Fluid Phase Equilibria 531 (2021) 112909

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Phase behaviour of confined associating fluid in a functionalized slit

pore: a Monte Carlo study
Sashanka Sekhar Mandal a, Sudhir Kumar Singh b, Sanchari Bhattacharjee a, Sandip Khan a,∗
a
Department of Chemical & Biochemical Engineering, Indian Institute of Technology Patna, Patna 801103, India
b
Department of Chemical Engineering, Thapar Institute of Engineering and Technology, Patiala 147004, India

a r t i c l e i n f o a b s t r a c t

Article history: Vapour-liquid phase equilibria of associating fluids under confinement are investigated using Grand-
Received 15 August 2020 Canonical Transition Matrix Monte Carlo (GC-TMMC) method. Various properties of coexistence phases
Revised 15 November 2020
and critical properties are estimated for multiple associating fluids at different slit widths. The structural
Accepted 18 November 2020
features of coexistence phases are examined through monomer fraction, density profile, and orientation
Available online 24 November 2020
profile. The role of surface sites on the phase behaviour under confinement is critically examined. It has a
Keywords: significant effect on the structural behaviour of coexistence phases, leading to a change in the properties
Phase transition of coexistence phases. In particular, the orientation of associating fluid molecules near the functionalized
Associating fluid surface is entirely different than in the case of a smooth surface. The orientation of two sites associating
Slit pore (when sites are located oppositely to each other) fluid molecules is normal to surface, forming bonds
Functionalized surface with surface sites in one direction and another bond with molecules in an adjacent layer.
© 2020 Published by Elsevier B.V.

1. Introduction level. The advantages of statistical mechanics and computer simu-

The fluid phase behaviour in a nanopore is significantly dif-
ferent than those in a bulk phase [1–6]. The relative strength
between fluid-fluid and fluid-substrate interaction induces vari-
ous phase transitions, including layering, prewetting, vapour-liquid,
melting/freezing, capillary condensation, along with a shift in crit-
ical properties of the system [7–18]. A detailed understanding of
such systems will provide significant insight into many biological,
natural, and engineering processes such as shale gas extraction,
microfluidics devices, fabrication of nanomaterials, nanotribology,
etc. [19]. Over the last few decades, substantial technological ad-
vancement in nano-fabrication technology made it possible to im-
print nano-scale surfaces with well-defined chemical, physical and
geometric characteristics [20]. Modern electronic devices are made
possible by extensive use of micro-electromechanical systems
(MEMS) and nanoelectromechanical systems (NEMS). Micro/nano-
fluidic devices like Lab-on-a-chip (LOC) have the potential to
change the way we diagnose complex samples in medical, envi-
ronmental, and many other industries [21,22]. Although we have a
relatively good understanding of phenomena like adsorption, cap-
illary action, phase transition, etc. at a macroscopic scale, new in-
sight is needed as the dimensions reduce to the molecular/atomic
∗
Corresponding author.
E-mail address: skhan@iitp.ac.in (S. Khan).
lation made it possible now to study these systems. Molecular sim-
ulations have been used for many years to study the properties of
molecular systems using mainly two approaches, namely, molecu-
lar dynamics (MD) and Monte Carlo(MC) [19,23].
In this direction, many investigations are performed using
molecular simulation for model fluids and molecular fluids con-
fined at the nanoscale to understand the various phase transitions
[6,16,17,24–32]. For example, square-well fluids are studied in a
slit pore from quasi 3D to 2D system to understand the effect of
confinement on the vapour-liquid transition. They observed four to
five distinct linear regimes based on the critical temperature shift
with slit width, clearly visible at higher surface strength. More-
over, the change in the critical pressure and critical density does
not show any specific trend; however, they approached the 3D
bulk value with an increase in slit pore width beyond 40 molec-
ular diameters [29]. In another work [33,34] triangle-well fluids
with variable well widths confined in different slit pores are in-
vestigated using Monte Carlo simulation. An interesting observa-
tion of this study is that inside the narrow slit pore the density
profile shows a higher value at the centre than to that near the
slit surface. In another study, MC simulation is used to investigate
the effect of pore shape on the vapour-liquid phase transition of
square-well fluid. In this work, cylindrical pores of varying pore
width and surface nature are investigated. This investigation in-
dicates that the surface nature can significantly alter the vapour-
liquid coexistence envelopes and the critical point [35]. Vapour-

https://doi.org/10.1016/j.fluid.2020.112909
0378-3812/© 2020 Published by Elsevier B.V.
S.S. Mandal, S.K. Singh, S. Bhattacharjee et al.
liquid phase equilibria of square-well fluids confined in patterned
slit pores are also investigated using Monte Carlo simulations [28].
