Journal of Unconventional Oil and Gas Resources 6 (2014) 54–59

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Journal of Unconventional Oil and Gas Resources

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Regular Articles

Kinetics of methane hydrate formation and its dissociation in presence

of non-ionic surfactant Tergitol
Vikash Kumar Saw b,⇑, Manojkumar Gudala a, G. Udayabhanu b, Ajay Mandal a, Sukumar Laik a
a
Gas Hydrate Laboratory, Department of Petroleum Engineering, Indian School of Mines, Dhanbad 82600, India
b
Department of Applied Chemistry, Indian School of Mines, Dhanbad 82600, India

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

Article history: The kinetics of methane hydrate formation and its dissociation has been studied in presence of a nonionic
Received 10 May 2013 surfactant Tergitol. Experiments were performed with 0 ppt, 1 ppt, 5 ppt, and 10 ppt of Tergitol in water.
Accepted 10 July 2013 The experimental results show that a certain degree of subcooilng is required to initiate hydrate forma-
Available online 13 September 2013
tion. Phase equilibrium pressure and temperature has been investigated extensively. It is observed that
the phase equilibrium curves of methane hydrate are not affected on varying the concentration of
Keywords: Tergitol. It is found that the rate of hydrate formation varies with concentration of Tergitol. The kinetic
Methane hydrate
rate constant is also found to vary with concentration of Tergitol during growth of hydrate. Induction
Induction time
Tergitol
time of hydrate formation has also been studied under different experimental conditions. The gas con-
Surfactant sumption is computed using real gas equation and it is found that 10 ppt Tergitol resulted in highest con-
Formation and dissociation sumption of gas.
Ó 2013 Elsevier Ltd. All rights reserved.

Introduction
In recent years gas hydrates have received much attention as a
new natural resource of hydrocarbon that is unexploited. Clathrate
hydrates are one type of inclusion compounds and hydrates are
crystalline compounds in which small molecules are entrapped
in a polyhedral framework composed of hydrogen-bonded water
molecules. Gas hydrates form when water and hydrate forming
gas comes in contact under high pressure and low temperature
conditions (Collett, 2002; Sloan and Koh, 2008). Recently signifi-
cant studies have been reported on storage and transportation of
natural gas in the form of hydrate. One volume of hydrates can
encage about 150 to 180 volumes of gas at STP if all of the cavities
are singly occupied. Natural gas storage is not yet commercialized
due to slow formation rate and the presence of water that does not
react with methane gas. The reason for this is the low solubility of
methane gas in water resulting in only a thin film of hydrate form-
ing at the interface. Some specific surfactants are found to increase
gas hydrate formation rate and alter formation mechanism for nat-
ural gas hydrates (Ganji et al., 2007a,b; Kalogerakis et al., 1993;
Zhong and Rogers, 2000; Sun et al., 2003; Mandal and Laik, 2008;
Zhang et al., 2007; Karaaslan et al., 2002; Karaaslan and Parlaktuna,
2000; Kwon et al., 2011; Fan et al., 2012; Fakharian et al., 2012).
Not only fast formation rate and gas consumption in hydrate are
important in commercializing their use in storage and transporta-
⇑ Corresponding author. Tel.: +91 9470186566
E-mail address: v_iitg@yahoo.com (V.K. Saw).
tion, but also the hydrate stability is vital for long distance trans-
portation and long period of storage. Surfactants have a
spontaneous catalyzing effect on hydrate formation and accumula-
tion. The phenomenon may be utilized to develop an economical
process for storing natural gas or methane gas in hydrate state
for industrial applications such as to transport the gas for long dis-
tances. Kalogerakis et al. (1993) studied the effect of anionic and
nonionic surfactants in a stirred cell. Methane hydrate formation
rate has been found to increase with concentration of anionic sur-
factant (SDS). Zhong and Rogers (Zhong and Rogers, 2000) studied
the effect of SDS on the hydrate formation mechanism using eth-
ane and natural gas as guest molecules. They suggest that micelles
act as nucleation point with increasing the solubility of hydrocar-
bon gas in the aqueous phase and by inducing the formation of
hydrate crystals around the micelle in the bulk water phase below
the gas/water interface. Ganji et al. (2007a,b) studied the effect of
different surfactants on methane hydrate formation rate, stability
and storage capacity. In their study, formation and dissociation
rates and storage capacities of the hydrates formed in presence
of 3 classes of surfactants (anionic, cationic and non-ionic) have
been studied. Mandal and Laik (2008) showed that micellar
surfactant solutions increase the gas hydrate formation rate and
storage capacity. According to this research, an anionic surfactant,
a nonionic surfactant, their mixtures and cyclopentane were used
to improve the hydrate formation of a synthetic natural gas and
their effects on hydrate formation was carefully compared. Mandal
and Laik (Zhang et al., 2007) studied effects of the anionic surfac-

