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Adsorption and Phase Behavior of Pure/Mixed Alkanes in Nanoslit Graphite

Pores: An iSAFT Application

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DOI: 10.1021/acs.langmuir.7b02055

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Cite This: Langmuir 2017, 33, 11189-11202 pubs.acs.org/Langmuir

Adsorption and Phase Behavior of Pure/Mixed Alkanes in Nanoslit

Graphite Pores: An iSAFT Application
Jinlu Liu, Le Wang, Shun Xi, Dilip Asthagiri, and Walter G. Chapman*
Department of Chemical and Biomolecular Engineering, Rice University, Houston, Texas 77005, United States
*
S Supporting Information

ABSTRACT: The prediction of fluid phase behavior in

nanoscale pores is critical for shale gas/oil development. In
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this work, we use a molecular density functional theory (DFT)

to study the effect of molecular size and shape on partitioning
to graphite nanopores as a model of shale. Here, interfacial
statistical associating fluid theory (iSAFT) is applied to model
alkane (C1 − C8) adsorption/desorption/phase behavior in
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graphite slit pores for both pure fluids and mixtures. The pure
component parameters were fit to the bulk saturated liquid
density and vapor pressure data in selected temperature
ranges. The potential of interaction between the fluid and graphite is modeled with a Steele 10-4-3 potential that is fit to the
potential of mean force from single-molecule simulations. Good agreement is found between theory and molecular simulation for
the density distributions of pure components in slit pores. The critical properties of methane, ethane, and their mixtures as well
as the shift in bubble point and dew point densities were studied, showing good agreement with simulation. The competitive
adsorption of mixtures of normal and branched alkanes in graphite pores was also studied. Heavier components more strongly
adsorb up to the point that the entropic penalty due to confinement reduces adsorption.

■ INTRODUCTION
The exploration and production of shale gas/oil requires a
reliable prediction of fluid-phase behavior under reservoir
conditions. The pores in shale are on the nanometer scale,
unlike that in conventional sandstones where the pore sizes are
in micrometers. The nanoconfinement of hydrocarbons can
affect the phase behavior and partitioning of components
between the matrix and production fractures as a result of the
strong interaction between the fluid molecules and pore
surface. Successful reservoir simulation can be achieved only
with an accurate model of hydrocarbon phase behavior, and a
number of studies have been performed to better understand
fluids in confined geometry. The physics of nanoconfinement
also affects other applications involving porous material, such as
gas storage using metal organic frameworks,1 catalysis in
zeolites,2 and gas mixture separation.3
One of the primary applications in the shale gas/oil industry
is to determine the density and phase behavior of the in-place
hydrocarbon mixture as a function of temperature and pressure
(ρ(T, P)). Standard adsorption and desorption experiments are
often used to characterize porous materials through capillary
condensation and hysteresis in nanoscale pores. In shale oil
production, the bubble point is one of the key parameters that
ensures a continuous flow of liquid production. Luo et al.4 used
differential scanning calorimetry to measure the bubble-point
temperature of octane and decane in controlled-pore glasses
(CPGs) with pore sizes of 4.3 and 38.1 nm. Cho et al.5
measured the bubble-point pressures of octane−methane and
decane−methane mixtures in mesoporous silica (SBA-15 and
SBA-16). Both of these experimental studies reveal the impact
of confinement on lowering the bubble point for pores of less
than 5 nm.
In addition to experimental work, molecular simulations have
been used extensively to understand the effect of confinement
on fluid properties. Severson and Snurr6 studied the single-
component adsorption of alkanes in carbon slit pores. Besides
the adsorption isotherms, the orientation profiles were also
reported, showing that short alkanes lay parallel to the walls
while longer alkanes have less distinct layering. To study how
confinement affects criticality, Akkutlu and Didar7 used the
NVT-Gibbs Monte Carlo method and Pitakbunkate et al.8 used
the grand canonical Monte Carlo method to obtain the critical
parameters of methane and ethane in graphite slit pores. Their
results, though different from each other, showed a large
deviation in critical properties from the bulk. The suppressed
critical point was shown to cause a large compositional change
in gas production. In a series of molecular dynamics studies by
Hu et al.,9−11 an activated kerogen model, namely, graphene
fragments with oxidized functional groups, was proposed in
comparison with the simple graphite model. They have studied
the behavior of water and hydrocarbons in model shale
nanopores. The activated kerogen model shows mixed wetting
Special Issue: Tribute to Keith Gubbins, Pioneer in the Theory of
Liquids
Received: June 15, 2017
Revised: August 29, 2017
Published: September 1, 2017