In this work, phase coexistence envelopes, spreading pressure, crit-
ical properties, and local density profiles of the confined square-
well fluid are reported for chemically and physically patterned slit
pores. Liu et al. [36] studied the effect of hard slit pore on the
vapour-liquid coexistence and critical properties of the confined
Lenard-Jones (LJ) fluid and ST2 model of water using GCMC sim-
ulations. In this study, they observe three distinct regions based
on the shift in critical temperature, critical density, and saturated
liquid density as a function of slit width while crossing from 2-
dimensional to a 3-dimensional system.
Along with simple fluids, molecular fluids such as water, alkane,
alkanes, etc. are also studied to understand the effect of structural
integrity and the polarity of a molecule on the various phase tran-
sitions under confinement. In this direction, Brovchenko and his
co-workers [17,37–39] have extensively studied the phase transi-
tions of water in nanopores using Gibbs Ensemble Monte Carlo
(GEMC) simulation and observed various kind of phase transi-
tions including vapour-liquid, layering, prewetting based on the
strength of wall-fluid interactions. In particular, the vapour-liquid
phase transition was observed in hydrophobic and moderately hy-
drophilic pores, whereas surface phase transitions such as prewet-
ting, layering, etc. were observed for strong substrate interac-
tion. Singh et al. [31] uses configurational-bias grand-canonical
transition-matrix Monte Carlo simulations to investigate various
thermophysical properties of alkanes (C1 - C8) in slit pore of
graphite and mica along with in bulk. The walls of slit pore geome-
try are taken as a featureless smooth surface. Wall-fluid interaction
is depicted by the 9-3 Steele potential. The critical temperature is
found to be sensitive to the nature of the surface, whereas critical
density decreases with the slit width until the system approaches
single layer 2D geometry. Bonnaud et al. [40]investigated the struc-
ture and dynamics of water in a hydroxylated silica nanopore us-
ing MD simulation and found multilayer adsorption prior to the
capillary condensation. The study also shows a strong layering of
water in the vicinity of the silica surfaces. They also report the
MC study of confined water in cementitious material (calcium-
silicate- hydrates) in Grand Canonical ensemble [30]. This study
shows how the relative humidity can affect the phase behaviour of
water confined in different pore sizes of calcium-silicate-hydrates
grain. The kinetics of capillary condensation and water evapora-
tion in a smooth, ideal hydrophilic mesopore were investigated us-
ing combined GCMC and MD by Yamashita et al. [27]. The effect
of the deviation in chemical potential between the gas phase and
pore surface on the dynamics of water evaporation and capillary
condensation was explored. GCMC method was employed to con-
trol the chemical potential of water vapour, whereas MD depicts
the dynamics of water adsorption/desorption on/from the pore sur-
face. Srivastava et al. [26] studied the phase transition of confined
water in graphite and mica slit pores of different sizes ranging
from 10Å to 60 Å. Their study found that the confinement de-
creases the critical temperature and introduces non-uniformity in
density profile. This heterogeneity leads to different vapour-liquid
coexistence densities at different layers. Hydrophilic surfaces like
mica reduced the critical temperature of confined water more ef-
fectively than hydrophobic graphite surfaces. The water molecules
at the surface layer of the pore behave more like a quasi-2D fluid.
The effects of the electric field on the vapour-liquid equilibria of
methanol and ethanol, confined in a graphite slit pore, is reported
by Bhandary et al. [41]. The critical temperature of ethanol and
methanol decreases with the increasing external electrical field to
a certain minimum value and then increases. The orientation or-
der for both alcohols is found to increase with a stronger external
electrical field. Srivastava et al. [42] report the effects of the ex-
ternal electrical field on confined water in graphite and mica pore
2
Fluid Phase Equilibria 531 (2021) 112909
by MD study. The critical temperature is found to decrease with
an increase in the external electric field. However, critical density
increases for graphite pore but decreases in mica pore with an in-
crease in the electrical field.
Although many studies on confined polar fluids such as water,
alkanes, etc. but very few studies explore the functionalized sur-
face effect on the phase transition of associating fluids [43]. In this
direction, we have extensively studied the phase behaviour of two-
site associating fluids confined in a functionalized slit pore to un-
derstand the role of associating sites present on the surface. The
presence of sites on the fluid molecules favor the bond formation
and leads to a chain-like structure for two-site associating fluids.
Therefore, it is quite expected that there would be an intense layer-
ing of associating fluid inside the pores. On the other hand, surface
sites can compete with the fluid-fluid association and may trigger
fluid molecules different orientation and result in different struc-
tural behaviour inside pores.
