Article

pubs.acs.org/JPCC

Molecular Dynamics Study on the Growth Mechanism of Methane

plus Tetrahydrofuran Mixed Hydrates
Jyun-Yi Wu, Li-Jen Chen, Yan-Ping Chen, and Shiang-Tai Lin*
Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan
*
S Supporting Information

ABSTRACT: Molecular dynamics (MD) simulations are

performed to analyze the dominating factors for the growth
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of CH4 + THF mixed hydrates, and the results are compared

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with the growth of single guest CH4 and THF hydrates. While
CH4 hydrate has a type I crystalline structure, the presence of
THF in the aqueous phase results in the growth the type II
structure hydrate. Compared to THF hydrates, the presence of
CH4 in the system enhances the dissociation temperature. The
growth rate of CH4 + THF mixed exhibits a maximum value at
about 290 K at 10 MPa. The growth rate is found to be
determined by two competing factors: (1) the adsorption of CH4 at the solid−liquid interface, which is enhanced with decreasing
temperature, and (2) the migration of THF to the proper site at the interface, which is enhanced with increasing temperature.
Above 290 K, which is about 10 K higher than the dissociation temperature of pure THF hydrate, the growth of cage can proceed
only when a sufficient amount of CH4 is adsorbed at the interface. The growth rate is dominated by the uptake of CH4 at the
interface, as in the case of pure CH4 hydrate. Below 290 K, the growth is not much affected by the presence of CH4. Instead, the
growth rate is determined by the rearrangement of THF molecules at the interface, as in the case of pure THF hydrate.

1. INTRODUCTION as much as 18 K12,14 when there is 5.56 mol % of THF in the

Clathrate hydrates are a class of crystalline solids consisting of
small guest molecules (such as methane or CO2) encapsulated in
the cage spaces formed by hydrogen-bonded water molecules.
Naturally occurring clathrate hydrates, mostly methane hydrates,
are found in permafrost region and sea floors. The amount of
methane trapped in the form of hydrate is so abundant such that
it is considered as a potential source of energy.1−4 Furthermore,
due to the characteristic of high gas density at relatively high
temperature and low pressure, gas hydrates are also considered as
a good means for transport and storage of large quantities of gas,
such as natural gas,5,6 carbon dioxide,5 and hydrogens.7−11
The knowledge of thermodynamic stability of clathrate
hydrates and how their stability limit can be enhanced or
reduced is important for developing processes involving them.
One possible means to change the dissociation temperature of
gas hydrates is to control the system pressure. For example, the
dissociation temperature of methane hydrate is 273 K at 25 atm
and can be enhanced with increasing pressure.12 An alternative
way to alter the stability of gas hydrate is to introduce additives to
the aqueous solution. For example, alcohols (e.g., methanol,
ethanol) are known to be effective inhibitors that reduce the
dissociation temperature under constant pressure. On the other
hand, cyclic ethers (e.g., tetrahydropyran, cyclobutanone,
methylcyclohexane) are promotors that increase the dissociation
temperature of gas hydrates.13
Tetrahydrofuran (THF) is known to be a very effective
thermodynamic promoter of gas hydrates.10,12,14,15 The
formation temperature of methane hydrate can be enhanced by
aqueous phase. In fact, the presence of THF results in a different
crystalline structure. Pure methane hydrates are of type I
structure, where methane molecules stay in both the small
(pentagonal dodecahedron, 512) and large (hexagonal truncated
trapezohedron, 51262) cages created by the hydrogen-bonded
water molecules. The presence of THF would result in the
formation of type II structure, with methane molecules
occupying the small 512 cages and the THF occupying the larger
(hexadecahedron, 51264) cages. Type I structure (sI) contains
two 512 and six 51262 cages, and type II structure (sII) consists of
sixteen 512 and eight 51264 cages. Although the occupancy of
methane increases with pressure, THF almost always occupies all
the 51264 cages in the type II structure.16,17 Therefore, the loading
of methane in the methane + THF mixed hydrate is significantly
less than that in pure methane hydrate.16
While THF is a powerful thermodynamic promotor of gas
hydrates, the growth rate of CH4 + THF hydrates is found to be
slower than that of CH4 hydrates under the same subcooling
temperature.18 However, the fundamental reason for the slower
growth kinetics with the presence of THF is not clearly known.
MD simulations have been used to provide molecular insights
into many important issues of gas hydrates, including
nucleation,19−24 guest replacement,25−27 growth/melting mech-
anism,28−31 and structure changes.32,33 It has been shown that
Received: June 5, 2015
Revised: August 6, 2015
Published: August 10, 2015

