J. Chem.

Thermodynamics 117 (2018) 2–8

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Hydrate phase equilibrium data of mixed methane-tetrahydrofuran

hydrates in saline water
Asheesh Kumar a, Sharanya Sharma Vedula a, Rajnish Kumar b, Praveen Linga a,⇑
a
Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 117 585, Singapore
b
Department of Chemical Engineering, Indian Institute of Technology Madras, India

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

Article history: Solidified natural gas (SNG) technology through clathrate hydrates formation has been considered a
Received 23 January 2017 viable opportunity for large scale stationary methane/NG storage application. In this work, we report
Received in revised form 8 May 2017 thermodynamic data on mixed methane (CH4)-tetrahydrofuran (THF) hydrates in pure water and in sal-
Accepted 9 May 2017
ine water. Hydrate phase equilibrium of mixed CH4-THF hydrates in presence/absence of NaCl (3.0 wt% or
Available online 13 May 2017
0.87 mol%) were determined employing a high-pressure micro-differential scanning calorimeter. The sto-
ichiometric amount of THF (5.56 mol%) was used in all the experiments which shifts the hydrate phase
Keywords:
equilibrium conditions toward milder region (lower pressure and high temperature). We report that
Gas hydrates
Calorimetry
the presence of 0.87 mol% NaCl has no significant effect on the equilibrium conditions of mixed CH4-
Phase equilibrium THF hydrates at low pressure (<1.2 MPa) for a temperature range of 285.9–290.5 K, however more devi-
Mixed hydrates ation in equilibrium curves occurs at higher pressure (>2.0 MPa). Clausius–Clapeyron plot for the exper-
Tetrahydrofuran imental results was employed to calculate the enthalpy of hydrate dissociation. The enthalpy of
sII hydrates dissociation of the mixed CH4-THF hydrates in presence of 0.87 mol% NaCl was found to be in the range
of 150–170 kJ/mol of gas.
Ó 2017 Elsevier Ltd.

1. Introduction
Natural gas is the best fossil fuel compared to coal and oil for
power generation and as a fuel, since it is the cleanest burning fos-
sil fuel. Recently, legislative measures to aid in the reduction of
carbon dioxide emissions from fossil fuel based power plants has
been proposed, which further encourage the use of natural gas
[1–4]. Moreover, the growing reliance on natural gas as a transition
fuel is evident from its high rate of consumption ranging up to
100 trillion ft3 in the production of industrial chemicals, trans-
portation, and for power generation [5,6]. Currently, about 23% of
the total natural gas production is traded globally [7]. The two
major modes of transport of natural gas are via pipelines or via liq-
uefied natural gas (LNG). LNG is the preferred and most economi-
cally feasible option for long distance transport in cases where
pipeline transport is not possible. Major countries that import nat-
ural gas like India, Singapore, South Korea, Japan etc in the form of
LNG would require the development of storage technologies for
long-term storage and for energy resilience. The climatic condi-
tions in these countries eliminate the use of LNG as a storage
option for long term storage.
⇑ Corresponding author.
E-mail address: Praveen.Linga@nus.edu.sg (P. Linga).
Another route that has recently been gaining attention for
large-scale natural gas storage is solidified natural gas (SNG) tech-
nology via clathrate hydrates [8,9]. Gas hydrates or clathrate
hydrates, are non-stoichiometric solid compounds formed by host
water molecules and small guest molecules like methane, ethane,
propane, tetrahydrofuran etc. [4,10,11]. Gas hydrates have been
extensively studied, and are deemed to be stable under conditions
of high pressure and low temperature [1,3,12]. The major limita-
tions of applying hydrate-based technology to natural gas storage
and transportation are (i) slow kinetics of hydrate formation, (ii)
severe operating conditions (high pressure and low temperatures)
required during the formation step, and (iii) loss of stability of
hydrates at ambient conditions. Recently, several kinetic promot-
ers and different materials have been utilized to enhance the
methane hydrate formation rate at milder operating conditions
[13–15]. In the recent literature, it has been reported that THF per-
forms both as a kinetic and thermodynamic promoter for methane
hydrate formation and improves the hydrate stability significantly
[9,16–18]. THF forms structure II (sII) hydrates on its own or when
utilized to form hydrates with smaller guest molecules like
methane [19–21]. The large cages are preferably occupied by
THF, while the smaller cages are occupied by methane, which facil-
itates greater hydrate stability at milder conditions [22].