2. Computational model and simulation methods
2.1. Model detail
In this work, a two-site associating fluid model is considered
in which Lenard-Jones potential is used for isotropic interaction
between fluid molecules and a short-range directional square-well
potential is used for site-site interaction [44]. The sites are located
oppositely on the surface of fluid molecules (off-cantered). Thus,
the complete potential for fluid-fluid interaction is as follows:
 
u f f ri j , θi , θ j = uLJ−tr (ri j ) + ua f (ri j , θi , θ j ),

  −εa f if σ <ri j < rc , θi < θc and θ j < θc ,
u a f r i j , θi , θ j =
0 Otherwise
   (1)
12  r 6 
4ε σi j
r
− σi j if ri j ≤ rcut ,
uLJ−tr (ri j ) =
0 Otherwise
where θ i , θ j are the angle between the centre-centre and centre-
site vectors for the molecule i and molecule j, respectively. The θ c =
27o and rc =1.0 are the angle, and the distance criteria, respectively,
to consider two molecules are in association with the well-depth
of ε af . Here, rc is the distance between two fluid particles. There-
fore, the association of particles can occur if the distance between
two particles is less than or equal to 1. Many groups have also
used these parameters and predicted various phase transitions us-
ing classical Density Functional Theory (DFT) and MC simulation
[45,46]. The size (σ ) and energy (ε ) parameters for LJ potential of
fluid-fluid interaction are taken as unity with a cut-off distance of
rcut =2.5. This short-ranged and orientationally dependent site-site
interaction can be compared with hydrogen bonding between two
molecules. For example, two-site associating fluid can represent
the hydrogen fluoride (HF) molecules, which can form two hydro-
gen bonds with neighbour molecules and can make a linear chain.
However, the associating strength of the site interaction in the case
of HF is comparatively large in comparison to the value used in
this work (ε af is varied from 4 to 10, which allows us to sample the
phase space efficiently and determine the critical properties accu-
rately). It should be noted that all the parameters are reduced with
respect to fluid-fluid interaction parameters (ε , σ ), such that pore
width H∗ =H/σ , number density ρ ∗ = ρσ 3 , temperature T∗ =KB T/ε
(where KB is Boltzmann constant) etc.
The fluid molecules are confined by the structure less surface
with active sites at different slit pore width. The sites are dis-
tributed uniformly in a rectangular grid on the surface based on
the site density, ρ s , defined as the number of associating surface
sites per unit area. The substrate-fluid interaction is represented by
steele 10-4-3 potential [47], which corresponds to argon-graphite
S.S. Mandal, S.K. Singh, S. Bhattacharjee et al.
Fig. 1. Schematic diagram of-two-site associating fluid confined in a functionalized
slit pore.
interaction [48] along with active site interaction as given below:
uw f = u10−4−3 (z ) + uaw (ri j , θ
i, θ j )
 σw f 10
u10−4−3 (z ) = 2π ρw εw f σ 2
 2
− −
 wf 5 z
−εaw i f ri j < rc , θi < θc and θ j < θc
uaw (ri j , θi , θ j ) =
0 Otherwise
where z is the distance between fluid and substrate molecules
along z-coordinate,  is the distance between two graphite lay-
ers, and ρ w is the density of carbon atom of graphite layers. The
effective interaction parameters ε wf and σ wf between fluid and
substrate molecules are calculated through Lorentz-Berthelot rule
[49]. However, the energy parameter for solid-fluid interaction is
taken weaker (ε wf = 0.2) to explore the effect of surface sites
on the phase diagram in confinement, whereas σ wf is equal to
0.9912, which is correspond the argon-graphite system. The site-
site interaction between associating fluid and the functionalized
surface is also represented by square-well potential with a cut off
distance of rc =1.0, and with associating strength of ε aw =5, which
is an intermediate value for the range of site-site interaction of
fluid particles to understand the interplay between fluid-fluid and
fluid-solid interaction on the phase diagram.
In this study, the surface is placed at z = 0 and z = H (pore
width), and active sites are placed on the top of the virtual sur-
face atoms. The centre of virtual molecules with the same radius
of fluid molecules, is located at z=0 and z =H. The schematic dia-
gram of the system is shown in Fig. 1.
2.2. Methodology
Grand Canonical Transition Matrix Monte Carlo [50] (GC-TMMC)
simulation, along with histogram reweighting [51] is employed to
extract the properties of the coexistence phases under confine-
ment. GC-TMMC is basically Grand Canonical Monte Carlo (GCMC)
simulation conducted at constant chemical potential μ, volume V,
and temperature T in which transition probability among differ-
ent microstates are also computed during different Monte Carlo
(MC) moves and collected in a matrix form. There are four basic
moves, namely displacement, insertion and deletion and, rotation
[52], which are used to sample the phase space efficiently. The
macro-state probability (probability distribution of particle states,
N ) is then evaluated from the collection matrix. At regular inter-
vals, the multi-canonical sampling technique [53] is used to sam-
ple all the particle states uniformly using macro-state probability
density obtained from the updated collection matrix. These simu-
lations are performed at a given chemical potential μ, and hence,
Fluid Phase Equilibria 531 (2021) 112909
the histogram reweighting technique is used to locate the coex-
istence chemical potential at which the probability of liquid and
vapour phase are the same. Details of GC-TMMC simulation tech-
niques are given elsewhere [50]. The coexistence probability distri-
bution is used to estimate the saturation pressure (P) using Eq. (3).
