density F*, with eqs 4 temperature and pressure intervals correspond to the
and 5. Having these values and using eqs 18-20 with ones we used for the calculation.
the coefficients given in Table 1 and with Ac ) 0.95, the Results shown in Table 3 clearly indicate that this
reduced viscosity η* is evaluated and, finally, the entirely predictive scheme is able to provide a really
viscosity η is obtained from eq 7. Additionally, for good estimation of the viscosity over a wide variety of
mixtures, the Lorentz-Berthelot combining rules, eqs thermodynamic states of simple nonpolar fluids with
2 and 3, are used to define the crossmolecular param- AAD < 5%. It is interesting to note that the AAD
eters, and then eqs 8-10 are applied for the calculation obtained are only slightly worse than those obtained by
of the equivalent pseudocomponent representative of the evolved methods that need at least two parameters to
mixture. be fitted per compounds1-7 and that are sometimes
5.1. Pure Compounds. We have first applied this restricted to gases.4
correlation to test its ability to reproduce viscosity of The general trends of the results are consistent with
simple nonpolar molecules. The methane has been what was expected. The results are very good for
chosen to be the reference component in order to deduce methane (P < 55 MPa), oxygen (P < 100 MPa), and
the optimum reduced critical density for viscosity nitrogen (P < 100 MPa), which are simple molecules.
estimation and the value of coefficient Ac appearing in Predictions are the worst in dense systems (which
eq 19. Fc* ) 0.302 and Ac ) 0.95 have been found to generally correspond to low-temperatures ones), as can
provide the best results on methane, compared to those be seen in Figures 3-6. In addition, deviations are
given in ref 48. These values have been kept for all the higher for larger molecules, mainly due to the fact that
components tested, except when stated. the LJ fluid is a spherical approximation (see Figures
Notice that the method is entirely predictive as 5-6). Multipolar effects, which are not included in such
already indicated (except for methane, for which Ac has an approach, also lead to non-negligible deviations, as
been adjusted), with the molecular parameters of pure shown in Figure 6 for carbon dioxide.

Table 3. Results Obtained for Different Pure Compounds on a Wide Variety of Thermodynamic States
compound Tmin-Tmax (K) Pmin-Pmax (MPa) AAD (%) ∆max (%) Nba database
methane 100-400 0.1-55 1.67 8.8 510 Friend et al.48
ethane 160-500 0.1-60 3.79 11.3 500 Friend et al.49
propane 180-600 0.1-100 4.89 15.62 510 Vogel et al.50
argon 90-500 0.1-400 4.4 24.45 550 Lemmon et al.51
nitrogen 70-600 0.1-100 2.35 24.15 510 Lemmon et al.51
oxygen 80-700 0.1-100 3.11 9.65 490 Lemmon et al.51
carbon dioxide 200-1500 0.1-300 4.53 24.8 525 Fenghour et al.52
a Nb ) number of data points.
6968 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005

Table 4. Critical Properties of Toluene and n-Decane

and Corresponding Lennard-Jones Molecular
Parameters Deduced from Eqs 11 and 12
compound Tc (K) Vc (cm3/mol) M (g/mol) σ (Å)  (J/mol)
toluene 591.75 316 92.141 5.412 3907.7
n-decane 617.7 624 142.286 6.789 4078.1

Table 5. Results Obtained on Two Nonspherical

Molecules (Toluene and n-Decane) in the Liquid Phase
Tmin-Tmax Pmin-Pmax AAD ∆max
compound (K) (MPa) (%) (%) Nb database
toluene 293-373 0.1-140 9.95 19.4 68 Canet9
n-decane 293-373 0.1-140 37.37 50.9 68 Canet9

Figure 4. Viscosity deviations for argon given by the correlation, Table 6. Results Obtained on Toluene and n-Decane in
eq 18, relative to the values of Lemmon and Jacobsen51. the Same Conditions as those in Table 5 with a Fit on
the Atomic Diameter
compound adjusted σ (Å) AAD (%) ∆max (%)
toluene 5.390 2.56 6.5
n-decane 6.728 3.25 9.6

