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Review
Molecular simulation of the thermophysical properties of fluids:
From understanding toward quantitative predictions
Philippe Ungerer a,, Carlos Nieto-Draghi a , Bernard Rousseau b ,
Gktug Ahunbay b,c , Vronique Lachet a
a
Institut Franais du Ptrole, 1-4 avenue de Bois Prau, 92852 Rueil-Malmaison, France
b
Laboratoire de Chimie Physique, Universit de Paris Sud CNRS, 91405 Orsay, France
c
Chemical Engineering Department, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey
Available online 7 March 2007
Abstract
The purpose of the present paper is to review what kind of thermophysical properties can be predicted, either qualitatively or quantitatively
with molecular simulation. In a first part, the main types of molecular simulation methods are introduced. Molecular dynamics (MD) can be used
to address equilibrium properties and dynamic behaviour as well. Monte Carlo simulation (MC) is particularly adapted to phase equilibria or
physisorption. Both methods require to represent the potential energy, which is classically decomposed into intramolecular (bending, torsion, etc.)
and intermolecular (dispersion, repulsion, electrostatic, polarization) contributions.
In a second part, the prediction of fluid properties (PVT relationships, enthalpy, heat capacity, JouleThomson coefficient, etc.) is reviewed.
Either MC or MD can be used to relate these properties and molecular structure, as shown by examples like high pressure hydrocarbon gases,
CFCs, acid gases, and natural gases.
Fluid phase equilibria are discussed in the third part. Examples are given in which MC is used to provide pure component properties when pure
chemicals are not commercially available, such as heavy hydrocarbons of complex structure. MC is also capable of predicting phase behaviour for
mixtures with little (or no) calibration on binary system data. This aspect is illustrated by the prediction of Henry constants of gases in polar liquids
and by the prediction of phase diagrams of acid gases (H2S, CO2) with water, methanol or hydrocarbons. The self-association of polar molecules
and the critical scaling behaviour are also described.
In the fourth part, transport properties (viscosity, diffusion coefficients, and thermal conductivity) are discussed. For many systems like
hydrocarbons, carbon dioxide or hydrogen sulphide, very good predictions are obtained, and simulation is shown to predict detailed features such
as the differences in viscosity between isomers.
In Conclusion and perspectives, the current limitations and possible improvements of molecular simulation methods are mentioned.
2007 Published by Elsevier B.V.
Keywords: Molecular simulation; Molecular dynamics; Monte Carlo simulation; Fluid phase equilibria; Transport properties; Viscosity
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2. Molecular simulation methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.1. Statistical ensembles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.2. Energy of molecular systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
2.3. Monte Carlo methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
2.4. Molecular dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
2.4.1. Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
2.4.2. Computing transport properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
Corresponding author.
E-mail address: presse@ifp.fr (P. Ungerer).
Fig. 1. The two ways of building a statistical ensemble: Molecular dynamics (MD) and Monte Carlo (MC) simulation. Average properties can be determined from time
averages in MD and from ensemble averages in MC. Both averages are equivalent, as a consequence of the ergodicity theorem.
P. Ungerer et al. / Journal of Molecular Liquids 134 (2007) 7189 73
Table 1
Statistical ensembles
Statistical ensemble Imposed variables Probability density Applications
Canonical ensemble N, V, T exp( E) Phase properties (P, H, Cv, , )
Grand Canonical Ensemble i, V, T ! Adsorption isotherms, selectivities
X
exp bE b li Ni
i
Gibbs Ensemble at imposed pressure (m phases) N = N1 + Nm, P, T exp( E PV) Phase equilibrium of mixtures
The probability density is given in phase space, i.e. the space of all positions and momenta. E is total energy (kinetic + potential), N is number of molecules, V is system
volume, T is temperature, P is pressure and i is chemical potential of molecular type i.