http://dx.doi.org/10.1016/j.jct.2017.05.014
0021-9614/Ó 2017 Elsevier Ltd.
 A. Kumar et al. / J. Chem. Thermodynamics 117 (2018) 2–8
Thermodynamic data (hydrate phase equilibria) with varying
concentration of THF in methane hydrates has also been presented
in literature. Methane-THF hydrate equilibrium data for lower con-
centrations of THF relative to water, ranging from 0.48 mol% THF to
1.05 mol% THF have been presented by Mohmmadi et al. [21]. Seo
et al. have presented equilibrium data for methane and 3.0 mol%
THF solution [23]. De Deugd et al. have evaluated the phase equi-
librium conditions for methane and THF hydrates with composi-
tions containing 1.07 mol%, 5.0 mol% and 10.08 mol% THF relative
to water [24]. Zhang et al. have investigated the mixed hydrate
phase equilibrium containing 6 mol% THF in water for a lower
pressure range starting from 0.13 MPa to 1.22 MPa [25]. Lee et al.
have further presented the phase equilibrium data for mixed
methane and THF hydrates containing stoichiometric 5.56 mol%
concentration of THF for pressures ranging from 0.33 MPa to
12.5 MPa [19]. They concluded that there was no significant shift
in methane-THF phase equilibrium upon varying the concentration
of THF in water between 3.0 to 6.0 mol% values.
Further, to improve the economic feasibility of methane gas
storage and transportation process via clathrate hydrate formation,
it is important to substitute the pure water with seawater. The
major components of seawater are dissolved salts, particularly
sodium chloride (NaCl) [26], and hence, it is imperative to study
its effect on hydrate formation and stability. Addition of electrolyte
salts like MgCl2 and NaCl inhibits the hydrate formation and shifts
the methane hydrate phase equilibrium curve to high pressure and
low temperature regions [27,28]. Dholabhai et al. have presented
the phase equilibrium data for methane-water systems containing
3.0 wt% NaCl for lower pressures ranging from 2.7 to 4.8 MPa [29].
Lafond et al. have offered the phase equilibrium data for methane
hydrates formed in conjunction with water containing 3.5 wt%
NaCl for pressures ranging from 7.0 MPa to 20.0 MPa, and illus-
trated the shift in phase boundary towards higher pressure and
lower temperature conditions [30]. However, thermodynamic
phase equilibrium data for systems containing methane and THF
with NaCl in water concurrently is scarce. Recently, Mech and
Sangwai have presented equilibrium data for methane-THF
hydrates with low THF mass fractions of 0.005 and 0.010 in con-
junction with aqueous NaCl solutions containing 0.03, 0.05, 0.10
mass fractions of NaCl, over a pressure range of 2.17 to 6.43 MPa
[20]. They concluded that despite the inhibition provided by NaCl,
the synergistic effect of adding both THF and NaCl aids in shifting
the phase equilibrium to milder conditions, as compared to pure
methane equilibrium. However, no data is available in open litera-
ture illustrating the effect on methane hydrate formation of adding
stoichiometric 5.56 mol% THF and NaCl simultaneously.
In the present work, high-pressure micro-differential scanning
calorimetry (HP-l-DSC) was employed to obtain the hydrate phase
equilibria of mixed CH4-THF hydrates. DSC is an advanced technique
to measure the thermodynamic stability of gas hydrates [25,31–34].
In this study, heat flow change during hydrate formation and disso-
ciation process of mixed CH4-THF hydrates formed for a ternary
solution of THF/NaCl/water (5.52/0.87/93.61 mol%) & binary solu-
tion of THF/water (5.56/94.44 mol%) along with the hydrate dissoci-