© 2015 American Chemical Society 19883 DOI: 10.1021/acs.jpcc.5b05393

J. Phys. Chem. C 2015, 119, 19883−19890
The Journal of Physical Chemistry C
Figure 1. Initial structure of the gas−liquid−hydrate three-phase model of CH4 + THF hydrate. This model corresponds to a liquid phase THF
concentration of xTHF
L = xTHF
H . The system contains 112 THF 416 CH4 and 1904 water molecules.
the solubility of CH4 in water, the transport of CH4 to the
hydrate/liquid interface, and the uptake of methane on the
interface are the key factors determining the growth rate of
methane hydrates.28 For pure THF hydrates, the transport of
THF to the interface and the migration of interfacial THF are the
dominating growth factors.34,35 Recent work of Erfan-Niya et
al.36 investigated the bulk properties of CH4 + THF mixed
hydrates. However, to the best of our knowledge, there has not
been any report on the kinetics and growth mechanism of CH4 +
THF mixed hydrates. Therefore, the aim of the present work is to
calculate the growth rates and analyze the growth mechanism of
CH4 + THF hydrate by MD simulations. Our results help to
provide insights into the kinetic inhibition effect of THF during
the growth of methane hydrates.
2. SIMULATION DETAILS
2.1. Molecular Model. The liquid−hydrate−liquid−gas (L-
H-L-G) three-phase model, as shown in Figure 1, was created
using Materials Studio37 for the simulation of dissociation
condition and growth rate of CH4 + THF hydrate. The √2 ×
√2 × 2 sII hydrate crystal with (100) crystal face has each of its
large cages filled with one THF molecule and each of small cages
filled with one CH4 molecule (a total of 32 THF and 64 CH4).
The (100) crystal face was chosen because it was found the
fastest growth face of THF hydrate in a previous study.35 For the
ease of future analysis, we define a unit hydrate layer (HL) as the
repeating unit in the hydrate phase (two HLs in the hydrate
phase in Figure 1). Each HL can be further divided into four
equally sized sublayers (SL) along the z-direction.34 Before filling
in guest molecules, the empty sII lattice was annealed by heating
and cooling with the position of oxygen atoms fixed. This allows
for the water molecules to rotate and reconstruct the hydrogen
bond network such that a structure of zero net dipole moment
can be obtained. The liquid phase initially contains only water
and THF (with the ratio of THF:water being the same as that in
the hydrate phase) and free of any CH4. It is expected that both
the CH4 diffusion and the THF rearrangement at hydrate
interface (which has been shown to be important at such high
THF concentration condition34) will affect the growth of CH4 +
THF hydrate in our simulation.
2.2. Molecular Dynamics (MD) Simulation. The MD
simulations were performed using GROMACS 4.5.38−40 The
initial structure was first energy minimized to eliminate any bad
contacts. A 20 ps MD simulation was then conducted at 200 K
under constant volume (NVT) to further relax any extra stress in
the system. A subsequent temperature rising process was then
performed to increase the temperature the desired value at a rate
of 0.5 K/ps, followed by an additional 100 ps simulation at the
19884
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target temperature. After these pre-equilibration steps (time zero
point in our analysis), long (up to 1.7 μs) NPT simulations were
then performed for analysis.
The leapfrog algorithm41 is used with a integration time step of
1 fs. The cutoff radius for both van der Waals and Coulomb
interactions is 0.95 nm. Long-range Coulomb interactions are
determined using the particle-mesh Ewald (PME)42 method.
The Nosé−Hoover thermostat43 with tau_t = 1 ps is used for
temperature control and the Parrinello−Rahman44 with tau_P =
10 ps for the pressure control. Anisotropic pressure control (one
for the growing direction and one for the other two directions) is
adopted for the liquid−hydrate−liquid−gas three-phase model.
Isotropic pressure control is adopted for the simulation without
hydrate phase (for the diffusivity and solubility tests).