and engineering models in various circumstances: unknown in microporous adsorbents. This technique is also expected to
chemicals, extreme conditions of temperature or pressure, toxic provide key interpretations and predictions, because the
compounds, among others. relevant length scales (interface thickness or pore diameter)
The first part of this article provides a brief review of the are comparable to molecular size.
main simulation methods applicable to determine the thermo-
physical properties of fluids. These comprise molecular 2. Molecular simulation methods
dynamics (MD), which consists in integrating Newton's
equations of motion for all particles with time, and Monte 2.1. Statistical ensembles
Carlo simulation (MC), in which a statistical method is used to
generate representative system configurations on the basis of Depending on the application desired, different statistical
the probability distribution of potential energy. The main ensembles can be used (Table 1), each ensemble being
features of the most common potential energy models are also characterized by the constrained variables and by its probabil-
given. ity density, i.e. the probability of occurrence of each system state
In the second part, we will review the application of mole- in the ensemble [1]. For a given problem, the selection of the
cular simulation to the equilibrium properties of fluids (PVT type of ensemble is generally made in such a way that the
relationships, enthalpy, heat capacity, JouleThomson coeffi- constraints correspond to variables that are controlled in the
cient). Either MC or MD can be used to relate these properties experimental set-up. The variables that are not constrained are
and molecular structure, as shown by examples like high pres- fluctuating, and their statistical averages provide predictions
sure hydrocarbon gases, CFCs, acid gases, and natural gases. that may be compared with experimental results.
In the third part, we will consider fluid phase equilibria, for The canonical ensemble, in which the temperature, number
which MC is the most efficient technique. It can be applied to of molecules and volume are imposed, is used for monophasic
the prediction of the vaporliquid equilibrium properties of fluids when density is known. The predicted average properties
pure compounds on the basis of their molecular structure, if the are then average energy, pressure, and chemical potential.
potential energy model has been previously parametrized. In the isothermalisobaric or NPT and ensemble, pressure is
Concerning mixtures, we will see that the distinction between imposed instead of volume, and the average volume of the
the major forms of energy (repulsion, dispersion, electrostatic) system is used to predict fluid density. This ensemble is used,
may result in excellent predictions of phase diagrams for for instance, when the properties of a fluid are to be determined
mixtures involving polar fluids like water or methanol. We will at known pressure and temperature.
show also how these techniques may be used to model the near- The ensemble which is the most widely used for phase
critical behaviour of fluid mixtures and to characterize equilibrium calculations is the Gibbs ensemble [7] in which two
association phenomena. phases are introduced without explicit interface. This may be
Transport properties can be addressed with MD, the results done either by imposing the global volume of the two phases, or
of which can be processed to determine transport coefficients: the pressure [3]. The temperature and the total number of
viscosity, diffusion coefficients, and thermal conductivity. We molecules are also imposed in the Gibbs ensemble. When
will show representative examples, and discuss which type of applied to pure compounds, this ensemble is applied as constant
potential energy model might be capable of providing general volume to respect the phase rule. Its outputs are then the
answers in this field which has been less systematically ex- equilibrium properties: saturated vapor pressure, vaporization
plored than equilibrium properties. enthalpy, and the coexisting densities of the liquid and vapor. In
Finally, we will briefly quote other applications of molecular the case of mixtures, the Gibbs ensemble may be applied either
simulation in the field of interfacial phenomena and adsorption at imposed volume or at imposed pressure. In both cases, it
74 P. Ungerer et al. / Journal of Molecular Liquids 134 (2007) 7189
provides the equilibrium compositions and densities of coex- 2.2. Energy of molecular systems
isting phases.