© 2017 American Chemical Society 11189 DOI: 10.1021/acs.langmuir.7b02055

Langmuir 2017, 33, 11189−11202
Langmuir
properties, and water tends to be trapped inside the pores.
They have also shown that a rough surface model adsorbs
alkanes more evenly while a smooth surface adsorbs alkanes in
layers. A more rigorous approach to modeling kerogen
molecules, which is based on an analysis of chemical structure,
elemental composition, and physical properties, was taken by
Ungerer et al.,12 and the adsorption isotherms of methane and
ethane on different-sized kerogen pores were generated.13 The
adsorption isotherms were modeled by an extended Langmuir
model and ideal adsorbed solution theory, which can capture
the adsorption behavior at low pressure but only works well for
large pores at high pressure. Molecular simulation by atomistic
models also helps to improve our understanding of kerogen
morphology and surface properties. Recent work by Vasileiadis
et al.14 has demonstrated the characterization of pore size and
pore surface elemental analysis using Ungerer’s model.
Computer simulation is a powerful tool for providing
detailed and accurate descriptions of real kerogen systems.
The high computing times of molecular simulation are
rewarded by the accurate prediction of system behavior.
However, for some purposes such as understanding the phase
behavior of a multicomponent system, density functional theory
is computationally more efficient. In particular, if one of the
components in the mixture is of extremely low concentration, it
becomes very challenging to obtain good statistics in molecular
simulation, resulting in increased computational cost. On the
other hand, a theoretical method such as density functional
theory can be validated versus molecular simulation and
efficiently extend the results to multicomponent mixtures and
trace components.
The molecular density functional theory applied here
combines several approaches to describe short-range repulsion,
long-range attraction, and molecular shape. Alkane molecules
are modeled as chains of spherical segments. The basic building
block of the theory is an inhomogeneous hard sphere fluid. The
fundamental measure theory15 proposed by Rosenfeld and a
few variants thereafter realized a quantitative description of
inhomogeneous hard sphere mixtures. The bonding of spheres
to form polyatomic molecules is accomplished through
extensions of Wertheim’s perturbation theory16−19 for associat-
ing and polymerizing spheres.20−22 Long-range attractions are
described using a mean field approximation (MFA) described
later. The mean field approximation (MFA), weighted density
approximation (WDA), and Wertheim perturbation
theory16−19 allow for modeling the molecular size and shape.
Spherical molecules such as Lennard-Jones spheres and
associating spheres in confined geometry have been studied
with DFT by numerous groups such as Peterson et
al.,23Sokolowski and Fischer,24 Segura et al.,21 Yu and Wu,25
Tripathi and Chapman,26 and Haghmoradi et al.27 The
adsorption isotherm kernel generated from DFT has been
used to characterize nanoporous carbon and silica28−30 and has
become one standard analysis tool in commercial adsorption
instruments. Although small molecules (e.g., nitrogen, argon,
and krypton) that are nearly spherical are mostly used in
nanoporous material characterization, polyatomic molecules in
confined media can be more fascinating in that practical
systems often involve mixtures such as in polymer synthesis,
lubrication, and hydrocarbon storage in shale. The develop-
ment of inhomogeneous statistical associating fluid theory
(iSAFT),22 modified iSAFT,31 and polymer-DFT25 has largely
enhanced our ability to model inhomogeneous systems of
complex fluids. The implementations of iSAFT or polymer-
11190
Article
DFT, to name a few, include the interfacial tension of
polymers,32 lipid assembly and confined block copolymers,33
tethered polymers within or without solvent,34 surfactant in
oil−water interfaces,35 the formation of micelles in oil/water/
surfactant systems,36 tethered polymer-modified pores,37,38 and
polymer adsorption.39 For applications in shale gas/oil systems,
other DFT approaches have also been proposed on the basis of
some common bulk equations of state. For example, the
adsorption and desorption behavior of hydrocarbon mixtures
was studied by Li et al.40 using a Peng−Robinson equation of
state (EoS) free energy functional.
A SAFT-41 or PC-SAFT-based42 free energy functional,
however, is more promising because molecular shape is
included in the free energy functional. To enable iSAFT to
match the dispersion contribution of the bulk PC-SAFT EoS,
several modifications of the dispersion functional have been
proposed. Shen et al.43,44 used a WDA in the dispersion term to
model methane and carbon dioxide adsorption on porous
carbon. Klink and Gross45 included the hard chain pair
correlation function in the dispersion functional and incorpo-
rated a local correction term to absorb the difference from the
PC-SAFT EoS chemical potential. Xu et al.46 decomposed the
dispersion term to a local and nonlocal contribution where the
surface-averaged density was used in a weighted-density-
approximated local term and a mean field manner was used
to account for the density variation. These developments can
lead to an improved prediction of the bulk pressure, density,
and chemical potential, which makes it easier to compare with
experiment and simulation. The accuracy of these dispersion
terms that reduce iSAFT to PC-SAFT EoS in the bulk is not
fully proven for confined fluids. A WDA alone does not account
for the long-range attraction sufficiently, and “local plus
correction” approaches47 have been applied only to fluid−
fluid interfacial systems. On the other hand, an addition of hard
sphere repulsion and mean field attractive interactions is still
the “simplest and very successful approach”48 to modeling
dispersion interactions.
In our current work, we use an MFA in describing the
dispersion contribution in iSAFT. Model parameters are fit to
pure component vapor pressure and saturated liquid densities.
Additionally, we have systematically evaluated the average
interaction between an alkane molecule and a graphite slab by
the potential of mean force, which quantifies the interaction
force of a molecule with a surface. The predictions of
adsorption/desorption, thermodynamic equilibrium, and crit-
ical properties are performed for a series of alkanes depicting
the hydrocarbons in a shale reservoir. The calculations for pure
and binary systems are verified by molecular simulation data,
and further studies on multicomponent systems suggest a
competition between enthalpic and entropic effects in
determining pore selectivity.
■
METHOD
Model Description. The modeled slit pore system can be
represented by the schematic shown in Figure 1. The two
infinitely large slabs of graphitic wall confine the hydrocarbons
inside. The graphitic wall is represented by layers of carbon
atoms, and here for simplicity, we assume that the wall is flat
and smooth. The fluid inside the pore is connected and in
equilibrium with a bulk fluid reservoir, which means an
equilibrium of temperature and chemical potential in each
species.
DOI: 10.1021/acs.langmuir.7b02055
Langmuir 2017, 33, 11189−11202
Langmuir Article
n mi
Aid [ρ(r)] = kT ∑ ∫ dr ∑ ρα(i)(r)[ln(ρα(i)(r)Λi3) − 1]
i=1 α=1
(4)
where k is the Boltzmann constant, mi is the segment number
in species i, Λi is the thermal de Broglie wavelength, and ρ(i)
α (r)
denotes the density of segment α in the ith molecule. A
correction of the atomic ideal gas free energy is included in the
chain term. For a homonuclear chain, all of the segments have
the same density, i.e., ρ(i)
1 (r) = ρ2 (r) = ... = ρmi (r) = ρi(r).
(i) (i)