c (N )
β PV = l n − l n (2 ) (3)
c (0 )
where, β = 1/KB T
The density difference between the two coexistence phases de-
creases as the system approaches the critical point. Thus, it is chal-
lenging to estimate the critical properties from a direct simulation.
The following scaling laws are used to determine the critical prop-
erties from the subcritical parameters [54]:
ρl − ρv = A(T − Tc )B (4)
ρ + ρ
v
l
= ρc + D(T − Tc ) (5)
2
  where subscript “c” denotes the corresponding critical properties.
 σw f 4 σw4 f A, B and D are fitting parameters. ρl and ρv are liquid and vapor
z 3(z+0.61)3 density at subcritical regime.
2.3. Simulation details
(2)
All simulations are carried out in a rectangle box with a length
of 9 in x and y direction, and the z dimension is equal to the width
of the slit pore, H. The top and bottom surfaces are placed in the
xy plane of the box at z = 0 and z = H. In this work, the pore
width is varied from 4 to 40 molecular diameter of fluid parti-
cles, and the associating strength is varied from 0 to 10. The differ-
ent MC moves are carried out with probability 0.1, 0.35, 0.35, 0.1
and 0.1 for translation, insertion, deletion, rotation and Unbonding-
bonding (UB) respectively. The UB technique [55] is used to bias
the sampling towards the bonding regime of associating fluids,
which is particularly important at lower temperature range and
higher associating strength. The attractive part of the GC-TMMC is
that the range of particle state for a specific simulation can be dis-
cretized among different cores [56]. Hence, multiple cores (8-32)
are used based on the range of particle state that depends on the
system temperature and the associating strength. In this work, the
statistical errors, calculated from four independent simulations, are
of the order of symbol size.
3. Result and discussion
3.1. Phase transition inside smooth slit pore
We start our discussion with the vapour-liquid phase transition
of confined associating fluids with various associating strength at
a slit width, H∗ = 6, as shown in Fig. 2(a). In general, the vapour
density increases and liquid density decreases with a temperature
rise and become indistinguishable at a critical temperature. With
an increase in associating strength, the critical temperature of the
coexistence phases increases, which is more sensitive at higher as-
sociating strength ε af ∗ > 6. The increase of critical temperature
is mainly due to the strong association of fluid molecules, which
increases the free energy barrier between the vapour and liquid
phase at a given temperature and raises the critical temperature.
Therefore, at a given temperature, the liquid density increases, and
vapour density decreases with an increase of associating strength,
which results in the broadening of the phase diagram. Interest-
ingly, an insignificant change in the critical density is observed
with the change in the associating strength of the fluid, attributed
3
S.S. Mandal, S.K. Singh, S. Bhattacharjee et al.
Fig. 2. (a). Temperature-density vapour-liquid coexistence envelope of associating
fluids in a slit pore of width H∗ =6. (b). Vapour-liquid coexistence envelope of an
associating fluids (ε af ∗ =6) in slit pore of width ranging from H∗ =3 to 60. The phase
coexistence envelope of the bulk fluid (black solid line with square symbol) is also
included in the plot for comparison. All parameters are in reduced unit. (c). Corre-
sponding state of vapour-liquid coexistence envelope of an associating fluid (ε af ∗ =6)
in slit pore of width ranging from H∗ =3 to 40. The phase coexistence densities of
the bulk fluid (black solid line with square symbol) are included in the plot for
comparison.
4
Fluid Phase Equilibria 531 (2021) 112909
to the symmetrical shift in the coexistence envelope with the as-
sociating strength. We have analysed the system size effect on the
critical properties of the system (ε af ∗ = 6 and H∗ = 6) with the
different surface area. We found the error associate with the es-
timation of critical points is within 1%, which is also reported by
other authors [29] for the simple fluid confined in an attractive slit
pore.
Fig. 2(b) presents the effect of confinement on the coexistence
envelopes of associating fluid for ε af ∗ = 6, at different pore widths
ranging from H∗ =3 to 60. Clearly, under confinement, the coex-
istence envelope shrinks, and the critical temperature decreases.