2213-3976/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.juogr.2013.07.001
 V.K. Saw et al. / Journal of Unconventional Oil and Gas Resources 6 (2014) 54–59
tant such as SDS on ethane hydrate formation, dissociation and
storage capacity in a static system.
The objective of the present work is to study the kinetics of
methane hydrate formation and to observe the formation condi-
tion of temperature and pressure in different concentrations of
Tergitol. Dissociation of hydrate has also been investigated to
observe the effects of Tergitol on phase equilibrium of methane
hydrate.
Experimental
Apparatus
The gas hydrate auto clave equipment used in the present study
is designed by Vinci Technology, France. The schematic of experi-
mental set up is shown in Fig. 1. It measures the induction time
of hydrate formation and monitors the pressure drop during hy-
drate formation. The video hydrate cell has a capacity of 250 cm3
and with pressure rating up to 20.7 MPa. The cell temperature is
controlled by a programmable thermostatic bath with a thermo-
couple which measures the temperature of the cell with an
accuracy of 0.1 °C. The cell pressure is monitored by a pressure
transducer. A computer is used for data acquisition of temperature,
pressure and time. The cell is also equipped with in built video
camera that continuously records the pictures of the system during
the different stages of hydrate formation. It has been found that the
conditions of hydrate formation as confirmed with visual observa-
tion are reasonably matched with the recorded pressure and tem-
perature data.
Materials
All the experiments were performed with 99.99% pure methane
(collected from Chemtron Science Laboratory, Navi Mumbai, India)
and reverse osmosis water from Millipore water system (Millipore
SA, 67120 Molshein, France). Tergitol 15-S-12 is procured from Sig-
ma–Aldrich Chemicals Pvt. Ltd., Germany.
Procedure
The required amount (130 cc) of Tergitol solution was poured
into the autoclave cell. Air in cell was removed by evacuating the
cell using a vacuum pump. Gas Booster is used to build up high
pressure inside the hydrate cell. Methane gas was injected into
Fig. 1. Schematic flow diagram of Gas hydrate auto clave apparatus.
55
the hydrate forming cell up to the desired pressure (11.60 MPa).
Initial temperature and pressure of each test were set at 293.62 K
and 11.60 MPa, respectively. The magnetic stirrer with speed of
1000 RPM is then turned onto agitate the mixture within the cell.
The stirring rate (Carroll, 2002) is an important parameter that
has an effect on the kinetics of hydrate formation. Hydrate forma-
tion is favored in regions where the fluid velocity is high. The dis-
solution of gas in water increases with increase in turbulence of
the system. The rate of formation (Hussain et al., 2006) is also af-
fected with increase in stirring speed or turbulence of the system.
As the present work emphasizes the effect of surfactant on hydrate
formation and dissociation, a constant RPM (1000) was maintained
throughout the experiments. The temperature of the system was
decreased slowly step wise at the rate of 1 K/h. Hydrate formation
was detected by observing a sudden sharp drop in pressure and
through video picture. Temperature of the system was kept con-
stant when sudden pressure drop was observed. Then temperature
was further decreased slowly to 271.15 K to observe pressure drop
due to growth of hydrate. At 271.15 K, no significant pressure drop
was observed indicating the completion of hydrate formation of
hydrate. The system is allowed to remain at the same temperature
for 6 h to attain a state of equilibrium. To observe the dissociation
of hydrate, the temperature of the system is increased slowly, step
wise at the rate of 1 K/h and kept at the same temperature for 2–
3 h to equilibrate the system. Dissociation of the hydrate was iden-
tified when the pressure of the system increased substantially.
Results and discussions
Methane hydrate formation and dissociation
The formation and dissociation behavior of pure methane hy-
drate is shown in Fig. 2. Pure methane hydrate is prepared with
99.99% pure methane and distilled water. Methane and water are
brought in contact at low temperature and high pressure to form
hydrate.
Hydrate formation should start at point ‘‘A’’ without metastabil-
ity (Fig. 2). However the pressure of the system continues to
decrease for a number of hours without hydrate formation. This
is due to dissolution of gas. This period ends when the gas
saturates the liquid. Thus the concentration of gas in liquid in-
creases and becomes super-saturated leading to clustering of
water molecules around gas molecules with sudden drop in
pressure at constant temperature (284.38 K). The sharp drop in
11
Formation Cooling
Subcooling
Dissociation
10
Hydrate Nucleation (B)
Equilibrium point (A)
9
Growth
Pressure (MPa)
7
Start Dissociation (D)
6
Heating (C)
280 281 282 283 284 285 286 287 288 289
Temperature(K)
Fig. 2. Temperature–pressure trace of methane hydrate formation and dissociation
in distilled water.
56 V.K. Saw et al. / Journal of Unconventional Oil and Gas Resources 6 (2014) 54–59