ation temperature (equilibrium conditions at different pressure)
was monitored employing a HP l-DSC. Moreover, a Clausius-
Clapeyron plot [35] for the experimental results was plotted and
from the slope, the enthalpy of hydrate dissociation was measured.
2. Experimental section
2.1. Materials
All the materials employed, their supplier and purities are listed
in Table 1.
3
2.2. Apparatus
The schematic diagram of the experimental setup is presented
in the Fig. 1. A high-pressure micro-differential scanning calorime-
ter (HP l-DSC7 Evo, Setaram Inc.) was used in this study. The lDSC
has two cells, a sample and reference cell; each cell is enclosed by
high sensitivity peltier elements ensuring thermal contact with the
calorimetric wedge. The detectors used in DSC are good thermal
conductors that keep the temperature in the cells indistinguish-
able. The presence of two transducers in the sample and reference
cells respectively, eliminates variations in the data and provides
precise evaluating accuracy. The detailed description and principle
of calorimetry is given elsewhere in literature [36]. Briefly, the
highly sensitive HP l-DSC offers a temperature range from
45
up to 120 °C. The high-pressure cell is designed to work up to
40 MPa. A specific high-pressure gas panel is used in the setup to
pressurize the cell, which keeps the pressure constant inside the
cell. The HP l-DSC has a resolution of 0.02 lW, temperature devi-
ation of ±0.15 K and deviation in pressure measurement of
±0.05 MPa. An external refrigerator is provided to keep the cell
temperature constant.
2.3. Procedure
The detailed description of the experimental procedure is given
elsewhere in our previous publications [18,37]. The HP-lDSC
experiments were carried out for two systems, namely one that
contains water, methane and stoichiometric 5.56 mol% THF (In this
system, 5.56 mol% THF was added in the water) and the other sys-
tem contains 3.0 wt% NaCl in water, methane and stoichiometric
amount of THF. In this system, the calculated weight of NaCl
(3.0 wt% of water) was first added in water and mixed properly,
Now 5.56 mol% THF (based on the volume of water) was added
in the water-NaCl solution and mixed properly. The composition
of the ternary aqueous solution is 93.61 mol% Water, 5.52 mol%
THF and 0.87 mol% NaCl.
To outline the procedure briefly, 150 ml of the solution was
charged to the sample cell (Accuracy of m-pipette is ±0.05 ml).
Thereafter, the DSC cells were purged with the methane gas at
least three times to remove any residual air. The sample cell was
then pressurized with methane to a desired experimental pressure.
An isothermal temperature program was used in all the experi-
ments as this method provides clear information of hydrate nucle-
ation events as established in the literature [38]. As a part of this
method, the temperature was dropped rapidly from 298.2 K to
either 268.2 K or 258.2 K at the rate of 1.0 K/min and kept constant
at 268.2 K or 258.2 K for at least 1–2 h. The hydrate nucleation
events were observed as onset of exothermic peaks. After hydrate
Table 1
Materials used in this study.
Chemical Name Source Purity Analysis
method*
Methane gas Singapore Oxygen 99.9 (mol%) GCa
Air Liquid (SOXAL)
THFb Fisher Chemicals 99.99 (mass%) GCa
NaClc Sigma Aldrich 99.0 (mass%) Titration with
AgNO3
De-ionized Elga Micromeg – –
water Deionizer
Accuracy of m-pipette is ±0.05 ml and analytical balance ±0.0001 g.
a
Gas-liquid chromatography.
b
Tetrahydrofuran.
c
Sodium chloride.
*
Analysis done by supplier.
4 A. Kumar et al. / J. Chem. Thermodynamics 117 (2018) 2–8