Because Λi is temperature-dependent and the temperature is a

Figure 1. Schematic representation of the modeled graphite slit pore
system (H, pore width; σs, carbon atom diameter; Δ, separation
between two graphite layers).
constant here, the ln(Λ3i ) term will be canceled by the
corresponding term in the bulk chemical potential in eq 1.
Hard Sphere Contribution. The hard sphere part accounts
for the excluded volume effect for an inhomogeneous fluid. We
use the original fundamental measure theory15 in which the
hard sphere free energy functional is
ΔAhs[ρ(r)] = kT ∫ Φex,hs[nj(r)] dr (5)
and Φ [nj(r)] is the excess Helmholtz free energy density. It
ex,hs

is a functional of six fundamental measure densities nj(r) of the

For a fluid with fixed chemical potential (μ), temperature inhomogeneous fluid,
(T), and volume (V), the grand potential or grand free energy
nn
(Ω) is a minimum in the equilibrium state, with Ω determined Φex,hs[nj(r)] = −n0 ln(1 − n3) + 1 2
by the chemical potential of each species (μi), the intrinsic 1 − n3
Helmholtz free energy of the fluid (A[ρ(r)]), and the external n23 n v1·n v2 n (n · n )
potential from the graphite wall (Vext(r)), + 2
− − 2 v2 v2 2
24π (1 − n3) 1 − n3 8π (1 − n3) (6)
n
Ω[ρ(r)] = A[ρ(r)] − ∑ ∫ ρi (r)(μi − V iext(r)) dr where the nj(r) values are calculated by fundamental weights,
i=1 (1) n

where n is the total number of species, Vext

nj(r) = ∑ ∫ ρi (r)ωi(j)(r − r′) dr′; j = 0, 1, 2, 3, v1, v 2
i (r) is the external i=1
potential acting on each species, and ρi(r) is the molecular (7)
density of the ith species. With Ω being a free energy
functional, the equilibrium density distribution is obtained by At each position, the summation runs over all of the species
minimizing the grand potential, in the mixture. The weight functions are given by
r
ωi(2) = δ(R i − r ) ωi(3) = Θ(R i − r ) ωi(v2) = δ(R i − r )
δ Ω[ρ(r)] r
= 0 for i = 1, 2, ... n (8)
δρi (r)
equilibrium (2)
and
The average density is then determined from the equilibrium
ωi(2) ωi(2) (v1) ωi(v2)
density profile of each component. ωi(0) = ωi(1) = ωi =
Free-Energy Functional. In density functional theory, the 4πR i2 4πR i 4πR i (9)
main challenge is to approximate the Helmholtz free energy
where δ(r) and Θ(r) are the Dirac function and Heaviside
functional, and this functional can be formed through a
function, respectively, and Ri = di/2 is the radius of the segment
perturbation approach. In the iSAFT method proposed by
in component i. The temperature dependency of the hard
Tripathi and Chapman,22 molecules are constructed by
sphere diameter is determined by an empirical correlation49 of
bonding the spherical beads or segments to form chains that
the Barker−Henderson hard sphere diameter, which is
resemble the structure of molecules. In this work, our interest is
only in alkanes, so the molecules are represented by chains of ⎡ ⎛ 1/2 ⎤−1/6
T * + 1.1287T *2 − 0.05536T *4 ⎞ ⎥
homonuclear spheres. For a mixture of n molecular species, we d = 21/6⎢1 + ⎜1 + ⎟ σ
⎢⎣ ⎝ 0.0007278 ⎠ ⎥⎦
have n types of segments with mi segments in each chain (10)
molecule. The Helmholtz energy is a summation of different where T* is the dimensionless temperature reduced by fluid−
contributions, namely, an ideal gas (Aid), hard sphere (Ahs), fluid interaction energy ϵαα(T* = kbT/ϵαα) and σ is the segment
chain formation (Ach), and dispersion (Adisp) contributions, diameter. For the numerical implementation in a one-
dimensional system, we refer readers to the work by Gross,50
A[ρ(r)] = Aid [ρ(r)] + ΔAhs[ρ(r)] + ΔAch [ρ(r)] where the density symmetry in x and y coordinates is
+ ΔAdisp[ρ(r)] (3) considered.
Chain Contribution. The free energy due to chain formation
Ideal Gas Contribution. The exact ideal gas free energy for has been developed by Tripathi and Chapman,22 where the
an atomic mixture of n species is chain free energy functional is formed by the complete
11191 DOI: 10.1021/acs.langmuir.7b02055
Langmuir 2017, 33, 11189−11202
Langmuir Article

association of spheres with directional association sites. The ⎧0 0 < r < σ αβ

⎪
free energy functional for mixtures of associating spheres was ⎪− ε − u LJ
σ αβ < r < rmin
developed by Chapman20 and Segura et al.21 based on ⎪ αβ cut
att
uαβ =⎨
Wertheim’s thermodynmaic perturbation theory (TPT1).16−19 ⎪ ⎡⎛ αβ ⎞12 ⎛ αβ ⎞6⎤
σ σ
A schematic representation of chain formation is shown in ⎪ 4εαβ ⎢⎜ ⎟ −⎜ ⎟ ⎥ − ucut
LJ
rmin < r < rcut
⎪ ⎢⎝ r ⎠ ⎝ r ⎠ ⎥⎦
⎩ ⎣ (15)
Figure 2, where spheres with directional association sites are
in which uLJ
cut is the Lennard-Jones pair potential evaluated at
the cutoff distance, and here we use rcut = 4σαβ. For mixtures,
the Lorentz−Berthelot mixing rule σαβ = (σα + σβ)/2 and
εαβ = εααεββ is applied.
Grand Potential. The formalism to calculate the equilibrium
density profile can be found directly from the original paper by
Tripathi and Chapman.22 To calculate the grand potential, we
use the form in modified iSAFT developed by Jain et al.31 that
is more convenient and does not assume homonuclear
molecules. Although modified iSAFT is more rigorous and
predicts the exact ideal chain distribution, it requires an integer
number of segments whereas original iSAFT (like the bulk
SAFT EoS) allows noninteger values. In our tests of both
methods using integer numbers of segments (m = 1, 2, 3...), we
find that there is hardly any difference between the converged
density profiles for a wide range of temperatures and pressures,
Figure 2. Schematic of the ith molecule in the mixture formed from mi which ensures the reliability to transfer a grand potential
associating spheres. functional from modified iSAFT to original iSAFT.
n
β Ω[ρ(r)] = ∑ ∫ [ρi (r)(miDi(r) − 1)] dr + β ΔAhs
i=1
forced to bond in a specific order to form chainlike molecules. disp
The resulting chain free energy functional for homonuclear + β ΔA (16)
chains is n αα ′
δ ln ycontact [ρi̅ (r1)] δ ΔAhs δ ΔAdisp
ch n ⎡ 1 δ(|r1 − r2| − σ αα ′
)
Di(r) = ∑ (1 − mi) ∫ ρi (r1) dr1 − −
ΔA δρi (r) δρi (r) δρi (r)
= ∑ 2(mi − 1)∫ dr1ρα(i)(r1)⎢− ln ∫ dr2 y αα ′ i=1
kT i=1
⎢⎣ 2 4π(σ αα ′)2 (17)
1⎤ Note that the terms that involve mi are just simplified from eq
(r1, r2)ρα(i)(r2) + ⎥
2 ⎥⎦ (11) 32 in the modified iSAFT grand potential31 with identical
segment densities ρ(i)
α (r) in each chain.
δ(| r1 − r2 | −σ αα ′) External Potential. As we see from eq 1, the effect of the
where enforces tangential bonding. The cavity
4π (σ αα ′)2 fluid−solid interaction is modeled only by the external
correlation function yαα′(r1, r2) is needed only at a contact potential. For a graphitic wall, this external field is modeled
distance of σαα′, and we evaluate it by the bulk reference fluid by a Steele 10-4-3 potential,51 and for slit pores, the potential
radial distribution function at some averaged density ρα̅ (i) (r1), from both walls can be added to give Vext j (z) = Vj
10‑4‑3
(z) +
i.e., Vj (H − z),
10‑4‑3