molecules in a liquid phase under pressure. These

Figure 5. Viscosity deviations for propane given by the correla-
tion, eq 18, relative to the values of Vogel et al.50
Figure 6. Viscosity deviations for carbon dioxide given by the
correlation, eq 18, relative to the values of Fenghour et al.52
Concerning the large deviations at very high pressure
on quasi-spherical molecules (see methane or argon,
Figures 3 and 4, respectively), it is probably due to the
simple repulsive form of the LJ potential, which is not
accurate enough in extreme pressure cases.53 To cir-
cumvent these relatively weak results in a very dense
phase, keeping a spherical approximation, a different
choice in the way to describe the repulsive part of the
potential, with a different repulsive exponent or an ex-
ponential description, may be a valuable alternative.54-56
But, more simply, a fit of the molecular parameters
using the viscosity database will certainly improve
results compared to a purely predictive scheme. Such
work to construct a viscosity-optimized database of
molecular parameters is in progress.
Finally, this method has been applied on pure toluene
and pure n-decane in order to have an idea of the
limitation of this scheme when dealing with larger
extreme conditions are normally the worst circum-
stances for such approach. In Table 4 are given the
molecular parameters and critical properties of both
species.
Results given in Table 5 indicate that the larger the
molecule, the worse the prediction. So this scheme
seems to be relatively inadequate for such nonspherical
compounds. Furthermore, as previously seen, in very
dense systems this predictive scheme is less adequate.
So, as the data taken for comparisons in Table 5 are
such that 0.975 > F* > 0.842 for toluene and 1.056 >
F* > 0.905 for n-decane, these deviations are not
surprising. To improve the results on both compounds,
we have tried to fit the atomic diameter on viscosity
results. The optimization has been done in order to
minimize the ∆max value.
It is clear from the results given in Table 6 that such
a procedure with only one fitted parameter strongly
improves the results, which become as good as those
coming from the most recent classical schemes. Using
this fitting procedure for toluene, σ is reduced from
5.412 Å, the value calculated with eq 12, to 5.390 Å
(variation < 0.5%). For n-decane, σ is reduced from
6.789 to 6.728 Å (variation ≈ 0.9%). Obviously, for such
a high-density system, viscosity amplitude is highly
sensitive to the σ parameter, i.e., to the accuracy of the
critical volume. This result is not surprising, as diffusion
is extremely sensitive to the value of the atomic
diameter in a dense system.22,35 Such a fitting proce-
dure, which corresponds to a modification of the critical
volume, is very similar to what is classically done for
cubic equations of state.27
5.2. Mixture Results. Dealing with mixtures is
always a tough problem. Concerning viscosity, efficient
schemes become a lot more complex than those in pure
fluids and are often limited to a certain kind of mixture.
In the proposed scheme, the viscosity for the mixture
is predicted using only a set of combining rules, eqs 2
and 3, and a one-fluid approximation, eqs 8-10; this
simple approach can then be considered as fully predic-
tive for mixtures. We have applied this scheme on
various binary mixtures and on synthetic natural gases
composed of three to five compounds.
5.2.1. Simple Binary Mixtures. We have first
chosen binary simple mixtures where high-pressure
data are available to test our predictive scheme. The
 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6969

Table 7. Results Obtained on Viscosity, Using the

Scheme Proposed in This Work, for Different Simple
Binary Mixtures (with LB Combining Rules and vdW1
Approximation)
Tmin-Tmax Pmin-Pmax AAD ∆max
mixture (K) (MPa) (%) (%) Nb
CH4 + N2 100-300 1.6-30 3.59 10.3 301
CH4 + CO2 323-473 3.3-68 1.95 6.6 159
CH4 + C2H6 120-300 1.5-30 3.29 12.3 223

Figure 8. Viscosity deviations from the natural gas mixture

measurements of Assael et al.2

Figure 7. Viscosity deviations for the methane-ethane system

from the results of Diller58 using eq 18 coupled with the vdW1
and LB combining rules: 2, xCH4 ) 0.345; [, xCH4 ) 0.5; and 1,
xCH4 ) 0.685; and O, pure methane and 0, pure ethane (the pure
compounds use the same reduced temperature range as for
mixtures).