2.3. Force Field. The TIP4P-Ice force field45 is choose in this
study for H2O molecules. This force field is known to reproduce
the phase boundary between liquid water and ice, the density of
both liquid water and ice, the melting enthalpy, and the slope of
the coexistence curve. For CH4 molecules, the OPLS-AA
model46 is employed. The geometric mean is used for the off-
diagonal terms for the Lennard-Jones (LJ) potential between
water and CH4. For THF molecules, model 7 of Girard et al.47
was slightly modified (see Table 1) to better reproduce the
Table 1. Density and Heat of Vaporization of THF at 300 K
and 1 atm Obtained Using Different Scaling Factors for the LJ
12−6 Potential Parameters of Girad
density
fσa fε a (kg/m3) Hvap (kJ/mol)
Girard 7a 1 1 904 34.32
modified Girard 7 1.003 0.933 880 31.92
exptl data 880b 31.803 ± 0.012c
a
Factors for modifying the LJ 12−6 parameters from Girad’s work47
σnew
i = fσ × σGirad
i and εnew
i = fε × εGirad
i with i = C, H, or O. σGirad
C =
0.385, σO = 0.350, σH = 0.190 (nm), εGirad
Girad Girad
C = 0.190, εGirad
O = 0.360,
and εGirad
H = 0.150 (kJ/mol). bAt 1 atm and 298.15 K.48 cAt 0.25 atm
49
300.80 K.
density and heat of vaporization of pure THF liquid. The off-
diagonal LJ potential parameters between THF and water were
taken from previous study.34 The solubility of THF in water and
the dissociation temperature of THF hydrate from these settings
are in good agreement with experiment. (Note that the solubility
of THF was underestimated and the dissociation temperature of
THF hydrate was slightly overestimated if the geometric mean
was used to determine the off-diagonal LJ parameters.) It should
be noted that no data of the mixed CH4 + THF hydrates were
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The Journal of Physical Chemistry C
used for the parameter optimization. The off-diagonal LJ
parameters are summarized in Table 2.
Table 2. Off-Diagonal LJ 12−6 Potential Parameters between
THF and Water
CTHF−OH2O OTHF−OH2O
force field ε (kcal/mol) σ (Å) ε (kcal/mol) σ (Å)
geometric mean 0.0944 3.496 0.1301 3.334
modified34 0.2547 3.430 0.1509 3.163
2.4. Growth/Melting Rate. The growth rate, r, of hydrate is
calculated from the number of water molecules added to the
hydrate phase from the 100 to 300 ns of the NPT simulation. The
data of initial 100 ns was taken as the time needed for the system
to reach steady growth.
number of water molecules increased THL
r=
200 ns WHL (1)
where THL and WHL are the thickness and number of water
molecules in one hydrate layer (HL). The values of these two
properties depends on the structure of the hydrates. For sII
hydrates (THF and CH4 + THF), THL = 17.2 Å and WHL = 272.
For sI hydrates (CH4), THL = 11.9 Å and WHL = 184. For better
statistics, the growth rates are averaged from the results of three
independent runs (generated using different random seeds for
the initial velocity). The method for determining the number of
water used in hydrate is the same as the previous study and
shown in Figures S1−S3 of the Supporting Information.34
3. RESULTS AND DISCUSSION
3.1. Validation of the Force Field. The thermodynamic
properties such as the solubility of guests in water, dissociation
temperatures of hydrates, and the thermodynamic promotion
effect of THF for CH4 hydrates can serve as a validation of the
force field used in this study. The solubility is determined using
NPT simulation for a two-phase (gas and liquid) model (as in ref
34). The solubility of methane in water is found to be 0.128 mol/
kg water (or 434 water per CH4) at 10 MPa and 305 K, which is
in good agreement with the experiment,50 0.111 mol/kg water
(or 500 water per CH4) at 10.22 MPa and 303.2 K. THF and
water are completely miscible at ambient conditions. However,
as shown in Figure S4a, the use of geometric mean for the off-
diagonal LJ terms between THF and water (see Table 2) results
in partially miscible two-liquid phases. This implies that the
interactions between THF and water are too weak. The modified