3. Results and discussion

The DSC thermograms for the two different aqueous solutions

Fig. 1. Schematic of the experimental setup along with a high-pressure micro-
differential scanning calorimeter.
formation step, the temperature was gradually increased to 308 K
at the rate of 0.5 K/min to observe hydrate decomposition as onset
of endothermic peaks. The experiments for both systems were car-
ried out for pressures ranging from 0.3 MPa to 8.0 MPa.
studied in this work were obtained using the same procedure out-
lined in the experimental procedure section. For the ease of read-
ing, we will refer to binary aqueous solution of 5.56 mol% THF in
water as ‘‘THF/water (5.56/94.44 mol%) solution” and the ternary
aqueous solution consisting of THF and NaCl in water as ‘‘THF/
NaCl/water (5.52/0.87/93.61 mol%)” solution. Fig. 2A and B illus-
trate a typical thermogram indicating the temperature and heat
flow variation with time for a system containing ternary solution
of THF/NaCl/water (5.52/0.87/93.61 mol%) at 3.0 MPa pressure of
methane. Two experimental cycles for hydrate formation and dis-
sociation are shown. In the first cycle, the sample is cooled to
263.2 K at 1.0 K/min, while in the next cycle it is cooled to
258.2 K at 1.0 K/min. For both cycles, a sharp exothermic peak in
heat flow associated with hydrate formation occurred on cooling
the sample. After keeping the sample at the low temperature, the
temperature was gradually increased to 308.2 K at 0.5 K/min to
decompose the hydrates formed. Two endothermic peaks (along
with an exothermic spike) were observed which includes the ice
melting and mixed CH4-THF hydrate dissociation. The expansion
of Fig. 2A is presented in the inset figures a1 and a2 for hydrate for-
mation and dissociation respectively.
As can be seen in Fig. 2(a2), after the completion of ice melting,
an exothermic peak appears at 2.5 h, which could be attributed to
the mixed CH4-THF hydrate crystallization. Recently, Kumar et al.

Fig. 2. Typical DSC thermograms of mixed CH4-THF hydrates for the ternary solution of THF/NaCl/water (5.52/0.87/93.61 mol%) along with heat flow and temperature profile
for hydrate formation and dissociation. Where a temperature ramp programed from 303.2 K to 263.2 K at 1.0 K/min & 263.2 K to 308.2 K at 0.5 K/min (section A) and again
cooling from 308.2 K to 258.2 K then heating to 308.2 K at 0.5 K/min (section B) at 3.0 MPa pressure of methane. Figure a1 and a2 present the expansion of section (A) for
hydrate formation and dissociation respectively.
 A. Kumar et al. / J. Chem. Thermodynamics 117 (2018) 2–8 5

[18] reported that the endothermic peak of pure THF hydrates (sII
hydrates having empty small cages) occurs at 278 K and the similar
exothermic peak just after the melting of THF hydrates occurred.
Further, they reported that the endothermic peak that occurs at
299 K corresponds to the dissociation of mixed CH4-THF (sII)
hydrates. Based on Kumar et al. [18], observations, we can specu-
late that the broad ice peak in this system (Fig. 2a2) is a combina-
tion of ice and pure THF melting peaks [39]. Thus, it is vital to
justify this speculation of merged ice and THF hydrate melting
peaks; in this direction, we plot the comparison of hydrate dissoci-
ation thermograms of THF/NaCl/water (5.52/0.87/93.61 mol%) sys-
tem and THF/water (5.56/94.44 mol%) system at 3.0 and 5.0 MPa
pressure of methane. As can be seen in Fig. 3a and b, the ice melt-
ing peak in presence of salt is very broad compare to non-salt sys-
tem. Moreover, it is evident from the Fig. 3a that in the presence of
NaCl, the onset dissociation temperature of mixed CH4-THF
hydrates is lowered from 297.2 to 294.5 K. This illustrates its role
as a thermodynamic inhibitor.
It was found that both the ice melting and pure THF hydrate dis-
sociation peaks could be distinctly separated for the ternary sys- Fig. 4. Comparison of hydrate dissociation thermograms of mixed CH4-THF
tem of THF/NaCl/water (5.52/0.87/93.61 mol%) at lower pressure hydrates for ternary aqueous liquid solution of THF/NaCl/water (5.52/0.87/
(0.5 MPa). As shown in Fig. 3c, the ice melting peak is seen to occur 93.61 mol%) at various pressures of methane (7.0 MPa to 0.3 MPa).

at a temperature of 272.5 K, while the onset temperature for the

pure THF hydrate occurred at 278.5 K, which is in the good agree-
ment with the values reported by Kumar et al. [18]. to 7.0 MPa, methane) for ternary aqueous liquid solution of THF/
Fig. 4 presents the comparison of DSC thermograms for hydrate NaCl/water (5.52/0.87/93.61 mol%). The onset temperature of the
dissociation obtained at the experimental range of pressures (0.3 mixed CH4-THF hydrate dissociation peak is the characteristic of