first mixture57 is composed of methane and nitrogen for
three molar fractions: xCH4 ) 0.317, 0.5, and 0.714. The
thermodynamic conditions correspond to gas, liquid, and
supercritical states. The second mixture46 is composed
of supercritical mixtures of methane and carbon dioxide
at three molar fractions: xCH4 ) 0.243, 0.464, and 0.755.
The third mixture58 is composed of methane and ethane
in gas, liquid, and supercritical phases at: xCH4 ) 0.345,
0.5, and 0.685.
The results given in Table 7 are really good, when
taking into account the simplicity of the scheme and
keeping in mind that this approach is predictive. It is
obvious that, in these cases, the LB combining rules
combined with the vdW1 approximation are able to
provide consistent values of mixture viscosity, with the
AAD < 4%. Elsewhere, it is interesting to note that, once
again, results are slightly worse in the liquid phase, as
for the methane-nitrogen or the methane-ethane
mixtures at low temperatures and high pressures, as
shown in Figure 7.
It can be deduced from Figure 7 that deviations on
mixture viscosity are mainly due to those on the pure
species, which leads to an overestimation in the very
dense state (F* > 0.85). In fact, the one-fluid approxima-
tion, including the LB combining rules, does not too
strongly alter the results; for mixtures, the results are
as good as those for pure species. Nevertheless, this
scheme is responsible for slight misevaluations because,
as seen in Figure 7, the deviations on the viscosities of
the mixture do not all lay between those of the pure
species. This is particularly true at low densities (F* ≈
0.1) and at very high ones (F* > 0.85), where unexpected
Figure 9. Viscosity deviations from the natural gas + H2
measurements of Nabizadeh and Mayinger:62 O, xH2 ) 0; 0, xH2 )
0.05; 4, xH2 ) 0.15; and 3, xH2 ) 0.30.
deviations appear mainly for xCH4 ) 0.5. These remarks
are consistent with previous works,59-61 which have
shown some limitations of the vdW1 approach.
5.2.2. Natural Gas. Because of the simplicity of the
vdW1 approximation and of the LB combining rules, the
scheme proposed is as easy to handle for multicompo-
nent mixtures as for binary ones. We have then applied
the correlation on synthetic natural gas mixtures on
which accurate measurements have been recently per-
formed.2,62 The first mixture is composed of methane,
ethane, propane, nitrogen, and carbon dioxide, and the
second one is composed of methane, ethane, nitrogen,
and hydrogen in various proportions (up to 30% in molar
fraction). Table 8 indicates that this predictive scheme
provides excellent results for both cases with an AAD
< 1% and a ∆max < 4%. The results are at the same
level as the most recent schemes,7 which need at least
a fit on the pure properties in the same thermodynamic
conditions, whereas our scheme does not.
It is interesting that the deviations shown in Figures
8 and 9 are well-distributed around the zero line.
Nevertheless, these figures exhibit a slight systematic
underestimation of the viscosity for the lowest densities.
These excellent results are not really surprising
because, for those mixtures, methane is the compound
on which the optimization of the reduced critical density
has been performed. Moreover, on this reduced density
range, results using this scheme are particularly good

Table 8. Results Obtained on Viscosity, Using the Scheme Proposed in This Work, for Natural Gases (with LB
Combining Rules and vdW1 Approximation)
mixture Tmin-Tmax (K) Pmin-Pmax (MPa) AAD (%) ∆max (%) Nb database
natural gas 240-450 0.1-14 0.72 3.53 40 Assael et al.2
natural gas + H2 298-400 0.1-6.5 0.68 2.17 190 Nabizadeh et al.62
6970 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005

Table 9. Results Obtained on Viscosity, Using the tures in various states are as good as those on pure
Scheme Proposed in This Work, for an Asymmetric fluids. Furthermore, this scheme is shown to be able to
Mixture (with LB Combining Rules and vdW1
provide results which are at the same level as the most
Approximation)
evolved ones on natural gas mixtures with a predictive
Tmin-Tmax Pmin-Pmax AAD ∆max approach. Finally, the limitations of such a simple
mixture (K) (MPa) (%) (%) Nb database scheme are shown on asymmetric mixtures composed
CH4 + C7H8 293-373 20-140 19.2 36.0 276 Canet9 of methane and toluene.