The ensemble that is most adapted to adsorption in Although the total energy E appearing in the probability
microporous solids is the Grand Canonical ensemble, where densities of Table 1 is the sum of the kinetic energy and potential
the temperature, the volume, and the chemical potential of each energy, only the latter needs to be provided as an explicit func-
species are the imposed variables. For such applications, the tion of molecular coordinates through a suitable intermolecular
computation must account for the interaction energy between potential energy model. In MD, this is sufficient to compute the
each molecule and the microporous adsorbent. The most desired forces acting between molecules or parts of molecules, and
output is the average number of molecules of every species in kinetic energy is an outcome of the simulation. In MC, an
the system, i.e. the amount adsorbed. analytical integration of the contribution of the kinetic energy is
Beside common average properties like density, pressure or performed, so that it does not need to be explicitly considered.
energy, the analysis of fluctuations allows to determine As summarized in Fig. 2, the potential energy is decomposed
thermodynamic properties like the heat capacity, the compress- classically into intermolecular (or external) energy and intra-
ibility, the thermal expansion coefficient or the JouleThomson molecular energy:
coefficient [8,9].
Practically, there are two main methods to simulate statistical U Uint Uext 3
ensembles (Fig. 1). The first is through molecular dynamics,
which consists in solving the equations of motion, and the The intermolecular energy arises from the interaction
second is Monte Carlo simulation, in which a statistical method between different molecules. In the applications considered
is used. here, it is decomposed as: Uext = Udr + Uel + Upol where Udr
Once a large number of configurations has been generated, arises from dispersion and repulsion interactions, and Uel is the
the statistical average of property X (such as volume, energy, ) electrostatic (or coulombic) interaction energy and Upol is the
may be computed by an arithmetic average over all configura- polarization energy [10].
tions: The dispersionrepulsion energy, which is dominant in low
polarity systems like alkanes, is obtained by a summation over
1X n
all the pairs of force centers. Although the Buckingham exp-6
hX i Xi 1
n i1 model has been shown to be more accurate on several important
systems [1113] the most popular model is still the Lennard
Similarly, thermodynamic derivative properties can be Jones 612
obtained from statistical fluctuations. For instance, heat ca-
X 12 6 !
pacity at constant pressure, Cp, is obtained from the fluctuations rij rij
Udr 4eij 4
of energy in the isothermalisobaric ensemble rij rij
i; j
1 ibj
Cp 2
hE PV 2 ihE PV i2 2
kB T where rij is the separation distance between force centers.
P. Ungerer et al. / Journal of Molecular Liquids 134 (2007) 7189 75
Potential energy models considering individual atoms as iation of the angle between two successive chemical bonds, 3
force centers are referred to as All Atoms [1416]. A specific the torsion energy arising from the variation of the dihedral
version of the All Atoms model has been proposed in which the angle defined by three successive chemical bonds, 4 the
hydrogen force centers are located at the mid-point of the dispersionrepulsion between distant atoms which prevents
carbonhydrogen bond [17]. If the force center represents a overlaps within the same molecule. When simulating the
group of atoms and is located on the main atom of the group, the thermophysical properties of common fluids, the bond lengths
model is said United Atoms [1820]. Alternatively, the force are often considered constant (they are taken from X-ray dif-
center may be located at an intermediate position between the fraction results), and the stretching energy is accordingly
atoms belonging to the group (Fig. 2), and the model is then neglected. This approximation allows to use longer time steps in
known as Anisotropic United Atoms or AUA [2123]. The molecular dynamics, and thus shorter computing time. However
parametrization of the AUA intermolecular potential for it should be noted that vibrational temperatures are often much
hydrocarbons, which is used for several examples discussed higher than investigated temperatures (more than 1000 K) so
in the present article, is outlined in Fig. 3. that the corresponding degrees of freedom are not fully ac-
The electrostatic energy is computed directly from the tivated from a quantum mechanical point of view. A classical
Coulomb law, assuming that the molecules bear electrostatic description of bond stretching using a harmonic potential is thus
point charges an approximation that may lead to wrong vibrational energies.