pressure at a particular temperature is due to hydrate nucleation Table 1

(at point ‘‘B’’ of Fig. 2) with appearance of turbidity in liquid phase Formation and dissociation parameters of methane hydrate in presence of Tergitol in
water.
and subsequent growth of hydrates. A sharp discontinuity is ob-
served in the formation curve due to encapsulation of gas in the Test Onset Dissociation Equilibrium Subcooling
cage of water molecules, with a slight rise in the solution temper- sample temp (K) temp (Teq) DT sub ¼ T eq  T 0 ðKÞ
Temp Pressure
(Tergitol) (K)
ature due to the heat release during the stable hydrate formation. (K) (MPa)
It is observed that hydrate formation does not take place in a single 0.0 ppt 284.38 10.13 281.46 287.75 3.37
stage but in multiple stages. Our interest in the present study is to 1 ppt 283.66 10.88 276.55 289.25 5.59
investigate the effect of nonionic surfactant on methane hydrate 5 ppt 285.64 11.0 276.89 289.23 3.59
10 ppt 283.75 10.85 276.15 288.36 4.92
formation and dissociation. Therefore different concentrations of
Tergitol in water are used to observe the influence on methane hy-
drate formation and dissociation. Fig. 2 shows the pressure–tem-
perature profile during the process of methane formation and The phase equilibrium of methane hydrate in presence of differ-
dissociation in presence of 1 ppt Tergitol. ent concentration of Tergitol is shown in Fig. 4. The phase equilib-
The pressure of the system is decreased with temperature upon rium curves are shifted to high temperature region on addition of
cooling and dissolution of gas in surfactant solution before hydrate Tergitol in water while there is no shift of phase equilibrium curve
nucleation. A sharp drop in pressure is observed at 283.66 K due to on variation in the concentration of Tergitol. This suggests that
nucleation of hydrate followed by rise in system temperature. The Tergitol thermodynamically promote hydrate formation.
spike in temperature during nucleation is on account of exother-
mic nature of hydrate crystallization. Pressure continues to de- Gas consumption
crease with temperature during growth of hydrate. After
complete formation the temperature of the system is increased The number of moles (n) of methane consumed is determined
to 276.55 K, a substantial rise in pressure was observed indicating by the real gas Eq. (1):
hydrate dissociation (Fig. 3). The thermodynamic parameters of  
V Pi Pf
hydrate formation and dissociation are noticeably affected upon Dn ¼  ð1Þ
R Zi T i Zf T f
the variation in concentration of Tergitol. When the concentration
of Tergitol increased from 1 ppt to 5 ppt, the nucleation tempera- where V is gas volume R is universal gas constant, P, T are pressure
ture and pressure of hydrate formation is shifted to higher values and temperatures respectively and Z is gas compressibility factor.
and also less subcooling is needed to initiate hydrate formation. Compressibility factor (Z) is calculated by Peng–Robinson equation
Hydrate formation and dissociation is further investigated with in- of state. Subscript ‘i’ indicates initial and ‘f’ indicates final states.
crease in concentration of Tergitol up to 10 ppt. It is observed that Fig. 5 shows gas consumption and pressure drop as a function of
the nucleation temperature and pressure of hydrate formation is time. The growth and gas consumption region shows two symmet-
decreased to lower values compared to that of system having ric plots that could be interpreted as conservation of mass during
5 ppt surfactant but it is relatively high for the system having the hydrate growth. The mass conservation take place only when
1 ppt Tergitol. The pressure drop of hydrate formation is also influ- the water in the liquid state is saturated with methane gas at the
enced on the variation of concentration of Tergitol. High concentra- desired temperature prior to time zero as shown in Fig. 5. Number
tion of Tergitol resulted in more pressure drop compared to the of methane molecules leaving the gas phase to hydrate phase is
system having lower concentration of Tergitol. It is can also be no- represented by the pressure drop, whereas the number of methane
ticed that the hydrate begins to dissociate just above the freezing molecules entering in the hydrate cages is represented by the gas
point of ice in presence of Tergitol while hydrate dissociate far consumption plot. Since mass must be conserved in an isochoric
above the ice point in absence of Tergitol. These results suggest system, the two plots shows symmetry about an axis passing
that the presence of Tergitol promote hydrate formation while through the intersection of the two plots and parallel to the time
the stability of hydrate is decreased (Table 1). axis. As shown in this Fig. 5, the process is divided into three re-
gions. First region is started at time zero where the system has less
consumption of gas and pressure slightly decreases due to dissolu-
tion of gas. Second region is after the induction time where gas
Start Cooling
12 g
Hydrate Onset Sub coolin
12 0.0ppt Tergitol
1ppt Tergitol
10
Equilibrium 5ppt Tergitol
rop
e