off-diagonal parameters (Table 2) increases the attractive
interactions between THF and water and thus results in a
completely miscible mixture (Figure S4b) as observed in
experiment.51
The dissociation temperature (Td) of hydrates is determined
by performing several NPT simulations with different temper-
atures under the same pressure. If the temperature is above Td,
the hydrate phase would melt and the potential energy would
increase. If the temperature is below Td, then the opposite would
happen.27−30,34,52 Figure 2 compares the dissociation temper-
atures as a function of pressure for CH4, THF, and CH4 + THF
hydrates from our simulation (open symbols) and experiment
(lines). Both the dissociation temperatures of THF hydrate and
CH4 hydrate are well reproduced. The dissociation temperatures
of CH4 + THF hydrates are slightly overestimated by 5−10 K.
19885
Article
Figure 2. Dissociation condition of CH4 hydrates (green triangles),
THF hydrates (red diamonds), and CH4 + THF hydrates (blue squares)
from MD simulations and the experiment (lines).12,53,54
Nonetheless, the promoting effect of THF for CH4 is correctly
predicted.
3.2. Growth Rate. The growth rates of CH4 + THF mixed
hydrate are determined at temperatures below the dissociation
condition (312.5 K) at 10 MPa. Figure 3 illustrates the time
evolution of the hydrate phase thickness (in terms of hydrate
layers, HL) from three independent sets of simulations at three
temperatures. In general, the thickness increases with time, but
there are ups and downs during the period of our growth
simulation. The cause of pauses and temporary dissociation will
be discussed in the next section. The slope of the curves in Figure
3d (average of the independent runs) gives the growth rates. The
data of initial 100 ns in our simulation are discarded (see eq 1) to
avoid the effect from the initial relaxation processes. (There is a
clear change of slope in Figure 3d in the initial 5−10 ns as a result
of the diffusion of methane to the aqueous phase.) Figure 4
summarizes the growth rate of CH4 + THF hydrate with different
subcooling temperatures at 10 MPa. The growth rate exhibits a
maximum value at 290 K (a subcooling temperature of 22.5 K).
Furthermore, the growth rate appears to be independent of
temperature below 280 K.
Table 3 shows the growth rate of CH4, THF, and CH4 + THF
hydrate at different temperature and pressure. Note that under
the same degree of subcooling (e.g., 7.5 K at 10 MPa) the growth
rate of CH4 hydrates, 4.08 ± 0.20 mm/s (275 K), is 3 times
greater than that of CH4 + THF hydrate, 1.20 ± 1.82 mm/s (305
K). Such a kinetic inhibition effect of THF to CH4 hydrate was
also observed in a previous experimental study.18 However, it is
noteworthy that the comparison of growth rate between CH4
hydrate and CH4 + THF hydrate is not meaningful because they
are of different crystalline structures. A more sensible comparison
is between THF hydrate and CH4 + THF hydrate, where it is
found that CH4, a thermodynamic promoter of THF hydrate, is a
kinetic inhibitor below the dissociation temperature of THF
hydrate and a kinetic promotor near and above the dissociation
temperature of THF hydrate.
It is noteworthy that factors such as the size of the molecular
model and the thickness of the aqueous layer can have an
influence on the value of the growth rate. The strength of MD
simulations is not to provide the quantitative value of growth rate
but to provide insights, as will be discussed in the following
section, into how the different factors (in our case the
temperatures) affect the growth rate.
3.3. Growth Mechanism. In Figure 3, we observe that the
growth of CH4 + THF hydrate is not a steady process. For
example, in 10 MPa−275 K−run 3, the growth pauses at 20−60
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Figure 3. Time evolution (growth) of CH4 + THF hydrate layers at 10 MPa and 275 K (a), 290 K (b), and 305 K (c). Shown in each figure are results of
three independent runs. The average values are compared in (d). The dissociation temperature at 10 MPa is 312.5 K.