⎡ ⎛ σ ⎞10 ⎛ σ ⎞4 σsj4 ⎤
αα ′
ycontact (ρα(i)(r1), σ αα ′) = ycontact
HS
(ρα̅ (i) (r1), σ αα ′) (12) V 10 −4−3 2 sj
(z) = 2πρs Δs σsj2εsj⎢ ⎜ ⎟ − ⎜ ⎟ −
sj
⎥
⎢⎣ 5 ⎝ z ⎠ ⎝z⎠
j
3Δ(z + 0.61Δ)3 ⎥⎦
Here we use the simplest weight within a sphere, i.e., (18)
ρα̅ (i) (r1) =
3
∫|r −r |<σ ρα(i)(r2) dr2 where ρs = 0.114 Å−3 is the carbon atom density, Δs = 3.35 Å is
4π (σα)3 1 2 α (13) the separation distance between two graphite layers, σsj and εsj
are the segment diameter and interaction energy that are
An alternative free energy functional for heteronuclear chains is estimated from the Lorentz−Berthelot mixing rules, σsj = (σs +
given in the work of Jain et al.31 σj)/2 and εsj = εsεj , where εs and εj are the interaction
Dispersion Contribution. For dispersion attractions, we use
the mean field approximation that assumes the pair correlation energies for solid−solid and fluid−fluid interactions and σs and
function between segments equals 1 beyond the hard sphere σj are the carbon atom diameter and segment diameter of the
contact. The dispersion contribution to the free energy component, respectively. The commonly used parameters for
functional is written as graphite are σs = 3.345 Å and εs/k = 28 K.52
n n
However, this external potential was derived for a spherical
ΔAdisp 1 molecule interacting with a surface assuming that the molecule
= ∑∑∫ dr1 dr2u att
αβ (|r2 − r1|) · mi ρi (r1) · has only one interaction site. For a chain molecule with
kT 2 i=1 j=1 |r2 − r1|> σαβ
multiple segments, the interacting force at each position is also
mjρj (r2) determined by the configurational change within the molecule.
(14)
Previous studies using an external potential in density
and the pair potential is given by a WCA-type perturbation, functional theory usually treat εsj as an adjustable parameter
11192 DOI: 10.1021/acs.langmuir.7b02055
Langmuir 2017, 33, 11189−11202
Langmuir Article

Table 1. Parameters for DFT Modeling of the Studied Components

AAD%
species m σ(Å) εj/k(K) vapor pressure liquid density temperature range (K) fluid−solid interaction εsj/k (K)
methane 1.0000 3.6754 202.8 2.2 3.1 100−180 63.9
ethane 1.5969 3.4557 243.0 5.6 2.2 200−300 65.7
n-propane 2.0049 3.4915 260.0 5.7 1.7 250−350 66.6
n-butane 2.3650 3.5923 275.5 5.3 2.1 250−350 67.5
n-pentane 2.6636 3.6808 290.0 6.0 2.1 250−350 69.1
iso-pentane 2.5321 3.7448 289.9 5.6 2.1 250−350 68.9
neo-pentane 2.3459 3.8459 281.7 5.7 2.1 260−360 64.1
n-hexane 3.0334 3.7295 296.1 7.9 2.3 245−365 70.7
n-heptane 3.4502 3.7357 298.5 7.4 2.1 250−350 70.4
n-octane 3.9598 3.7034 296.2 8.1 2.1 250−350 69.7

to fit the experimental data. For example, in the work by Shen The averaged density inside the slit pore is defined as
et al.,43 the interaction energy between solid and fluid was H − σs /2
adjusted along with pore size to achieve the best fit of the 1
experimental isotherm on porous carbon. However, such an
ρiavg =
H − σs
∫σ /2
s
ρi (z) dz
(21)
approach can mask the deficiency of the free energy functional
and confound the interpretation of other contributions to the which is used to calculate the adsorption isotherms.
functional. Numerical Procedures. An advantage of the original
Here we determine the interacting force between a single iSAFT is the simplicity in the chain free energy that requires no
molecule and a surface by molecular simulation and apply the recursive integrals. This method shows stable and satisfactory
simulated potential of mean force to the DFT model. The convergence performance with a simple Picard iteration starting
adaptive biasing force method53 is selected in which a force from a uniform density profile in the pore. The discretization
profile is applied to the center of mass of the molecule, and resolution we use is dz = 0.01σ, and a symmetric density profile
eventually the molecule is allowed to move freely in the is assumed to impose a reflective boundary condition. In
specified domain as if there is no attractive surface. In this way, calculating the adsorption or desorption isotherms, we take the
the force is averaged for all possible configurations of the converged density profile from the last pressure (Pi) as an initial
molecule, which has a different magnitude from a simple guess for calculation at the next pressure (Pi+1).The initial guess
summation of the interacting forces on each site with only one plays an important role because the metastable state in
configuration. Detailed information on the potential of mean hysteresis can be established only with an appropriate initial
guess density profile.