Fig. 3. (a), (b) Comparison of hydrate dissociation thermograms of mixed CH4-THF hydrates for a ternary solution of THF/NaCl/water (5.52/0.87/93.61 mol%) and binary
solution of THF/water (5.56/94.44 mol%) at 3.0 MPa and 5.0 MPa pressure of methane. (c) Comparison of thermograms of mixed CH4-THF hydrates for ternary aqueous liquid
solution of THF/NaCl/water (5.52/0.87/93.61 mol%) at 6.0 MPa and 0.5 MPa pressure of methane.
6 A. Kumar et al. / J. Chem. Thermodynamics 117 (2018) 2–8

Table 2
Summary of the pressure and onset temperature data of the mixed CH4 -THF hydrates
for a ternary aqueous liquid solution of THF/NaCl/water (5.52/0.87/93.61 mol%)
system along with the enthalpy of dissociation (DHd) calculated using Clausius-
Clapeyron equation.

Sr No. Pressure Average Temperature DHd*

(MPa) (K) ± SD (kJ/mol)
1 7.17 298.7 ± 0.26 151.64
2 6.21 297.5 ± 0.14 154.36
3 4.87 295.7 ± 0.30 158.16
4 3.99 294.5 ± 0.67 160.66
5 3.04 294.0 ± 0.51 163.35
6 2.15 292.3 ± 0.21 165.88
7 1.20 290.5 ± 0.36 168.57
8 0.64 288.2 ± 0.60 170.16
9 0.25 285.9 ± 0.43 171.27

SD-Standard Deviation calculated using 3–4 data points.

The combined expanded uncertainties (Uc) are Uc (P) = ±0.031 MPa, Uc (T) = 0.73K
and Uc (DHd) = ±0.70 kJ/mol. Standard uncertainty in mass is U(w) = ±0.0001 g.
*
Variation in DHd value is due to change in compressibility factor (z, calculated
by Pitzer’s correlation) with respect to temperature/pressure [20].

Table 3
Summary of the pressure and onset temperature data of the mixed CH4-THF hydrates
for a binary aqueous liquid solution of THF/water (5.56/94.44 mol%) in absence of
NaCl along with the enthalpy of dissociation (DHd) calculated using Clausius-
Clapeyron equation.

Sr No. Pressure Average Temperature DHd*

(MPa) (K) ± SD (kJ/mol)
1 7.81 302.2 ± 0.06 135.42
2 6.92 301.9 137.64
3 6.65 301.6 138.31
4 6.24 300.7 139.33
5 5.24 300.1 141.82
6 5.08 300.2 142.22
7 5.04 299.9 142.32
8 4.08 298.6 ± 0.41 144.71
9 3.14 297.2 ± 0.34 147.06
10 3.00 296.8 147.41
11 1.94 294.7 ± 0.20 150.05
12 0.97 291.7 ± 0.39 152.46
13 0.33 288.4 154.06

SD-Standard Deviation calculated using 3–4 data points.