interface are notably different. The difference can be understood

from the distribution of guest molecules at the interface. Figure 6
illustrates the cross section of the sublayer 1 (SL1) on the left-
and right-hand sides of the initial hydrate crystal at 30 ns and 1 μs.
At 30 ns (near the beginning of simulation), the sublayer 1 on
both sides are both solid−liquid interfaces. Both the THF and
CH4 molecules adsorbed on the small and large cage sites (see
Figure 6a,b). However, all the large cage sites are occupied by
THF molecules, and some of small cage sites are filled by CH4
molecules after the growth finishes, i.e., Figure 6c,d. The
rearrangement of guest molecules to the proper sites at the
interface is necessary for the successful growth of a SL.
To investigate the reason for intermittency in the growth
Figure 4. Growth rate of CH4 + THF hydrate as a function of process in more detail, the number of guest molecules (THF and
temperature at 10 MPa. CH4) absorbed to different sublayers (SL) during the course of
simulation is analyzed. Figure 7 shows the number of guest
Table 3. Growth Rate of CH4, THF, and CH4 + THF Hydrates molecules (THF and CH4) absorbed to different sublayers (SL)
from MD Simulations at 297.5 K during the course of simulation. It should be noted
system P (MPa) T (K) growth rate (mm/s) that each SL has four large cage (51264) sites and eight small cage
CH4 hydrate (512) sites (see Figure 6). As the growth process begins, the THF
10 260 3.56 molecules are adsorbed on both large and small cage sites, and
10 267.5 3.62 ± 0.61 thus the total number of THF quickly exceeds 4 (see SL1 before
THF hydrate 10 275 4.08 ± 0.20 200 ns (Figure 7a), SL2 from 200 to 400 ns (Figure 7b), and SL3
0.1 270 8.15 ± 1.57 from 400 to 700 ns (Figure 7c)). To proceed with the growth, the
CH4 + THF hydrate 10 262.5 7.37 ± 0.80 excess THF molecules, in particular those adsorbed on the small
10 262.5 3.91 ± 1.48 cage sites, must be desorbed. At high temperatures (e.g., above
10 270 3.13 ± 2.24 dissociation temperature of pure THF hydrate, 276 K at 10
10 275 2.83 ± 3.06 MPa), the THF molecules can escape from the interfacial cage
10 280 2.92 ± 0.81 sites more easily. As can be seen in SL3 from 400 to 700 ns, the
10 285 2.93 ± 2.02 number of THF molecules in both large and small cage sites
10 290 6.10 ± 2.89 changes quickly. Notice that the growth of SL3 (from 390 to 820
10 297.5 2.28 ± 2.10 ns) is slower than that of SL1 (from 0 to 180 ns) and SL2 (from
10 305 1.20 ± 1.84 180 to 390 ns). One obvious reason is the number of CH4 in SL3
remained at a low value (fluctuating between 0 and 1 most of the
ns, 70−145 s, 180−220 ns, and 240−270 ns. The duration of time) compared to those in other SLs. Before 700 ns, the number
pauses may take as long time as 100 ns (e.g., 70−300 ns in 10 of CH4 molecules at the interface is always equal to or smaller
MPa−275 K−run 2 or 20−300 ns in 10 MPa−305 K−run 3). than 2 (Figure 8g). After 700 ns, the number reaches 4 or 5 and
These pauses result in a slower value and higher uncertainty in the growth of the SL quickly finishes. In other words, the
the calculated growth rate. Figure 5 illustrates an example of the adsorption of enough CH4 at the interface is important at this
growth of CH4 + THF hydrate at 10 M Pa and 297.5 K. After 1 μs temperature. This is sensible because without CH4 the THF
(Figure 5b) the thickness of the CH4 + THF hydrate increased to hydrate would not from as the simulation temperature is already
4 hydrate layers. The growth rates of the left interface and right above the dissociation temperature of THF hydrate. In other
19886 DOI: 10.1021/acs.jpcc.5b05393
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The Journal of Physical Chemistry C Article