■
force simulation can be found in Supporting Information A.
Equilibrium Density Profile. Solving eq 2 results in the
equilibrium density profiles for n species in the system. On the RESULTS AND DISCUSSION
basis of the functional contributions described above, the Parameters for n-Alkanes and External Potentials.
density profiles are obtained from Within the framework of iSAFT, the alkane molecules is
described using three parameters, which are the chain length or
⎡μ ext {0,1,2,3, v1, v 2} ⎤
⎢ i − V i (r) − dr ∂Φex,hs ⎥ number of segments (m), the segment size (σ), and the
⎢ mi mi
∫ 1 ∑ ωi(j)(|r − r1|)
∂nj(r1) ⎥
⎢ j
⎥
⎢ n ⎥
⎢ −∑ ∫ att
dr1uij (|r1 − r|)mjρj (r1) ⎥
⎢ j=1
|r − r1|> σij ⎥
ρi (r) = exp ⎢ ⎥
⎢ m⎡ δ ln λ (r) ⎤⎥
⎢ + i ⎢ln(y cont (r)λii(r)) − 1 + dr1ρ (r1) ∫ ii ⎥⎥
⎢ 2 ⎢⎣ ii i
δρi (r) ⎥⎦ ⎥
⎢ ⎥
⎢ mi − 1 δ ln yiicont (r1) ⎥
⎢ + ∫dr1ρi (r) ⎥
⎢⎣ mi δρi (r) ⎥⎦
(19)
i = 1, 2, ...n

where
δ(|r1 − r| − σi)
λii(r) = ∫ dr1 4π (σi)2
ρi (r1)
(20)

It should be noted that eq 19 has been simplified from Tripathi

and Chapman.22 For the ith chain, even though the two end
segments would have different chain contribution from the
middle segment, we take the average over all of the segments
and assume that all of the segment density distributions are
identical.
Figure 3. Methane reduced density profiles from theory (solid lines)
and Monte Carlo simulations (circles), at bulk pressures of (a) 5.0 bar,
(b) 7.2 bar, and (c) 10.2 bar in a slit pore at 155 K. σ is the segment
diameter.

11193 DOI: 10.1021/acs.langmuir.7b02055

Langmuir 2017, 33, 11189−11202
Langmuir
Figure 4. Heptane reduced segment density profile from theory (solid
line) and molecular dynamics simulation (circles) in a slit pore at a
bulk pressure of 1 atm and a temperature of 298 K.
dispersion energy of each segment (εk). As was described
above, the dispersion contribution is solely accounted by the
mean field approximation, which means that the radial
distribution function is set equal to 1 outside of the hard
sphere contact. It is therefore expected that the dispersion
energy between molecules will not be the same as parameters
from the bulk SAFT. To retain both efficiency in inhomoge-
neous calculation and accuracy in bulk property prediction, we
refitted parameters for alkanes based on their saturated liquid
densities and vapor pressures. Unlike in modified iSAFT31 and
polymer DFT,25 the formalism of the chain contribution
according to Tripathi and Chapman22 allows us to have
noninteger numbers for the chain length, which has the
advantage of more accurately modeling the phase behavior of a
full-range of alkanes. The reference data is from the online
library of National Institute of Standards and Technology
(NIST).54 The absolute average deviation
Figure 5. (a) Adsorption and desorption isotherms of ethane in a 3 nm pore at 230 K. (b) Corresponding grand potential change with the chemical
potential for adsorption and desorption isotherms, with the intersection being the equilibrium transition, which is located at the circles in plot a.
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100
Nref qical − qiref
AAD % = ∑
Nref i=1 qiref
from saturated liquid densities and vapor pressures is
minimized to find the three model parameters. As mentioned
in Dominik et al.,32 the chain length and segment diameter
were not significantly changed in comparison to the parameters
regressed by Gross and Sadowski,42 so we first fix the chain
length and segment diameter parameters by keeping them the
same as the PC-SAFT parameters and adjust only the attraction
energy. We then adjust the chain length and segment diameter
to obtain the smallest error to the reference data. The fitted
parameters and fitting errors are presented in Table 1. As we
see, the errors are fairly large in comparison to the PC-SAFT
EoS,42 especially for the vapor pressures. This is expected
because the dispersion term has only one parameter while the
PC-SAFT EoS dispersion term is correlated to simulation
results of linear alkanes. Overall we consider this mean field
approximated equation of state accurate enough for the current
study.
For fluid−solid interactions, we find that the potential of
mean force (PMF) predicted by molecular dynamics (MD)
simulation nearly conforms to the Steele 10-4-3 potential, but
with a different well depth. Considering that the Steele
potential has an analytical formula, we use this equation after
calibrating the interaction energy parameters according to the
potential well values from simulation. The solid−fluid
interaction energies are also listed in Table 1.
Pure Component Adsorption, Desorption, and Phase
Equilibrium. Before predicting the phase behavior of different
components in nanopores, we first verify our model in
predicting density profiles by comparing with grand canonical
Monte Carlo (GCMC) and MD simulations. As previous work
presented, this model shows good performance in model
molecules like hard chains.22 In this work, we mainly focus on
the modeling of real molecules, in which case the dispersion
contribution plays an important role. In particular, the mean
field approximation may bring up some inaccuracy, so it is
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Figure 6. (a) Density pressure (ρ−P) diagram. (b) Temperature−density (T−ρ) diagram of methane confined in a 3 nm slit pore in comparison to
the bulk phase. Circles show the equilibrium densities at each temperature, which read 105, 110, 115,120, 125, 130, 135, 140, 145, 150, 155, 160,
165, 170, and 177 K, respectively.