The combined expanded uncertainties (Uc) are Uc (P) = ±0.031 MPa, Uc (T) = 0.40 K
and Uc (DHd) = ±0.51 kJ/mol. Standard uncertainty in mass is U(w) = ±0.0001 g.
*
Variation in DHd value is due to change in compressibility factor (z, calculated
by Pitzer’s correlation) with respect to temperature/pressure [20].
the stability of the hydrate, which is found to decrease with a
decrease in pressure from 7.0 to 0.3 MPa (Fig. 4). Tables 2 and 3
summarizes the onset temperature at various pressure along with
the calculated heat of dissociation (kJ/mol) in presence and
absence of salt respectively. The repeatability of the experiments
have been presented in the Supplementary Fig. S1. Fig. S1 presents
the DSC thermograms of mixed CH4-THF hydrates for a ternary
aqueous liquid solution of THF/NaCl/water (5.52/0.87/93.61 mol
%) along with heat flow and temperature profile. Fig. S1
illustrations the hydrate formation and decomposition using a
temperature ramping program, cooling from 308.2 K to 258.2 K
at 1.0 K/min and heating to 308.2 K at 0.5 K/min at 7.15 MPa pres-
sure of methane (Fig. S1a). Pressure is almost constant throughout
the experiment (Fig. S1b). Fig. S1c shows the change in heat flow
with respect to temperature and Fig. S1d presents the comparison
of dissociation peak of mixed CH4-THF hydrates for four experi-
mental runs.
The phase equilibrium plot obtained for the binary THF/water
system under this study containing 5.56 mol% stoichiometric THF
Fig. 5. (a) Thermodynamic phase equilibrium plots for systems with methane and
THF in water: CH4 + 5.56 mol% THF (this work, average value); CH4 + 5.56 mol% THF
[19]; CH4 + 5.0 mol% THF [24]; CH4 + 10.08 mol% THF [24]; CH4 + 3.0 mol% THF [23]
and pure methane hydrate equilibrium [40]. (b) Thermodynamic phase equilibrium
plots for systems with methane and mixed CH4-THF hydrates with and without
NaCl: CH4 + THF/water (5.56/94.44 mol%)[this work, average value]; mixed CH4/
THF hydrates for ternary aqueous liquid solution of THF/NaCl/water (5.52/0.87/
93.61 mol%) [this work]; CH4 + NaCl/water(0.92/99.08 mol%) [29].
in water with methane is shown in Fig. 5a and the corresponding
data has been summarized in Table 3. Equilibrium data from liter-
ature for similar systems containing 5.0 mol% THF [24], 5.56 mol%
THF [19], and for higher THF concentration (10.08 mol% THF) [24]
in water have also been plotted along with our data. As can be seen
from Fig. 5a, our experimental data (obtain from DSC thermo-
grams) is in the good agreement with the literature values. Upon
comparison with pure methane hydrate equilibrium data [40], it
can be seen that the addition of stoichiometric (5.56 mol%) THF
shifts the hydrate stability region to milder conditions of low pres-
sure and high temperature. Lee et al. [19] have previously illus-
trated that a lower concentration of THF (in the range of 1 to
1.5 mol%) can also considerably shift the equilibrium conditions
to lower pressure and higher temperature. However, with stoichio-
 A. Kumar et al. / J. Chem. Thermodynamics 117 (2018) 2–8
metric concentration the rate of hydrate formation was found to be
significantly high compared to low THF concentration, which has
been presented in our previous publications [9,16]. Moreover, as
can be seen in Fig. 5a, the increase in thermodynamic promotion
provided by THF becomes insignificant in the range of 3.0 to
10.08 mol% THF.
Fig. 5b presents the phase equilibrium data obtained for a ternary
aqueous liquid solution of THF/NaCl/water (5.52/0.87/93.61 mol%)
system and its comparison of non-salt system. The corresponding
data of this ternary aqueous liquid solution has been summarized
in Table 2. Fig. 5b also compares the phase equilibrium data for a bin-
ary aqueous solution of NaCl/water (0.92/99.08 mol% or 3.0/97.0 wt
% [29]). It is evident that NaCl acts as a thermodynamic inhibitor. It
shifts the equilibrium curve to conditions of higher pressure and
lower temperature but the thermodynamic shift is not very signifi-
cant. Mech and Sangwai [20] presented equilibrium data for systems
containing a mixture of NaCl (3.0, 5.0 and 10.0 wt%) and low concen-
tration of THF (0.5 and 1.0 mol%). They concluded that the shift in the
equilibrium curve in presence of NaCl was not significant. From
Fig. 5b, it is evident that ternary aqueous liquid solution of THF/
NaCl/water (5.52/0.87/93.61 mol%) system shows a cumulative
promotion effect and shifts the equilibrium curve to milder condi-
tions compared to binary aqueous solution of NaCl/water
(0.92/99.08 mol%) equilibrium conditions. Moreover, there is no
significant shift in the equilibrium curves of salt and non-salt sys-
tems in presence of THF. The presence of NaCl has no significant
effect on the equilibrium conditions of mixed CH4-THF hydrates at
low pressure (<1.2 MPa) for a temperature range of 285.9 to
290.5 K, however more deviation in equilibrium curves occurs at
higher pressure (>2.0 MPa), the shift in temperature was found to
be in the range of 2–3 K.
The Clausius-Clapeyron equation was employed to calculate the
enthalpy of dissociation [35]. Plots of the logarithm of the experi-
mental pressure against the reciprocal of the hydrate dissociation
temperature has been presented in Supplementary Information
(Fig. S2). The enthalpies of dissociation was calculated using the
Clausius
Clapeyron equation presented as below.
dðlnPÞ DH d