Moreover, with the increase in the degree of confinement or the
decrease of slit width, the coexistence envelope shrinks further,
and the critical temperature monotonically decreases. However,
critical density under confinement shows nonmonotonic behaviour
with respect to bulk critical density. This behaviour can be at-
tributed to a significant change in coexistence densities with the
change in the slit pore width. Similar nonmonotonic behaviour of
critical density with respect to bulk is observed with simple fluids
[29,31] confined in attractive slit pores. Further, to understand the
phase coexistence behaviour under confinement on the reduced
scale, we have plotted the corresponding state coexistence en-
velopes of associating fluid for ε af ∗ =6 at different pore widths and
shown in Fig. 2(c). The corresponding state behaviour has shown
an interesting trend of coexistence envelopes. The highest shrink-
age in the corresponding state coexistence envelope is observed
with the slit pore width, H∗ = 15, as shown in Fig. 2(c). Further,
with the decrease in the slit pore width, the corresponding state
coexistence envelope broadens, and finally, at H∗ = 4, it overlaps
with the bulk corresponding state behaviour. Moreover, at H∗ = 3,
the coexistence envelope further broadened up and exceeded the
bulk coexistence envelope. Similar behaviour is also observed with
associating fluid for ε af ∗ =4 at the studied pore widths (not shown).
Interestingly, with the largest studied slit pore width, H∗ = 40, the
corresponding state coexistence envelope again starts broadening
as compared to H∗ =15, as reflected in Fig. 2(c), which indicates
that at a much larger slit pore width, it would approach towards
bulk corresponding state coexistence envelope, as expected.
3.2. Monomer fraction
The structure of coexistence phases of associating fluid largely
depends on the association of molecules and can be examined
through monomer fraction present in the system. Monomer frac-
tion is defined as the fraction of molecules that are not bonded
with other molecules. Fig. 3(a) shows the values of the monomer
fraction of coexistence phases for different associating strength at
a slit width, H∗ = 6, as well as for bulk. The solid line with
an open symbol represents the monomer fraction for respective
bulk systems. At a given associating strength, for both the bulk
and confined systems, the values of monomer fraction signifi-
cantly increase for the liquid phase with a decrease in temper-
ature, whereas for the vapour phase, the change of monomer
fraction is very small or negligible, depending on the associat-
ing strength, which is in line with previous studies employed in
bulk [57,58]. Therefore, it is quite expected that there would be
a more compact arrangement in the liquid phase through associa-
tion and result in an increase of liquid density with a decrease in
temperature.
On the other hand, at a given temperature, the monomer frac-
tion value for the liquid phase increases and that for the vapour
phase decreases under confinement compared to the respective
bulk systems. For the liquid phase, the presence of the substrate
hinders the bond formation of fluid molecules near the surface,
and hence the monomer fraction in the liquid phase increases.
S.S. Mandal, S.K. Singh, S. Bhattacharjee et al.
Fig. 3. (a). Monomer fraction of different associating fluid at slit width H∗ =6. Here
open symbol with solid line represent the respective bulk systems, (b) monomer
fraction at different slit width for associating fluid ε af ∗ =6.
On the other hand, in the vapour phase, the numbers of fluid
molecules are significantly less, and hence, the association of the
fluid molecules is typically found to be less in bulk. However, the
presence of attractive surface in the vapour phase, induces strong
layering near the surface (can be observed from the density pro-
file discussed in the next section), and therefore, bond formation
within the layer (near the surface) increases and hence the de-
crease in monomer fraction.
The degree of association increases significantly with an in-
crease in associating strength, and therefore the phase envelops
shifts to the lower monomer fraction with an increase in associat-
ing strengths. In particular, the degree of association in the vapour
phase is more influenced compared to the liquid phase due to con-
finement for higher associating fluids (ε af ∗ > 6), which may be due
to the layering formation of vapour phase near the surface can be
examined through density profile (discussed in the next section).
Fig. 3(b) shows the effect of confinement on the monomer frac-
tion of an associating fluid (ε af ∗ = 6) at coexistence. Interestingly,
at a given temperature, the monomer fraction of the liquid and
vapour phase increases with the degree of confinement, which in-
dicates the association of molecules in the vapour phase as well
as in the liquid phase increases with an increase in slit width at
5
Fluid Phase Equilibria 531 (2021) 112909
Fig. 4. Saturation pressure for different associating strength at H∗ = 6. Solid lines
with open symbols represent the saturation pressure at bulk for corresponding as-
sociating strengths.
a given temperature, which is due to the decrease in saturation
pressure with slit width, discussed in the next section.