Figure 7. (a) Density pressure (ρ−P) diagram. (b) Temperature−density (T−ρ) diagram of ethane confined in a 3 nm slit pore in comparison to
the bulk phase. Circles show the equilibrium densities at each temperature, which read 205, 225, 230, 235, 240, 245, 250, 255, 265, and 275 K,
respectively.

necessary to compare the density profile to molecular
simulation, i.e., grand canonical Monte Carlo (GCMC)
simulation or molecular dynamics (MD) simulation. We have
performed GCMC simulation for vapor methane adsorption
and MD simulation with NAMD55 for liquid heptane
adsorption. The parameters in the simulation are from a
united-atom model TraPPE force field,56 which is widely used
for alkanes. In MD simulation, the system setup follows the
work by Hu et al.,11 where the simulation box includes both the
confined alkane between two blocks of graphite and the bulk
region.
We start with methane, a spherical molecule, in which there
is no contribution from the chain free energy. Figure 3
compares the density profiles of adsorbed methane with those
from GCMC simulation for a slit pore of H = 5 nm at 155 K
and different bulk pressures. Although different molecular
models are used in the two methods, the agreement between
them is satisfactory. We have normalized the position with
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respect to the diameter of the molecule in each case. The
success is mainly attributed to fundamental measure theory
because the structure is primarily determined by repulsion. The
theory and GCMC simulation both show growing layers and
then capillary condensation of vapor methane as the pressure
increases, which is due to the strong attraction from the
graphite surface. However, it is much more challenging to
obtain excellent agreement between simulation and theory for a
chain molecule. As we see the density distribution of heptane in
a slit pore of H = 3 nm at 298 K and 1 atm in Figure 4,
although simulation and theory show similar magnitudes of
peaks and valleys, the wavelength of oscillation is much
different. The chain modeled in DFT is much too flexible
relative to that modeled by atomistic simulations, thus the
distance between two peaks is a little larger than the segment
diameter, whereas in density functional theory the distance can
be even smaller than one segment diameter. Given the fact that
the density profile cannot be fully captured by theory as a result
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Figure 8. Critical temperature and pressures at different pore sizes for methane (a, b) and ethane (c, d) from iSAFT prediction and a Monte Carlo
simulation of the literature.8,7 The bulk critical points predicted by this mean-field-approximated EoS are 202 K, 54.8 bar for methane and 325 K,
58.3 bar for ethane, whereas the experimental values are 190.6 K, 46.1 bar for methane and 305.3 K, 49 bar for ethane.