(see Figure 4, for instance). Furthermore, all the species Acknowledgment

are quite small molecules, and the thermodynamic
This work is a part of the ReGaSeq project managed
conditions are well-adapted for this predictive scheme.
by TOTAL and the Institut Francais du Pétrole. We
Nevertheless, it was not obvious that a one-fluid ap-
wish to thank François Montel for fruitful discussions
proximation combined with a simple combining rule
and for having initiated this work. We thank the Centre
would be able to yield such good results on ternary,
Informatique National de l’Enseignement Supérieur in
quaternary, and quinary mixtures.
Montpellier (France) and the pôle de SImulation et
5.2.3. Asymmetric Mixture. To have an estimation MOdélisation en Aquitaine in Bordeaux (France) which
of the limitations of such a scheme when applied to more provided a large part of the molecular dynamic simula-
complex mixtures, a test on a methane-toluene mixture tion computer time for this study.
(an asymmetric mixture) has finally been performed.
This mixture was experimentally studied by Canet9 for
a large range of thermodynamic states (see Table 9) and Appendix A
for various molar fraction: xCH4 ) 0.25, 0.37, 0.5, 0.64, New LJ Viscosity Values.
and 0.95. The accurate prediction of viscosity in this
mixture has been shown to be difficult.8
Table 9 exhibits the poorest results obtained with this F* T* P* η* F* T* P* η*
scheme, with the deviations being two times larger than 0.212 1.5 0.186 0.244 0.778 1.5 2.804 1.738
those of the worst results for pure compounds (toluene). 0.212 1.75 0.266 0.274 0.778 1.75 3.763 1.701
It should be noticed that the largest deviation (36%) has 0.212 2 0.346 0.299 0.778 2 4.675 1.657
0.212 2.25 0.423 0.323 0.778 2.25 5.559 1.693
been found for the equimolar mixture at the lowest 0.212 2.5 0.498 0.339 0.778 2.5 6.412 1.711
temperature and the highest pressure. Nevertheless, 0.3 1.5 0.220 0.321 0.8 0.7 -0.545 2.307
despite its simplicity, this predictive scheme is not 0.3 2 0.483 0.362 0.8 0.8 -0.008 2.223
completely out of range compared to some classical 0.3 2.5 0.741 0.402 0.8 0.9 0.509 2.085
models.8 0.3 4 1.495 0.511 0.8 1 0.998 2.061
0.354 1.5 0.242 0.366 0.8 1.5 3.278 1.878
The weaknesses of such a scheme when applied to 0.354 1.75 0.415 0.390 0.8 4 12.132 1.865
asymmetric mixtures (apart from the limitation of the 0.354 2 0.588 0.418 0.85 0.6 -0.587 4.035
LJ fluid model) come certainly from the combining rules 0.354 2.25 0.753 0.444 0.85 0.7 0.090 3.432
as well as from the one-fluid approximation itself. It is 0.354 2.5 0.925 0.466 0.85 0.8 0.732 3.120
known that the use of a corresponding state approach 0.4 1.5 0.281 0.414 0.85 0.9 1.342 2.927
is less and less valid for molecules having a very 0.4 4 2.321 0.625 0.85 1 1.922 2.807
0.495 1.5 0.396 0.578 0.9 0.6 0.311 6.495
different shape from the reference compound.32 0.495 1.75 0.721 0.602 0.9 0.7 1.101 5.360
0.495 2 1.043 0.625 0.9 0.8 1.850 4.802
6. Conclusions 0.495 2.25 1.358 0.641 0.9 0.9 2.566 4.476
0.495 2.5 1.668 0.671 0.9 1 3.260 3.997
In this work, a predictive scheme for the viscosity of 0.5 1.5 0.405 0.586 0.9 1 3.261 4.157
pure fluids and of mixtures of simple molecules has been 0.5 2 1.065 0.622 0.9 1.5 6.363 3.197
built. This scheme relies on the microscopic formulation 0.5 2.5 1.704 0.671 0.9 2 9.099 2.985
of the law of the corresponding states for a Lennard- 0.5 4 3.520 0.794 0.9 2.5 11.598 2.764
0.6 1.5 0.769 0.835 0.9 4 18.229 2.675
Jones fluid. To estimate viscosity, we have developed a 0.6 4 5.315 1.011 0.919 1 3.893 4.819
correlation based on previous and new Lennard-Jones 0.636 1.25 0.397 0.915 0.919 1.25 5.595 4.123
molecular dynamics results. Results for mixtures are 0.636 1.5 0.994 0.934 0.919 1.5 7.165 3.564
deduced through a van der Waals one-fluid approxima- 0.636 1.75 1.572 0.957 0.919 1.75 9.419 3.460
tion combined with Lorentz-Berthelot combining rules. 0.636 2 2.132 0.985 0.95 0.7 2.602 10.300
0.636 2.25 2.679 1.012 0.95 0.8 3.463 8.457
This new scheme is valid for 0 e Fr e 4.05 and 0.45 e
0.636 2.5 3.211 1.051 0.95 0.9 4.290 7.107
Tr e 4.5. 0.7 1 0.018 1.228 0.95 1 5.068 6.174
The molecular parameters of pure species are deduced 0.7 1.5 1.583 1.221 0.95 1.2 6.551 5.300
from the critical temperature and volume. Using these 0.7 2 3.022 1.239 1 0.9 6.623 12.900
parameters, the correlation is shown to provide average 0.7 2.5 4.366 1.257 1 1 7.506 11.100
absolute deviations <5% for some small molecules, on 0.7 4 8.032 1.348 1 1.2 9.197 8.630
0.778 1 0.697 1.776 1 1.5 11.596 6.740
a wide thermodynamic state range covering gas, liquid, 0.778 1.25 1.789 1.698 1 4 27.101 3.853
and supercritical phases from low to high pressures. The
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Received for review February 8, 2005
Revised manuscript received May 18, 2005
Accepted June 7, 2005
IE050154T