X 1 qi qj Bending and torsional parameters are determined to match
Uel 5 equilibrium conformation angles, infrared spectroscopy data
4peo rij and quantum chemistry results [15]. In flexible molecules, these
i; j
ibj contributions are summed over all bending and torsion angles in
the molecule. If a molecule (or a part of molecule) is considered
where the sum runs over all possible pairs i, j of partial charges rigid, these contributions are not taken into account.
qi, qj, rij is the separation distance and o = 8.8541910 12 C2
N 1 m 2. Point charges may be determined from dipole 2.3. Monte Carlo methods
moment or quadrupole moment for small molecules like N2 or
CO2 but they are more frequently regressed from quantum The basis of Monte Carlo (MC) methods is to generate
chemistry results [15,2426]. successive configurations of the simulated system by a statis-
The polarization energy may be computed on the basis of the tical method to respect the probability distribution of the desired
molecular polarizabilities, which are known from experimental statistical ensemble. This method describes the configuration
measurements. space, in which only positions are considered, momenta (or
The intramolecular energy is assumed to be the sum of four velocities) being treated implicitly. Each configuration is gen-
terms (Fig. 2): 1 the stretching energy associated with bond erated by applying an elementary change (or MC move) to the
length variations 2 the bending energy arising from the var- previous configuration of the chain. In order to sample correctly
Fig. 3. Parametrization of the Anisotropic United Atoms intermolecular potential for hydrocarbons. The LennardJones parameters for each group have been
determined from the saturation pressure, vaporization enthalpy and liquid density of 14 hydrocarbons comprising three n-alkanes [22], isobutane [75], two cyclic
alkanes [30], two aromatics [7678] and six olefins [79].
76 P. Ungerer et al. / Journal of Molecular Liquids 134 (2007) 7189
the desired equilibrium distribution, it is sufficient to respect the statistical bias. The analysis of the interaction energy of the test
microreversibility criterion, which states that the flux of con- particle with the rest of the system allows to determine the
figurations from state i to state j is equivalent of the inverse flux chemical potential of the species [31]. This is useful because
from j to i: chemical potential cannot be obtained by simple thermody-
namic averages like volume or energy.
qi pij qj pji 6 The determination of energetic properties must take into
where i is the probability of configuration i, which is pro- account the fact that the kinetic energy is not computed in MC,
portional to the Boltzmann weight exp( U), and pij is the while it contributes to properties like enthalpy and heat capacity.
transition probability from configuration i to j. More precisely, Thus the enthalpy must be obtained by summing the residual
the probability density in the configuration space is enthalpy, which can be obtained from MC, and the ideal gas
enthalpy which may be taken from experimental data or group
V N expbU contribution methods [8,32]. However the calculation of the
qi ~ 7
KN N ! vaporization enthalpy does not require the knowledge of the
ideal contribution, as the latter is assumed identical in the liquid
where is the de Broglie wavelength, which includes the
and vapor phases [33].
kinetic contribution to the probability distribution, and U is the
Similarly, the residual heat capacity obtained by MC from
potential energy, including both inter- and intramolecular terms.
fluctuations, cpres, must be combined with the ideal heat capacity
In a Monte Carlo move, the microscopic reversibility crite-
cpid (i.e. the heat capacity in absence of intermolecular inter-
rion is used to determine appropriate transition probability from
actions) to obtain the total heat capacity at constant pressure, cp
i to j. The Metropolis algorithm provides the more commonly
[8]
way to satisfy this requirement
cp T ; P cres
p T ; P cp T
id
10
qj
pij min 1; 8
qi Na D E D E
p
cres U ext H hUext i H
If we consider the example of a translation move in the kB NT 2 D E D E
Na P
canonical ensemble, the test configuration is accepted with the 2
V H hV i H Na kB 11
following acceptance probability kB NT
vary with time. In many respects, MC and MD are equivalent simulations in the desired statistical ensembles, namely NVT
techniques. Identical results should be obtained for structural and NPT ensembles. The most widely used method consists in
and thermodynamic properties. However, dynamic properties adding external degrees of freedom (called extended Hamilto-
can be studied only with MD, either at equilibrium or far from nian methods) to the system in order to describe the coupling
equilibrium. between the set of particles and a heat or pressure bath [37,38].