Figure 5. Snapshots of CH4 + THF hydrate growth at 10 MPa and 297.5 K at 30 ns (a) and 1 μs (b). The location of the solid−liquid interface at time 0
ns is indicated by bold dashed lines. The blue dashed lines are used to illustrate the ID of sublayers (SL) for discussion in the main text.

Figure 6. Cross section of left and right (b, d) sublayer one (SL1) from CH4 + THF hydrate growth at 30 ns (a: left surface, b: right surface) and 1 μs (c:
left surface, d: right surface).

words, the occupancy of CH4 in the small cages is important to
stabilize the hydrate structure at high temperatures.
Figure 8 shows the situation at 262.5 K, which is below the
dissociation temperature of pure THF hydrate. In this case, the
presence of CH4 molecules is not indispensable for the growth of
structure II hydrate. As can be seen in Figure 8e,f, the growth of
the hydrate layer can proceed even without any CH4 at the
interface. On the other hand, the rearrangement of THF at the
interface becomes more difficult because of the lowered mobility
of water and THF. (The result was shown in the previous study;
the ideal liquid THF concentration in THF hydrate growth is
higher in higher temperature.34) For example, the growth of SL2
(from 80 to 150 ns) does not finish until all the THF molecules
leave the small cage sites. The rate-determining process thus
changes to the rearrangement of guest molecules at the interface
at low temperatures.
It is interesting to note that the adsorption of CH4 at the
interface is favored at lower temperatures as the solubility of
19887
methane is enhanced.28 However, the rearrangement of THF at
the interface is easier at high temperatures because of enhanced
molecular mobility.34 The different temperature dependence of
these two competing factors results in a maximum growth rate at
a temperature (about 290 K) that is slightly higher than the
dissociation temperature of pure THF hydrate (276 K). It is
reasonable to presume that between 276 and 290 K the growth is
dominated by the rearrangement of THF.
The temperature dependence of growth rate also affects the
occupancy of CH4 given in Table 4. At 10 MPa and 290 K the
CH4 occupancy of small cages reaches a minimum value of 0.269.
Above 290 K, the occupancy of CH4 must be higher because the
hydrate interface would not be stable otherwise. Below 290 K, the
low growth rate (limited by THF rearrangement) allowed
enough time for more CH4 adsorbing on the interface. The
occupancy of the large cages is close to unity in all cases. This is
because that the THF hydrates are not stable without the large
cages being occupied.34 The high concentration of THF results
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Figure 7. Number of THF (a, b, and c for layers 1, 2, and 3, respectively) and CH4 (d, e, and f for layers 1, 2, and 3, respectively) molecules located at the
aqueous phase near the left-hand-side interface. The system is at 10 MPa and 297.5 K.

Figure 8. Number of THF (a, b, and c for layers 1, 2, and 3, respectively) and CH4 (d, e, and f for layers 1, 2, and 3, respectively) molecules located at the
aqueous phase near the left-hand-side interface. The system is at 10 MPa and 262.5 K.