point 10ppt Tergitol

T ris

10
Pr d
Pressure (MPa)

8
Pressure (MPa)

Formation 8

6
Dissociation

Heating Dissociation start 4

2
270 275 280 285 290 295
Temperature (K) 280 285 290 295
Temperature(K)
Fig. 3. Temperature- pressure trace of methane hydrate formation in presence of
1 ppt Tergitol. Fig. 4. Phase equilibrium of methane hydrate in presence of Tergitol.
 V.K. Saw et al. / Journal of Unconventional Oil and Gas Resources 6 (2014) 54–59 57

0.35 12 12

Onset Pressure 290

0.30 11 11
Moles of methane gas consumed

0.25
gas consumption 10 288
10
pressure

growth region
0.20

Pressure (MPa)

Pressure (MPa)

Temperature (K)
Region 3
9
Region 1

9 Induction
0.15 286
Time
8
0.10 8
7 284
0.05
7
Region 2
6
0.00
282
6 Onset Temperature
-0.05 5
-50 0 50 100 150 200 250 300 350
-50 0 50 100 150 200 250 300 350
Time (Min)
Time (min)
Fig. 5. Gas consumption and reactor pressure vs time in presence of 10 ppt of
Fig. 7. Pressure and temperature with respect to time during kinetic experiment in
Tergitol.
presence of 10 ppt Tergitol.

consumption increases, this is due to the hydrate growth. In the temperature during measurement of induction time is shown in
third region, since the hydrate is formed, the free gas content Fig. 7. The pressure of the system decreases with temperature be-
reduction or consumption of gas disappears. fore hydrate formation. It is observed that at constant temperature
Except the gas consumption rate in pure water, which is appar- there is still fall in pressure followed by sudden rise in tempera-
ently slow, all other set of experiments, have spontaneous and fast ture, which indicates hydrate formation. The difference of hydrate
rate of gas consumption. It is observed that the rate of gas onset time and the time of start of experiment is the induction
consumption increases monotonically with increase in the time of hydrate formation (Fig. 7).
concentration of Tergitol. 10 ppt Tergitol resulted in the highest The measured induction time of hydrate formation in presence
consumption of gas during hydrate formation (Fig. 6). of different concentration of Tergitol in water is given in Table 2. It
is noticed that the induction time of hydrate formation is reduced
on adding Tergitol in water. The induction is reduced when hydrate
Effect of Tergitol on induction time of hydrate formation formation is carried out in presence of 1 ppt Tergitol in water. Also
it is observed that induction time increases with increase in
Volmer (1939) defined the induction time as the period neces-
sary for the appearance of the very first hydrate crystal. The induc-
tion time/period is a measure of the ability of a supersaturated Table 2
system to remain in the state of metastable equilibrium and has Induction time of hydrate formation.
the physical significance of the system’s lifetime in this state Test sample (Tergitol) Subcooling (°C) Induction time (min)
(Kashchiev et al., 1991; Kashchiev, 2000). The induction time of hy-
0.0 ppt 3.37 161
drate formation is measured in presence of different concentration 1 ppt 5.59 20
of Tergitol in water. To measure induction time in this study, the 5 ppt 3.59 71
process sample is adjusted to the temperature and pressure where 10 ppt 4.92 100
hydrate is completely dissociated (i.e. dissociation point) and then
allowed the system to form hydrate. The variation of pressure and
Zone 2

Zone 3
Zone 1

0.35
1.0
0ppt
0.30 1ppt
5ppt 0.9
Moles of methane gas consumed

10ppt
0.25
Region 1

0.8
Region 3

0.20
Region 2
N/N0

0.15 0.7

0.10
0.6

0.05
0.5
0.00

-50 0 50 100 150 200 250

0 50 100 150 200 250 300
Time (min)
Time (Min)
Fig. 8. Change of moles of methane during hydrate formation in presence of 10 ppt
Fig. 6. Rate of gas consumption during hydrate formation. Tergitol.
58 V.K. Saw et al. / Journal of Unconventional Oil and Gas Resources 6 (2014) 54–59