¼

d 1T zR
where P and T are the absolute pressure and temperature of hydrate
equilibrium, R is the universal gas constant, and z is the gas com-
pressibility factor calculated by Pitzer’s correlation. Based on the
slopes, the enthalpy of dissociation of mixed CH4-THF hydrates in
presence NaCl was found to be in a range of 150–170 kJ/mol of
gas however in absence of NaCl, it is slightly lower (135–154 kJ/mol
of gas). The calculated data of enthalpies of dissociation has been
presented in Tables 2 and 3 in presence and absence of salt respec-
tively. Hence, we can infer that the mixed hydrate formed structure
II (sII) hydrates. However, the structure needs to be confirmed by X-
ray diffraction (XRD) measurements. Further, a detailed study of
hydrate formation kinetics for such a ternary aqueous liquid solu-
tion of THF/NaCl/water (5.52/0.87/93.61 mol%) system and molecu-
lar level studies on the formed mixed hydrates are currently being
carried out to understand the cage occupancy of THF and methane
in the hydrate phase.
4. Conclusion
Hydrate phase equilibrium of mixed CH4-THF hydrates in pres-
ence/absence of NaCl were determined employing a high pressure
micro-differential scanning calorimeter. From the experimental
results, we conclude that NaCl has negligible effect on the equilib-
rium conditions of mixed CH4-THF hydrates at low pressure;
7
however, more deviation occurs at higher pressure. Moreover,
the enthalpy of hydrate dissociation was calculated using Clau-
sius–Clapeyron equation, which confirms the structure II (sII)
hydrate domain for mixed CH4-THF hydrates. Thus, we can con-
clude that mixed CH4-THF hydrates are very stable even in pres-
ence of salt, which provides a great opportunity to utilize
seawater as a feed solution for solidified natural gas technology
via clathrate hydrate for energy storage.
Acknowledgments
The work was funded in part under the Energy Innovation
Research Programme (EIRP, Award No. NRF2015EWTEIRP002-
002), administrated by the Energy Market Authority (EMA) and
funded by the National Research Foundation (NRF), Singapore.
The authors also acknowledge the support from the National
University of Singapore (R-261-508-001-646/733) for the DSC
equipment.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jct.2017.05.014.
References
[1] Z.R. Chong, S.H.B. Yang, P. Babu, P. Linga, X.-S. Li, Appl. Energy 162 (2016)
1633–1652.
[2] A. Bahadori, Liquefied Natural Gas (LNG), Gulf Professional Publishing, Boston,
Natural Gas Processing, 2014, pp. 591–632 (Chapter 13).
[3] E.D. Sloan, Nature 426 (2003) 353–363.
[4] E.D. Sloan, C.A. Koh, Clathrate Hydrates of Natural Gases, CRC Press, 2007.
[5] F.-Y. Liang, M. Ryvak, S. Sayeed, N. Zhao, Chem. Cent. J. 6 (2012) S4.
[6] R.W. Baker, K. Lokhandwala, Ind. Eng. Chem. Res. 47 (2008) 2109–2121.
[7] C. Giavarini, F. Maccioni, Ind. Eng. Chem. Res. 43 (2004) 6616–6621.
[8] J.S. Gudmundsson, Method for production of gas hydrates for transportation