In MD, the dynamics of molecules is usually assumed to Other methods based on the Gauss constraint principle [39] or
obey classical equations of motion, which is a satisfactory simple velocity and/or particle rescaling are also used.
approximation for translational motion as the de Broglie Another important feature of molecular dynamics concerns
wavelength of a typical molecule is much less than the average the description of the internal degrees of freedom of flexible
distance between molecules, i.e. molecules, like alkanes. Stretching, bending and torsion
motions can be described using intramolecular potential func-
Kt V =N 1=3 12 tions (see Section 2.2). However, in most applications the fastest
modes can be freezed using a constraint algorithm like
h
where Kt p is the translational de Broglie wavelength. SHAKE [40] or Gauss constraints [41] which maintains bond
2kmkB T distances to a constant value. Equations of motion can therefore
In this limit, there is a continuous distribution of accessible
be integrated using a larger time step, hence enabling simu-
energy states. Rotational motion can also be treated classically
lations on a larger time scale.
provided the rotational energy spacing is much less than kBT.
These criteria are true for the vast majority of molecules under
2.4.2. Computing transport properties
ordinary conditions and the classical approximation is routinely
Different methods exist to compute transport coefficients in
used in MD. As indicated above, vibrational degrees of freedom
MD. From a practical point of view, the simplest approach
may be affected by quantum effects. However, they are either
makes use of equilibrium MD simulations and of the Green
removed (for instance by considering constant bond lengths)
Kubo (GK) relationships [42]. The GK relationships relate
or treated classically with a harmonic potential. The description
equilibrium fluctuations of the fluxes to the corresponding
of the dynamics follows from the Hamiltonian of the system H
phenomenological (or Onsager) coefficients Lij
(rN, pN)
Z l
V
X p2 Lij hJi tJj 0ieq dt 16
HrN ; pN i
U rN 13 3kB 0
i
2m i
Given a microscopic and instantaneous expression for the
where rN and pN represent the set of particle positions and fluxes Ji(t), one can compute the Lij's from a single equilibrium
momenta, mi the particle mass and U(rN) the potential energy run. Within the framework of irreversible processes, the Lij's
function as defined in Section 2.2. The Hamiltonian equations can therefore be connected with the transport coefficients [43].
of motion are given by For example, self-diffusion D, shear viscosity and thermal
conductivity can be computed at equilibrium from the fol-
AH p dp AH jr U rN
rd i i 14 lowing expressions
Api mi i
Ari i
Z lX
N
1
The equations of motion are integrated numerically using a D hvi tdvi 0idt 17
3N 0 i1
finite-difference method. The Verlet based or the Gear
predictorcorrector algorithms are the most commonly used Z l
V
integrators because they can be easily implemented in NVE and g hrxy trxy 0idt 18
other statistical ensembles [2]. Repeatedly integrating for kB T 0
several thousand times produce individual trajectories from
Z l
which time averages A can be computed for macroscopic V
properties from instantaneous values of any mechanical k hJq tdJq 0idt 19
3kB T 2 0
property A(t)
Z where vi(t), xy(t) and Jq(t) are respectively particle i velocity,
t0 t
1 pressure tensor component and heat flux. In the case of heat
hAi lim Asds 15
t Yl t t0 transfer, it should be noticed that there is no microscopic ex-
pression for heat flux. The thermal conductivity in mixtures is
At equilibrium, this average cannot depend on the initial time given from the integral of the autocorrelation of the heat flux,
t 0. given as
The solution of the above Hamiltonian equations of motion X
samples the microcanonical NVE ensemble. In order to com- Jq J e hi Ji 20
i
pare MD results with experimental data, it is often desirable to
work at conditions where temperature and/or pressure are held where Ji is the mass flux of particles i, hi is the specific enthalpy
constant. Different techniques have been developed to enable of species i and Je, is the internal energy flux whose
78 P. Ungerer et al. / Journal of Molecular Liquids 134 (2007) 7189
(i.e. the difference between the real and the ideal heat capacity at coefficient of a refrigerant, difluoromethane, has been comput-