3.3. Saturation pressure
The saturated vapour pressure of the system is estimated us-
ing the Clausius-Clapeyron equation and is shown in Fig. 4. As ex-
pected, the saturated vapour pressure decreases linearly with a de-
crease in temperature, which is also observed for various model
fluids [59–61]. The slope of the line decreases with an increase in
associating strength, which is also seen for other associating flu-
ids in bulk [57,58]. The increase in associating strength and the
degree of association in the liquid phase increases the latent heat
of vaporization and, hence, decreases the saturated vapour pres-
sure in the system. Therefore, the saturation pressure of associat-
ing fluids in confinement increases at a given temperature as the
degree of association decreases. The difference of saturation pres-
sure between bulk and confinement (H∗ =6) at a given temperature
decreases with an increase of associating strength. Therefore, the
effect of confinement on the saturation pressure is less for higher
associating strength fluids.
3.4. Density and orientation profile
To understand the effect of association strength on the coex-
istence phases, we examine the number density profile along z-
direction normal to the surface. Fig. 5 represents the z-density pro-
file for different association strength at a pore width of H∗ =6. Due
to the substrate interaction, the fluid molecules are found in an
ordered structure near the surface. The density near the surface
is more compared to that of the middle regime. With an increase
in association strength, the density of each layer increases due to
an increase in orientational ordering and, hence, compact packing
in the fluid layers. On the other hand, the layering in the vapour
phase decreases due to a decrease in vapour pressure. The number
of layers in the vapour phase is less compared to the liquid phase,
and hence bulk regime is visible in the vapour phase, whereas for
the liquid phase, we do not observe bulk regime at H∗ =6. How-
ever, the bulk regime for the liquid phase, can be observed at slit
width H∗ > 10, as shown in Fig. 5(b). To understand the orienta-
tional ordering of fluid molecules confined in slit pore, we examine
the orientational order parameter, as shown in Fig. 6(a). The aver-
S.S. Mandal, S.K. Singh, S. Bhattacharjee et al.
Fig. 5. (a). Density profile for different associating fluids at slit width H∗ =6 and at
T∗ =1.1. Solid line represents the liquid density and dash-dot line represents the
correspondingvapour density. (b). Density profile for a associating fluid (ε af ∗ =6) at
different slit width H∗ =6,8 and 10 and, at T∗ =1.1. Solid line represents the liquid
density and dash-dot line represents the corresponding vapour density profiles.
age orientation order parameter is evaluated as follows:
 substrate strength [62]. However, in this study, the interaction be-
3cos2 (θ ) − 1
Sz = (6)
2 fore, it is quite expected that the sites on the fluid particles would
where, θ is the angle between the z-coordinate normal to the sur-
face and site vector of the fluid molecule.
We observe strong orientational ordering near the surface with
an increase in association strength. The centre to site vector of a
fluid molecule near the surface tends to lie parallel to the surface,
which is more pronounced at higher association strength (ε af ∗ =8).
The orientational ordering of fluid molecules slowly diminishes in
the subsequent layers. However, the orientational ordering of fluid
molecules in all layers is preferentially parallel to the surface.
6
Fluid Phase Equilibria 531 (2021) 112909
Fig. 6. Orientational order parameter for different associating fluids at H∗ =6 and at
T∗ =1.1. Solid line represents the liquid orientation profiles and dash-dot line repre-
sents the corresponding vapour orientation profiles.
Fig. 7. Temperature-density vapour-liquid coexistence envelope of an associating
fluid (ε af ∗ =6) in a slit width H∗ =6 for different surface site density.
3.5. Phase transition inside functionalized slit pore
The effect of surface sites on the phase transition of confined
fluid is shown in Fig. 7. At a given temperature, with an increase
in surface sites, the vapour density significantly increases. In con-
trast, the liquid density remains the same at lower surface site
density and slightly increases at higher surface site density. This
implies that the surface sites play an important role in triggering
the arrangement of the fluid molecules in coexistence phases. Con-
sequently, the critical density increases and critical temperature
decreases with an increase in surface site density. A similar ob-
servation is also found for other model fluids with an increase in
tween associating fluid molecules is directional dependent; there-
be oriented towards the surface, which is just opposite in the case
of a smooth surface. Hence, we examine the z-density profile and
the orientational profile to understand the molecular ordering in-
side the system, which is discussed in the next section.
3.6. Density and orientation profile
The density profile normal to the surface is analysed in Fig. 8
at different surface site density. It can be observed from Fig. 8 that
S.S. Mandal, S.K. Singh, S. Bhattacharjee et al.
Fig. 8. Density profile of associating strength ε af ∗ =6 at slit width H∗ =6 and at T∗
=1.00 for different surface site density. Solid line represents the liquid density and
dot line represents the corresponding vapour density profiles.
the liquid density near the surface is quite high and is very sharp,
which means that the fluid molecules are strongly ordered near
the surface, shift the subsequent layers toward the surface, and
result in a partial split in the middle peak at high surface site
density. Overall, the structural behaviour of the coexistence phases
completely different in the presence of surface sites. To understand
Fig. 9. (a). Orientational order parameter of liquid phase of an associating fluids (ε af ∗ =6) at H∗ =6 and at T∗ =1.0 for different surface site density. Corresponding snapshots
are shown in right panel of the figure. (b). Orientational order parameter of vapour phase of an associating fluids (ε af ∗ =6) at H∗ =6 and at T∗ =1.0 for different surface site
density. Corresponding snapshots are shown in right panel of the figure.