of different assumptions, we compare the average density inside
the pore, which is our major interest of study. The DFT-
predicted excess adsorption differs from the simulation result
by only 1.8%, which shows that theory still predicts the excess
adsorption in a convincing manner.
Because methane and ethane are the major components in
shale gas, we study the phase behavior of pure methane and
ethane first. Consider the adsorption and desorption shown in
Figure 5a for ethane in a 3 nm slit pore. When we have a
gaseous phase outside the pore, increasing bulk pressure would
lead to an increasing number of layers adsorbed in the pore, so
part of the pore is filled with adsorbed fluid that has a liquidlike
density and in the middle the density is still vaporlike, which is
called free gas. As the pressure increases, a first-order vapor−
liquid transition or capillary condensation can be seen when the
density everywhere is liquidlike. This phase transition happens
below the bulk saturation pressure and depends strongly on the
pore size. However, a decrease in pressure from the saturated
adsorption produces a phase transition at a lower pressure. This
hysteresis is a prominent feature of confined fluids. In this way,
two different density profiles can be obtained corresponding to
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two local minima of the grand potential. To determine the
stable state at the corresponding pressure, we need to examine
the grand potential change along each isotherm and the
thermodynamic transition that is located at the intersection of
the two grand potential isotherms. In Figure 5, the adsorption/
desorption isotherms of ethane in a 3 nm pore at 230 K are
shown and the thermodynamic transition point is located in
Figure 5b.
The same routine was followed at other temperatures for
methane and ethane in a 3 nm slit pore, and the vapor−liquid
equilibria are displayed in Figures 6 and 7. The bulk phase
density−pressure diagrams are also calculated with this MFA
type EoS, which are inserted into the confined phase diagrams.
In the confined system, the critical point is reached when
adsorption−desorption hysteresis disappears and the disconti-
nuity in density diminishes. For methane, we find the critical
temperature and pressure in the 3 nm slit pore to be around
177 K and 12.48 bar, respectively. Compared to the bulk critical
point based on MFA type EoS of 202 K and 54.8 bar,
confinement dramatically shifts the critical point. Similarly for
ethane, the critical point is also shifted by more than 20 K in
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Figure 9. (a) Adsorption/desorption isotherms of a methane/ethane mixture in different bulk compositions at T = 250 K with a slit pore size of H =
5 nm. Isotherms from left to right correspond to bulk ethane fractions of 0.9, 0.75, 0.65, 0.5, 0.4, 0.35, 0.3, 0.27, 0.25, 0.23, and 0.22. The critical
point is predicted at a bulk ethane concentration of ∼0.22 and a bulk pressure of ∼50 bar. (b) Equilibrium pressure vs ethane fraction diagram in
comparison with GCMC simulation and the bulk phase.
temperature and more than 30 bar in pressure. Overall the
phase boundaries are narrower in the pore than in the bulk.
The high density of the dew curve is due to the strong
attraction from the wall that causes the first layer of fluid near
the wall to have a liquidlike density. This liquidlike density
region occupies a fairly large fraction of the pore space, so the
average density in the pore is no longer comparable to a bulk
vapor phase. As the pressure increases, the fraction of the liquid
part becomes larger, which makes the average density in the
pore deviate more and more from vaporlike density.
Critical properties can influence the gas compressibility,
viscosity, and formation volume factor predictions in reservoir
simulators and thus impact the production scheme.7 In Figure
8, we show the iSAFT-predicted critical properties in
comparison with literature data for different pore sizes. The
predictions are qualitatively consistent with Monte Carlo
simulations. For methane, the theory predicts critical temper-
atures closer to the NVT-Gibbs MC, and the predicted critical
pressure lies between the two simulation studies. It is known
that a bulk equation of state overpredicts the critical point, and
the difference between theory and simulation critical points
appears to be due, in part, to differences in bulk critical points.
The theory predicts the trend in the critical point with respect
to pore size consistent with simulated data. The data set in
Figure 8 is listed in Table 1 and Table 2 in Supporting
Information B.
Binary Systems. The prediction of hydrocarbon mixture
partitioning between the kerogen matrix and fractures is
essential to production management in shale reservoirs.
Pitakbunkate et al.8 performed a GCMC study of the pore-
filling process of a methane/ethane mixture at 250 K in a 5 nm
graphite pore, and the phase boundaries and critical point were
determined from simulation data. Here we calculate the same
properties with iSAFT and compare the results with their
simulation data. The adsorption and desorption isotherms with
different bulk ethane concentrations are shown in Figure 9a. As
the bulk ethane concentration decreases, the phase-transition
pressure increases, and the hysteresis disappears as the pore
fluid reaches a critical point. The calculated critical point is 50
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bar at a bulk ethane fraction of 0.22 as adsorption/desorption
hysteresis disappears when the bulk ethane concentration
decreases from 0.23 to 0.22. The equilibrium transition was
determined from the grand potential of adsorption/desorption
isotherms. The equilibrium dew point and bubble-point curves
of ethane are also shown in the same figure in comparison with
the bulk ethane phase boundaries. Because the exact bulk
concentration corresponding to each isotherm was not reported
in Pitakbunkate et al.,8 we compare only the predicted bubble/
dew curves of ethane with their simulated ones. We see that our
calculated equilibrium phase boundary is in very good
agreement with the GCMC adsorption isotherm. We present
the bulk phase ethane density to better illustrate the shift of
phase boundaries and suppression of critical point in the pore.
Because of fluctuations in the simulations, it is difficult to trace
the full adsorption curve. Thus, we suspect that the adsorption
phase boundary from simulation is close to the equilibrium
state. Finally, we compute the composition of the methane/
ethane mixture at each equilibrium point and obtain the
pressure−fraction diagram in the pore. Again we compare this
result with that from adsorption simulation and that of the bulk
phase. From Figure 9b, we see that the theory predicts a higher
critical pressure and lower ethane concentrations. This is
consistent with the performance of the iSAFT bulk EoS as we
see that it overpredicts the critical pressure and underestimates
the ethane concentration when comparing to bulk PC-SAFT
EoS predictions.
As we can see from the last example, ethane is always
preferred over methane in the 5 nm graphite pore because of
the larger affinity of ethane for the graphite surface. However,
as the chain becomes longer, the entropy loss of entering the
confined space will compete with the enthalpy benefit so that
the longer chain partitions to the bulk. Here we study the
adsorption of a Cn/Cn+1 binary mixture and characterize the
pore preference of the longer alkane Cn+1 by the ratio of the
pore fraction and bulk fraction. In Figure 10a, gas mixtures of
different compositions at 298 K, 1 atm show different selectivity
behavior in a 3 nm pore. For the C4/C5 mixture, the maximum
C5 fraction is 0.5, which is below the mixture saturation
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Figure 10. iSAFT prediction of (a) a binary gas mixture adsorption in different compositions, (b) C1/C2 mixture adsorption in different pore sizes,
(c) binary liquid mixture adsorption in different compositions, and (d) C7/C8 mixture adsorption in different pore sizes. The temperature and
pressure are fixed at 298 K and 1 atm.
Figure 11. Simulated potential of mean force and radius of gyration
for n-, iso-, and neo-pentane in vacuum.
composition. The preference for the longer alkane partitioning
to the pore is ranked as C1/C2 < C2/C3 < C4/C5 < C3/C4.
As we notice, an interesting transition is seen in that C4/C5
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mixture lies between C2/C3 and C3/C4. This implies that the
entropy loss of pentane plays a more important role than in the
C3/C4 mixture.The selectivity has a completely different trend
for liquid alkane mixtures under ambient conditions, as shown
in Figure 10c with C7/C8 < C6/C7 < C5/C6. For the C5/C6