constant pressure) shown in Fig. 4b is an example of ed along several isenthalps, using an original Monte Carlo
thermodynamic derivative property that can be computed procedure to simulate a statistical ensemble at imposed pressure
from the analysis of energy fluctuations in NPT calculations and enthalpy [54]. An intermolecular potential involving elec-
[8]. The maximum of the residual heat capacity is a trostatic point charges was used, in which the dispersion and
phenomenon which is linked with the strong variations of repulsion parameters were calibrated against equilibrium pro-
molar volume in the supercritical region. Simulation has been perties. As shown in Fig. 5, the agreement between simulation
also shown to describe qualitatively the maximum of Cv, the results and reference data is excellent over a large range of
heat capacity at constant volume for a constant temperature conditions. Other simulations conducted on carbon dioxide
(220 K) when density increases [52]. This maximum, which [55,56] have shown that the whole JouleThomson inversion
announces the non-classical anomaly of Cv in the critical curve i.e. the locus of the points where the sign of the Joule
region, is not reproduced with standard equations of state. It is Thomson coefficient changes in the P,T diagram is accurately
remarkable that these results have been obtained with a very predicted. The use of statistical fluctuations for computing the
simple model, as it involves only the two parameters of the JouleThomson coefficient is also applicable to mixtures [8]. In
LennardJones potential [53]. Fig. 6, it is applied to a mixture of 19 components representing a
Such calculations are not restricted to pure fluids of simple natural gas. This natural gas contains dominantly methane
structure like methane. For instance, the JouleThomson (65 mol%) and a complex distribution of hydrocarbons up to 30
carbon atoms [57]. At the reservoir temperature of 463 K, the
inversion of the JouleThomson effect is predicted to occur at a
pressure of 42 MPa [9]. This prediction was confirmed by
volumetric measurements. These results, associated with previ-
ous work [58] confirm the feasibility of selecting a represen-
tative component for each fraction of a complex fluid, so that
most of the fluid behaviour is captured and yet the simulation is
tractable.
Fig. 8. Saturated liquid density computed with the AUA potential for various Fig. 9. Vaporization enthalpy computed with the AUA potential for various
hydrocarbons, compared with experiment-based correlation from the DIPPR hydrocarbons, compared with experiment-based correlation from the DIPPR
data bank. data bank.
P. Ungerer et al. / Journal of Molecular Liquids 134 (2007) 7189 81
Table 2
Comparison of critical parameters and boiling temperatures determined by simulation with the AUA potential and experimental measurements
Compound Critical temperature Critical density Normal boiling temperature
(K) (kg/m3) (K)
Exp. Simulation Exp. Simulation Exp. Simulation
Ethane 305.4 311 202 210 184 nd
n-pentane 469.7 469 237 218 307.7 307
n-heptane 540.3 547 232 231 372 376
n-decane 617.7 616 236 225 447 445
n-dodecane 658.2 652 239 217 489 481
n-pentadecane (708) nd (250) nd 543.1 541
n-eicosane (768) nd (251) nd 617 609
Isobutane 407.8 nd 229 nd 261.4 268
2-methylhexane 530.4 537 227 238 362 362
2,4-dimethylpentane 519.8 529 240 247 354 357
Cyclopentane 511.8 507 271 275 322.4 311
Cyclohexane 553.6 559 273 271 353.9 352
Cyclooctane 647.2 647 283 303 424.3 nd
Ethylene 282.3 280 214 212 169.2 166
Propene 365 373 223 226 225.1 224
1-butene 419.5 420 233 236 267.1 262
1-pentene 464.7 462 234 232 303.3 298
1-hexene 504 499 237 241 336.6 328
1-octene 567.1 566 241 240 394.4 388
cis-2-butene 435.6 448 240 238 276.8 279
trans-2-butene 428.6 439 236 234 274 265
isobutene 417.9 426 234 232 266.2 260
Butadiene 425 422 245 237 268.6 264
trans-2-pentene 475 480 234 243 309.5 316
Benzene 562.2 558 302 302 353.2 350
Toluene (methylbenzene) 591.8 580 292 307 383.8 376
p-xylene (1,4 dimethylbenzene) 616.2 598 280 303 411.5 403
o-xylene (1,2 dimethylbenzene) 630.3 610 289.1 311 417.2 401
1,3,5 trimethylbenzene 637.4 622 280.2 285 437.8 415
n-propylbenzene 638.2 627 273 281 432.4 421
Naphthalene (748) 716 (315) 323 487.8 491
Reference compounds.