and storage, Google Patents, 1996.
[9] H.P. Veluswamy, A.J.H. Wong, P. Babu, R. Kumar, S. Kulprathipanja, P.
Rangsunvigit, P. Linga, Chem. Eng. J. 290 (2016) 161–173.
[10] P. Englezos, Ind. Eng. Chem. Res. 32 (1993) 1251–1274.
[11] D.W. Davidson, Clathrate Hydrates, Water: A Comprehensive Treatise, Plenum
press, New York, 1973.
[12] J. Javanmardi, K. Nasrifar, S.H. Najibi, M. Moshfeghian, Appl. Therm. Eng. 25
(2005) 1708–1723.
[13] A. Kumar, G. Bhattacharjee, B.D. Kulkarni, R. Kumar, Ind. Eng. Chem. Res. 54
(2015) 12217–12232.
[14] P. Linga, M.A. Clarke, Energy Fuels 31 (2017) 1–13.
[15] A. Kumar, T. Sakpal, R. Kumar, Energy Technol. 3 (2015) 717–725.
[16] A. Kumar, O.S. Kushwaha, P. Rangsunvigit, P. Linga, R. Kumar, Can. J. Chem.
Eng. 94 (2016) 2160–2167.
[17] H.P. Veluswamy, S. Kumar, R. Kumar, P. Rangsunvigit, P. Linga, Fuel 182 (2016)
907–919.
[18] A. Kumar, N. Daraboina, R. Kumar, P. Linga, J. Phys. Chem. C (2016).
[19] Y.-J. Lee, T. Kawamura, Y. Yamamoto, J.-H. Yoon, J. Chem. Eng. Data 57 (2012)
3543–3548.
[20] D. Mech, J.S. Sangwai, J. Chem. Eng. Data 59 (2014) 3932–3937.
[21] A.H. Mohammadi, D. Richon, Ind. Eng. Chem. Res. 48 (2009) 7838–7841.
[22] P. Linga, R. Kumar, P. Englezos, Chem. Eng. Sci. 62 (2007) 4268–4276.
[23] Y.T. Seo, S.P. Kang, H. Lee, Fluid Phase Equilib. 189 (2001) 99–110.
[24] R.M. de Deugd, M.D. Jager, J. de Swaan, Arons, AlChE J. 47 (2001) 693–704.
[25] Y. Zhang, P.G. Debenedetti, R.K. Prud’homm, B.A. Pethica, J. Phys. Chem. B 108
(2004) 16717–16722.
[26] N.O.S. <http://oceanservice.noaa.gov/facts/whysalty.html>.
[27] K.K. Godishala, J.S. Sangwai, N.A. Sami, K. Das, J. Chem. Eng. Data 58 (2013)
1062–1067.
[28] N.A. Sami, K. Das, J.S. Sangwai, N. Balasubramanian, J. Chem. Thermodyn. 65
(2013) 198–203.
[29] P.D. Dholabhai, P. Englezos, N. Kalogerakis, P.R. Bishnoi, Can. J. Chem. Eng. 69
(1991) 800–805.
[30] P.G. Lafond, K.A. Olcott, E. Dendy Sloan, C.A. Koh, A.K. Sum, J. Chem.
Thermodyn. 48 (2012) 1–6.
[31] S.R. Davies, K.C. Hester, J.W. Lachance, C.A. Koh, E. Dendy, Sloan, Chem. Eng.
Sci. 64 (2009) 370–375.
[32] M. Kharrat, D. Dalmazzone, J. Chem. Thermodyn. 35 (2003) 1489–1505.
[33] G. Li, D. Liu, Y. Xie, J. Therm. Anal. Calorim. 102 (2010) 819–826.
[34] R. Susilo, J.A. Ripmeester, P. Englezos, Chem. Eng. Sci. 62 (2007) 3930–3939.
8 A. Kumar et al. / J. Chem. Thermodynamics 117 (2018) 2–8

[35] E.D. Sloan, F. Fleyfel, Fluid Phase Equilib. 76 (1992) 123–140. [39] A. Delahaye, L. Fournaison, S. Marinhas, I. Chatti, J.-P. Petitet, D. Dalmazzone,
[36] P. Le Parlouër, C. Dalmazzone, B. Herzhaft, L. Rousseau, C. Mathonat, J. Therm. W. Fürst, Ind. Eng. Chem. Res. 45 (2006) 391–397.
Anal. Calorim. 78 (2004) 165–172. [40] S. Adisasmito, R.J. Frank, E.D. Sloan, J. Chem. Eng. Data 36 (1991) 68–71.
[37] H.P. Veluswamy, A. Kumar, R. Kumar, P. Linga, Appl. Energy 188 (2017) 190–
199.
[38] N. Daraboina, J. Ripmeester, V.K. Walker, P. Englezos, Energy Fuels 25 (2011)
4392–4397. JCT 17-69