mixture, C6 still partitions to the pore more than C5 does.
However, for the C6/C7 mixture, the pore fluid has almost the
same composition as that in the bulk. What is surprisingly
predicted is that for the C7/C8 mixture the preference to
longer alkane no longer holds as the fraction of C8 in the pore
is smaller than that in the bulk. The results demonstrate the
competition between the enthalpy benefit from surface
attraction and entropy loss due to geometric confinement.
We are not aware of experimental studies that would provide
insight into long alkane adsorption in nanopores. For longer
alkanes, the advantage in surface affinity becomes less dominant
as the long alkanes lose more configurational entropy upon
entering the pore space. In Figure 10b,d, the pore size effect is
studied for a C1/C2 gas mixture and a C7/C8 liquid mixture.
As the pore size decreases from 8 to 2 nm, an increasing
selectivity for the larger molecule is seen for C1/C2 whereas
the opposite is observed in C7/C8. This suggests that in short
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Figure 12. Selectivity of n-pentane and iso-pentane to neo-pentane in H = 1.5 nm at T = 300 K when the bulk is (a) a vapor phase or (b) a liquid
phase with equimolar composition.
Figure 13. Ratio between the pore fraction and bulk fraction of C1/C2/C3/C4/C5 in H = 1.5 nm at T = 300 K when the bulk is (a) a vapor phase
or (b) a liquid phase with molar composition C1/C2/C3/C4/C5 = 5/4/3/2/1.
alkane adsorption the selectivity is mainly determined by the
surface affinity; however, for long alkanes in the liquid state,
adsorption is a competition between attraction to the surface
and the loss of configurational entropy.
Competitive Adsorption of Multicomponent Systems.
The competitive adsorption of a multicomponent (n > 3)
system is of interest both for shale reservoir characterization
and other applications such as gas separation and chromatog-
raphy. Jiang et al.57 performed a configurational-bias Monte
Carlo simulation of linear (C1−nC5) and branched (C5)
alkane mixtures on single-walled carbon nanotube bundles.
They discussed the different competitive adsorption behavior at
low and high pressures, where short alkanes partition to the
pore more strongly at high pressures. In this section, we have
performed a similar study and find a similar trend in a slit pore.
We first study the adsorption of an equimolar mixture of C5
isomers, namely, n-/iso-/neo-pentane = 1:1:1, at 300 K in a 1.5
nm slit pore. Because of the different arrangements of carbon
atoms, the surface attraction force for each molecule is different.
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This can be verified by the potential of mean force calculation
from single-molecule simulations shown in Figure 11. The
radius of gyration of each isomer is also presented because we
see that n-pentane is mostly stretched and thus has the
strongest interaction with the surface. In partitioning to the
pore space, we see in Figure 12 that n-pentane is most strongly
adsorbed, with iso-pentane being next. The calculation is
conducted both for vapor and liquid bulk phases, with the
vapor phase showing a larger selectivity of linear pentane to
neo-pentane. Here we show the selectivity as the molar density
ratio between one species to neo-pentane. A similar trend is
seen in the adsorption in carbon nanotubes. At higher pressure,
decreased selectivity is due to the packing limit when
approaching adsorption saturation. Although n-pentane is
preferentially adsorbed by the pore, as the pressure increases
the configurational entropy loss of entering the pore would
hinder the continuous increase in the stretched molecule in
pores. If we take a look at a mixture of more dispersed chains,
as in the next example, a mixture of C1/C2/C3/C4/C5 = 5/4/
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3/2/1, this pressure effect is more clearly seen. Figure 13a,b
⎛ x pore ⎞
shows the partition coefficient ⎜ ibulk ⎟ of this mixture in a 1.5
⎝ yi ⎠
nm pore at 300 K with the bulk being a vapor in Figure 13a and
a liquid in Figure 13b. Compared to the bulk composition, we
see in (a) that pentane strongly adsorbs in the pore with a large
difference from the bulk concentration. Before capillary
condensation in the pore, the n-pentane fraction continuously
increases. However, the n-pentane fraction decreases after
condensation whereas other molecules increase in adsorption.
The calculation is stopped before the mixture’s bulk dew point
pressure, and the fraction of each species approaches a
constant. For a liquid mixture in the bulk, the liquid density
changes slowly with the increase in pressure as a result of the
packing limit. In Figure 13b, we observe a smaller enhancement
of pentane in the pore compared to the bulk concentration
than in Figure 13a. The greater than 1 partition coefficients of
propane, n-butane, and n-pentane indicate a preference for
these large molecules, but in the case of a bulk liquid, methane
is a major component in the pore, similar to its bulk
concentration. Again, this result is consistent with the
simulation study on carbon nanotubes, which implies that our
model produces reasonable results. This study also suggests
that a quite different gas composition from produced gas is
expected to be in the reservoir fluid and the production
simulation should take into account a reasonable molar
composition of the reservoir fluid.
■
CONCLUSIONS
The promising development in shale gas/oil makes it critical to
better understand the fluid properties in a shale reservoir. The
nanoconfinement effect will greatly shift the fluid thermody-
namic properties, which makes the exploration and production
challenging. Because the pore shape, pore size, and solid
composition can all affect the fluid behavior, the prediction of
fluid properties in shale networks is an active area of research.
In this work, we present a model to provide a physical
understanding of the confined alkane properties in shale. As a
computationally efficient method, iSAFT has been applied to
predict the phase behavior of pure and mixed hydrocarbons in
graphite slit pores. In quantifying the fluid−solid interactions,
we have introduced the potential of mean force from molecular
simulation to evaluate the external potential in a nonlocal DFT
framework.
To summarize, we have examined the density distribution of
adsorbed molecules in the adsorption of methane and heptane
by comparison to molecular simulation. The pore size
dependency of pure methane and pure ethane critical
properties has been studied, and the phase diagrams were
established for methane and ethane in a 3 nm pore. The
mixture phase behavior was studied by taking the methane and
ethane mixture as a showcase. The predicted properties are
comparable to molecular simulation, with the errors mainly
arising from the mean field approximation in treating the
dispersion energy. After the initial verification of the theory on
pure and binary systems, we predicted the selective adsorption
of a series of binary (Cn/Cn+1) mixtures up to n-octane. The
selectivities have been shown in different sized pores, where we
see for short alkanes in the gaseous state that Cn+1 always
partitions more to the pore whereas for longer alkane mixtures
in the liquid state this is not always true. This observation
implies that selective adsorption is determined not only by
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surface affinities but also by the change in configurational
entropies, which is also mentioned by Jiang et al.57 Further
studies on the selectivies of multicomponent systems, which are
branched pentanes and C1−C5 mixtures, have shown similar
trends as reported by simulation57 and also imply the same
mechanism. Selectivities from molecular simulation will be
considered for future work. Because fluid in shale is a complex
mixture confined in nanoscale pores, the partitioning of
different components between fractures and the pore matrix
should be considered to obtain a realistic fluid composition in a
reservoir. As reported by other works,7,8,40 an adjustment of the
fluid thermodynamic properties is inevitable in reservoir
simulation.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.lang-
muir.7b02055.
Potential of mean force simulation and critical point data
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: wgchapman@rice.edu.
ORCID
Dilip Asthagiri: 0000-0001-5869-0807
Walter G. Chapman: 0000-0002-8789-9041
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors thank The Robert A. Welch Foundation (grant no.
C-1241) for financial support.
■
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DOI: 10.1021/acs.langmuir.7b02055
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11202 DOI: 10.1021/acs.langmuir.7b02055

Langmuir 2017, 33, 11189−11202

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