Values in parentheses are likely results of extrapolations rather than true measurements [99].
explained by their larger CC bond length, which is 1.535 as Indeed, the characteristic size of density or energy fluctuations
compared to 1.40 in aromatic rings. More generally, the increases when the critical point is approached, and larger
good agreement between simulation and experimental results in systems should be considered [85]. In the case of a pure com-
Figs. 68 illustrates the good reliability of the proposed pound, the critical coordinates may be obtained by assuming the
potential for a large range of molecules, as it comprises olefins, following scaling law
naphthenoaromatics, alkylaromatics, etc.
A first application of these intermolecular potentials is to qV qL AT Tc b 21
compute the properties of organic compounds that are not
commercially available in the pure form. This is the case for where 0.325 is a universal critical exponent, V and L are
instance of most branched alkanes beyond ten carbon atoms, the densities of the coexisting vapor and liquid phases, and Tc is
and this has motivated some systematic studies by molecular the critical temperature. This relationship may be used to regress
simulation with the NERD potential [81]. The TRAPPE the critical temperature and critical density from Gibbs ensem-
potential has been also used for predicting the properties of ble calculations performed at lower temperatures [3]. An alter-
heavy isoalkanes [82,83]. The Anisotropic United Atoms po- native, more rigorous method consists in using finite size
tential has been applied in several industrial projects to obtain scaling [85,86]. Table 2 provides the critical coordinates of
the properties of poorly known compounds including organic various hydrocarbons according to AUA potential.
sulphides and thiols [25], ketones and aldehydes [80], heavy
isoalkanes and alkyl-substituted polyaromatics [84]. 4.2. Mixtures
A characteristic feature of molecular simulation is that it
cannot be used in the close vicinity of the critical point, because The second major application of well calibrated force fields
it would be necessary to simulate systems of excessively large is of course the determination of phase diagrams for real mix-
size that are incompatible with reasonable computing times. tures, and we will mention only a few among the numerous
82 P. Ungerer et al. / Journal of Molecular Liquids 134 (2007) 7189
5. Transport properties differences in models and methodology, and the fact that both
examples underestimate the experimental value, the trend in
Prediction of transport properties of fluids with industrial viscosity with pressure is captured reasonably well for both
interest is one of the main motivations to perform MD simulations. Deviations become more important when the
simulations. The comparisons of simulation results with the pressure of the system is increased, the difference being more
available experimental data become the key point to determine pronounced for the AUA model. In this case the average
which intermolecular potential model should be employed to absolute deviation between simulations and experiments is of
analyze a particular system. In this section we intend to present the order of 40%. Dysthe et al. [117] have found that the mean
a series of cases where MD simulations have been employed to deviations on diffusion and viscosity of different UAAUA
compute transport properties such as shear viscosity, self- models analyzed over different states were of the order of 24%
diffusion and thermal conductivity of different systems. Our for AUA2, 26% for SKS2, 30% for AUA3, 48% for OPLS1 and
goal is to show illustrative examples to the reader where 54% for SMMK [118]. In general, all models tend to under-
different models have been applied to reproduce transport estimate the viscosity and to overestimate the self-diffusion.