in fast adsorption of THF to the large cage sites, and thus the
growth rate is dominated by slower processes, adsorption of CH4
at high temperatures and THF desorption/migration at low
temperatures. Also shown in Table 4 is the occupancy reported
from NMR study at 4 MPa and 292 K.16 The occupancy from our
simulation at 5 MPa and 290 K agrees quite well with the
experiment, which again confirms the reliability of our
simulation.
19888
4. CONCLUSION
The growth mechanism of methane and tetrahydrofuran
clathrate hydrates was investigated by MD simulations. The
force field used provides reasonable accuracy for a variety of
relevant thermodynamic properties, including the melting point
of ice, dissociation temperature of THF, CH4, and CH4 + THF
hydrates, and solubility of CH4 and THF in water. The kinetic
inhibition effect of THF in CH4 hydrate was also observed. Our
simulations show that the growth of CH4 + THF mixed hydrate
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Table 4. Occupancy of Guests in the Newly Grown CH4 + THF Hydrate Layers
512 51264
source P (MPa) T (K) CH4 THF CH4 THF CH4 + THF
16
NMR 4 292 0.3701 0.9989 0.9989
MD 5 290 0.4262 0 0.0227 0.9769 0.9996
10 262.5 0.4419 0 0 0.9694 0.9694
10 270 0.5900 0 0.0128 0.9872 1.0000
10 275 0.4175 0 0.0198 0.9802 1.0000
10 280 0.4312 0 0.0025 0.9662 0.9687
10 285 0.3654 0 0.0003 0.9997 1.0000
10 290 0.2937 0 0.0519 0.9481 1.0000
10 297.5 0.4224 0 0 1 1
10 305 0.6141 0 0 1 1

is dominated by the adsorption of CH4 to the growing interface
and the migration and rearrangement of THF at the interface. At
temperature higher than the dissociation temperature of pure
THF hydrate, the presence of CH4 provides the necessary lattice
framework in order to stabilize the crystalline structure.
Therefore, the growth rate is dominated by the rate of CH4
accumulation at interface at high temperatures. At temperature
below the melting point of THF hydrate, the growth can proceed
without the aid of CH4. Under such circumstances, the growth
rate is dominated by the escape of THF from the incorrect sites
on the interface, which is also the dominating factor for the
growth of pure THF hydrate observed previously.34 The
different temperature dependence of these two phenomena
results in a competing effect. The adsorption of CH4 is enhanced
as the temperature is decreased, but the migration of THF is
enhanced with increasing temperature. As a result, the growth
rate of CH4 + THF hydrate exhibits a maximum value at around
290 K at 10 MPa.
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*
ASSOCIATED CONTENT
S Supporting Information
(11) Ogata, K.; Tsuda, T.; Amano, S.; Hashimoto, S.; Sugahara, T.;
Ohgaki, K. Hydrogen Storage in Trimethylamine Hydrate: Thermody-
namic Stability and Hydrogen Storage Capacity of Hydrogen Plus
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(13) Mooijer-van den Heuvel, M. M.; Peters, C. J.; de Swaan Arons, J.

■ AUTHOR INFORMATION
Corresponding Author
Influence of Water-Insoluble Organic Components on the Gas Hydrate
Equilibrium Conditions of Methane. Fluid Phase Equilib. 2000, 172, 73−
91.
(14) Chari, V. D.; Sharma, D. V. S. G. K.; Prasad, P. S. R. Methane
*E-mail stlin@ntu.edu.tw (S.-T.L.). Hydrate Phase Stability with Lower Mole Fractions of Tetrahydrofuran
Notes (Thf) and Tert-Butylamine (T-Bunh2). Fluid Phase Equilib. 2012, 315,
The authors declare no competing financial interest. 126−130.

■
(15) Strobel, T. A.; Koh, C. A.; Sloan, E. D. Thermodynamic
Predictions of Various Tetrahydrofuran and Hydrogen Clathrate
ACKNOWLEDGMENTS Hydrates. Fluid Phase Equilib. 2009, 280, 61−67.
The authors are grateful to the financial support of this research (16) Seo, Y. T.; Lee, H. C-13 Nmr Analysis and Gas Uptake
from the Ministry of Economic Affairs (103-5226904000-03-03) Measurements of Pure and Mixed Gas Hydrates: Development of
and the Ministry of Science and Technology (MOST 103-3113- Natural Gas Transport and Storage Method Using Gas Hydrate. Korean
M-002-006) of Taiwan. J. Chem. Eng. 2003, 20, 1085−1091.

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19890 DOI: 10.1021/acs.jpcc.5b05393

J. Phys. Chem. C 2015, 119, 19883−19890