7
Fluid Phase Equilibria 531 (2021) 112909
the effect of surface sites on the ordering of the fluid molecules,
we analyse the orientation order parameter profile of the liquid
phase, as shown in Fig. 9.
Interestingly, we found that the orientation of fluid molecules
near the surface in the presence of surface site is perpendicular
to the surface, which is just opposite without surface sites. There-
fore, the orientation of the subsequent layers also gets affected and
preferentially oriented toward the surface. The orientation profile
of the middle layer (for ρ s =1) also suggests that the layer has
two kinds of molecules with different orientations. Like the liquid
phase, the surface site also influences the vapour phase and leads
to strong layering near the surface, as shown in Fig. 9(b). Interest-
ingly, the density of the layering near the surface is very close to
the liquid density and increases with an increase in surface site
density. The orientation of the fluid molecules in the vapour phase
is very similar to that of the liquid phase, i.e., the fluid molecules
are preferentially oriented toward the surface.
3.7. Monomer fraction profile
To understand the association of fluid molecules in different
layers, we analyse the monomer fraction profile along the axis nor-
mal to the surface, as shown in Fig. 10. It should be noted that
the molecules bonded with only surface sites are also treated as
a monomer. It can be observed that the values of monomer frac-
tion in the layer near the surface are quite high (~0.7). Also the
molecules in that layer are highly (orientational order parameter ~
0.7, i.e., almost normal to the surface) oriented towards the surface,
as seen from the orientation profile in the presence of surface sites
S.S. Mandal, S.K. Singh, S. Bhattacharjee et al.
Fig. 10. (a). Monomer fraction profile of liquid phase of an associating fluids
(ε af ∗ =6) at H∗ =6 and at T∗ =1.0 for different surface site density. (b). Monomer frac-
tion profile of vapour phase of an associating fluids (ε af ∗ =6) at H∗ =6 and at T∗ =1.0
for different surface site density.
(for ρ s =1). Therefore, the probability of forming bonds between
molecules within the layers is very less. Hence, it suggests that
some fraction of fluid molecules in that layer form bonds with the
surface site in one direction, and in other direction, it forms bonds
with the molecules in the adjacent layers. Therefore, the bond for-
mation with the surface sites allows propagating the bond forma-
tion to the adjacent layers, which result in shifting of density peaks
towards the surface, which is found from the density profile. The
maximum density for second layers from the surface is found at
z~1.8 in the presence of surface sites where the orientation order
parameter is maximum, and the monomer fraction is found to be
minimum, which implies that the molecules in the layers preferen-
tially bonded with adjacent layers. A similar observation is found
in the vapour phase shown in Fig. 10(b).
3.8. Effect of site location
From the above discussion, it is understood that in the case
of two-site associating fluids (sites are on opposite sides termed
as type A), the fluid molecules near the surface form bonds with
surface sites in one direction. In another direction, it forms bonds
with adjacent layers and, hence, affects the structural behaviour
of confined fluids. Therefore, two-site associating fluids, with op-
positely located sites, promote the interlayer bond formation and
propagate the effect of the surface to the adjacent layers. To under-
stand the impact of site location of fluid molecules on the phase
8
Fluid Phase Equilibria 531 (2021) 112909
Fig. 11. (a). Density profile of coexistence phases of an associating fluids (ε af ∗ =6) at
H∗ =6 and at T∗ =1.0 for different surface site density. (b). Monomer fraction profile
of coexistence phases of an associating fluids (ε af ∗ =6) at H∗ =6 and at T∗ =1.0 for
different surface site density.
behaviour of confined fluids, we also study the phase behaviour of
the two-site associating fluids in which the sites are located at an
angle of 90 degrees (termed as type B). Fig. 11(a) represents the
density profile of coexistence phases for two types of associating
fluids at H∗ =6 and T∗ =1.0. In general, we do not observe much sig-
nificant difference in the density profile for type B with and with-
out surface sites and found to be less ordered compared to that of
type A. In particular, in the case of type B with surface sites, the
density of the layer close to the surface is quite sharp and higher
than that without surface sites. However, this change in 1st layer
does not affect much in the subsequent layers, and therefore the
behaviour of density profile for type B is more or less similar with
and without surface sites except in the 1st layer. This behaviour is
mainly due to the site location in the fluid molecules. In the case
of type B, when fluid molecules form a bond with surface sites,
then another site of the molecules is not available to form bonds
with adjacent layers, and therefore surface sites only affect the 1st
layer. On the other hand, in the case of type A, the formation of
bond with surface sites also enhance the bond formation with ad-
jacent layers, and hence the effect of surface sites can be visualized
to adjacent layers.