properties at different thermodynamic conditions and to a wide The deviations increase when the density of the system is
range of systems. increased [45,119] as it is observed at high pressure in the
examples of n-octane and n-hexane in Fig. 13. However, there
5.1. Viscosity are certain cases where simple empiric intermolecular potentials
are robust enough to predict well the behaviour or fluids in a
Simple linear hydrocarbons are the first type of systems of wide range of conditions. This aspect is of particular interest
our list of examples. In Fig. 12 we present our simulation results when the fluid is toxic and corrosive, or when the domain of
for the effect of temperature variations on the shear viscosity of application requires extreme conditions of pressure and
ethane, n-pentane and n-dodecane computed with the AUA4 temperature or when the experimental determination of
model [22] at low-moderate pressures (0.1 to 5 MPa). A physicochemical data requires expensive equipment. This is
remarkable agreement is observed between the simulations and the case of hydrogen sulphide that is encountered in a
the experimental data [114,115] despite the wide range of significant amount in certain oil reservoirs. Nieto-Draghi et al.
temperatures employed, particularly for the case of ethane and [120] have investigated the transport properties of H2S along the
n-pentane. For the case of n-dodecane, it is worth to mention liquid vapor coexisting line using equilibrium MD simulations
the ability of the AUA4 to reproduce the strong change in the at constant pressure (NPT). In Fig. 14 we can observe the
viscosity experimentally observed [114] between 298 K and comparison of the simulation results (using the model of Kristof
473 K. Here, the average absolute deviation between the et al. [60]) and the experimental data [121] of the shear viscosity
simulation and the experimental data at this condition is of the of H2S at the LV equilibrium. The agreement between the
order of 20%. experimental data and the simulation results is very good. In this
Though the effect of temperature changes is well reproduced case the maximum deviation is lower than 20%, the difference
in simulations, the effect of changes in the pressure of the being more important at the low temperature and high density
system is more subtle. In Fig. 13 we can observe the pressure liquid phase. This example shows the prediction capacity of
variation of the shear viscosity of n-octane at 348 K using the molecular simulation method in direct industrial applications
UA-TraPPE [19,68] model using the non-equilibrium MD such as mixtures of H2S, CO2 and hydrocarbons in oil and gas
method from the work of Kioupis et al. [116] and our simulation production, for instance.
data for n-hexane at 333 K using the AUA4 model computed Molecular simulation techniques can also be used as sub-
with equilibrium MD in the NPT ensemble. Despite the stitute of experiments, for instance, in the understanding of the
Fig. 11. Phase diagram of the H2Smethanol system mixture at 348.15 K from Gibbs ensemble simulations, compared with experimental data [162].
84 P. Ungerer et al. / Journal of Molecular Liquids 134 (2007) 7189
Fig. 13. Pressure variation of the shear viscosity of n-octane at 348 K Fig. 14. Comparison of the experimental shear viscosity () [115] of H2S along
(simulations (), experimental data (---)[116]) and n-hexane at 333 K the liquidvapor coexistence curve with MD simulations () using the NPT
(simulations (), experimental data () [115]). ensemble [120].
P. Ungerer et al. / Journal of Molecular Liquids 134 (2007) 7189 85
Fig. 16. Influence of pressure at T = 323 K on the viscosity of xylene isomers Fig. 17. Comparison of the self-diffusion of pure alkanes of 110 carbons
using the OPLS model [124] (open symbols) and the AUA model (this work, obtained with MD simulations () and the experimental data () of Helbaek
full symbols) compared with experimental data [127] (full lines). [130] at 333 K and 30 MPa.
86 P. Ungerer et al. / Journal of Molecular Liquids 134 (2007) 7189
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