0.00 -0.33

-0.05 -0.36

-0.10 -0.39

ln(N/No)
-0.15

ln(N/No)
-0.42
-0.20
-0.45
-0.25
-0.48
-0.30
-0.51
-0.35
-0.54
0 10 20 30 40 50 50 60 70 80 90 100 110
Time (min) Time (min)

-0.52

-0.54
ln(N/No)

-0.56

-0.58

-0.60

-0.62

100 110 120 130 140 150 160

Time (min)

Fig. 9. Semi-logarithmic plot of change of moles of gas during hydrate formation in presence of 10 ppt Tergitol.

concentration of Tergitol from 1 ppt to 10 ppt but less than that in
water.
Kinetics of methane hydrate formation
As observed, the slope of the curves after nucleation exhibits an
exponential behavior (Fig. 8) from which a first-order reaction can
be assumed. A first order reaction is defined by the following Eqs.
(2) and (3).
N ¼ N0 ekt
N is fast which decreases exponentially with time. Hydrate formation
ln ¼ kt
N0
where N is total number of moles at time t, N0 is initial number of
moles, k is rate constant (min1) and t is time in min. The slope
of the curve of ln(N/N0) vs t gives the rate constant (k) of hydrate
formation. The hydrate formation in region 2 (Fig. 5) was divided
into three zones of time as shown in Fig. 8 (0–50, 50–100 and
100–150 min) after nucleation. This may be due to different rate
of hydrate formation which give different reaction rate and hence
different rate constant. The data of three zones are used to estimate
the rate constant of hydrate formation (Fig. 8 and 9). The formation
rate is usually expressed through the rate by which the amount of
methane molecule is converted to hydrate (Hussain et al., 2006).
Hydrate formation rate is expressed by the following expression:
dN kt
¼ N0 ke ð4Þ
dt
The rate of hydrate formation is different in all the three zones
ð2Þ of time. Initially (0–50 min after nucleation) the rate of formation
ð3Þ rate is increased initially (0–50 min) 156 times more in presence of
1 ppt Tergitol compared to hydrate formation rate in pure water
(Table 3). It is also noticed that the rate of hydrate formation varies
with concentration of Tergitol. When the concentration of Tergitol
0.006
1ppt
Methane hydrate formation rate (mol/min)

5ppt
0.005 10ppt
Table 3
Methane hydrate formation rates with Tergitol. 0.004
Test sample Time zone Rate constant, k Formation rate
(Tergitol) (min) (min1) (mol/min)
0.003
0.0 ppt 0–50 3.9077E04 2.4097E05
50–100 2.1002E04 8.80059E06
100–150 8.7949E04 1.5433E06 0.002

1 ppt 0–50 4.04E03 3.51E03

50–100 2.42E03 1.93E03
0.001
100–150 1.47E03 1.12E03
5 ppt 0–50 4.42E03 3.74E03
50–100 2.59E03 2.02E03 0.000
100–150 2.00E03 1.51E03 0-50 50-100 100-150

10 ppt 0–50 6.40E03 6.03E03 Time zone (min)

50–100 3.43E03 2.78E03
100–150 1.87E03 1.40E03 Fig. 10. Comparison of hydrate formation rates in presence of different concentra-
tion of Tergitol.
 V.K. Saw et al. / Journal of Unconventional Oil and Gas Resources 6 (2014) 54–59
increases from 1 ppt to 5 ppt the hydrate formation rate increases
in all the three different zones of time and the further increase in
concentration of Tergitol from 5 ppt to 10 ppt, the rate of hydrate
formation is increased drastically in zone 1 and 2, while it is
slightly low in zone 3 (Fig. 10).
Conclusions
The kinetics of methane hydrate formation and its dissociation
has been discussed. Hydrate formation rate is greatly increased by
addition of Tergitol in water. It is more pronounced when the con-
centration of Tergitol is increased to 10 ppt. Gas consumption is
found to increase with increase in Tergitol concentration. The
induction time of hydrate formation is reduced in presence of Terg-
itol compared to the system without Tergitol. Phase equilibrium
curve is shifted to high temperature and pressure region in pres-
ence of Tergitol. These results suggest that Tergitol promote hy-
drate formation kinetically as well as thermodynamically.
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