Monomer fraction profile, as shown in Fig. 11(b), also suggests
less association of type B compared to that of type A molecules.
For type B, the monomer fraction profile for both the liquid and
S.S. Mandal, S.K. Singh, S. Bhattacharjee et al.
vapour phase is similar with and without surface sites except in
the 1st layer. On the other hand, for type A, the monomer fraction
profile is found to be more layering in the case with surface sites
for both the phases and results in a more ordered structure in the
coexistence phases.
4. Conclusions
In this work, the vapour-liquid phase equilibria of associating
fluids under confinement are investigated through grand-canonical
transition matrix Monte Carlo (GC-TMMC) simulations. Various
properties of coexistence phases, and critical properties, are esti-
mated for multiple associating fluids at different slit widths. For a
given slit width, with an increase in associating strength, the crit-
ical temperature of the coexistence phases increases. Interestingly,
an insignificant change in the critical density is observed with the
change in the associating strength of the fluid, which is attributed
to the symmetrical shift in the coexistence envelope with the as-
sociating strength. The corresponding state coexistence behaviour
has also investigated for an associating strength, ε af ∗ = 4 & 6 at dif-
ferent pore widths varied from H∗ = 4 to 40. Corresponding state
behaviour has shown an interesting trend of coexistence envelopes.
The highest shrinkage in the corresponding state coexistence enve-
lope is observed with the studied slit width, H∗ = 15. Further, with
the decrease in the slit width, the corresponding state coexistence
envelope broadens and overlaps the bulk corresponding state co-
existence envelope at H∗ = 4 and even broader than that of the
bulk phase at H∗ = 3. Moreover, at larger slit pore widths, such as
H∗ = 40, the corresponding state coexistence envelope again starts
broadening and indicating its approach towards bulk, as expected.
The structural properties of coexistence phases are exam-
ined through monomer fraction, density, and orientation profiles.
Monomer fraction of different associating fluid at a particular slit
width, H∗ =6, and monomer fraction at different slit width for a
given associating fluid, ε af ∗ =6 are also investigated. At a given as-
sociating strength, with a decrease in temperature (for H∗ =6), the
values of monomer fraction significantly decrease for liquid phase
while the change of monomer fraction in the vapour phase is very
small or negligible depending on the associating strength. On the
other hand, at a given temperature, the values of monomer frac-
tion for the liquid phase increases and the vapour phase decreases
under confinement compared to the respective bulk systems. In-
terestingly, for an associating fluid at a given temperature, the
monomer fraction of the liquid and vapour phase increases with
the increase in the degree of confinement. The saturation pressure
of associating fluids in confinement increases at a given tempera-
ture as the degree of association decreases. The difference of sat-
uration pressure between bulk and confinement at a given tem-
perature decreases with an increase of associating strength. This
indicates that the effect of confinement on the saturation pressure
is less for higher associating strength fluids. To understand the im-
pact of association strength, the local densities, and the orientation
profile of the coexistence phases, are also examined. The density
near the surface is more compared to that of the middle regime.
With an increase in association strength, the densities of each layer
increases due to an increase in orientational ordering and hence
result in compact packing in the fluid layers. Strong orientational
ordering is observed near the surface, with an increase in asso-
ciation strength. The orientational order of fluid molecules slowly
diminishes in the subsequent layers. However, the orientational or-
dering of fluid molecules in all layers are preferentially parallel to
the surface.
Further, the role of surface sites on the phase behaviour un-
der confinement is critically examined, and found that with an in-
crease in surface sites, the vapour density significantly increase. In
contrast, the liquid density slightly increases at a given tempera-
9
Fluid Phase Equilibria 531 (2021) 112909
ture. This behaviour is further supported by the local density, ori-
entation, and monomer fraction profiles. It can be observed that
the molecules near the surface are highly oriented towards the sur-
face in the presence of surface sites, which promote the interlayer
bond formation to the adjacent layers. Thus, the presence of sur-
face site propagates the effect of a surface to the adjacent layers in
the coexistence phases.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
CRediT authorship contribution statement
Sashanka Sekhar Mandal: Methodology, Formal analysis, Writ-
ing - original draft, Visualization, Investigation. Sudhir Kumar
Singh: Writing - review & editing, Visualization, Investigation.
Sanchari Bhattacharjee: Writing - review & editing, Visualization.
Sandip Khan: Conceptualization, Supervision, Writing - review &
editing, Project administration.
Acknowledgement
We would like to acknowledge the Department of Chemical and
Biochemical at IIT Patna for providing computational resources for
this research.
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