Ind. Eng. Chem. Res.

2005, 44, 7373-7379 7373

NMR and Viscosity Investigation of Clathrate Hydrate Formation

and Dissociation
Shuqiang Gao,† Walter G. Chapman,*,† and Waylon House*,‡
Chemical Engineering Department, Rice University, Houston, Texas 77251, and Petroleum Engineering
Department, Texas Tech University, Lubbock, Texas 79406

To better understand clathrate hydrate mechanisms, nuclear magnetic resonance (NMR) and
viscosity measurements were employed to investigate tetrahydrofuran (THF) hydrate formation
and dissociation processes. In NMR experiments, the proton spin lattice relaxation time (T1) of
THF in deuterium oxide (D2O) was measured as the sample was cooled from room temperature
down to the hydrate formation region. The D2O structural change around THF during this process
was examined by monitoring the rotational activation energy of THF, which can be obtained
from the slope of ln(1/T1) vs 1/T. No evidence of hydrate precursor formation in the hydrate
region was found. T1 measurements of THF under constant subcooling temperature indicate
that THF hydration shells do not undergo much structural rearrangement during induction.
The T1 of THF was also measured as the sample was warmed back to room temperature after
hydrate dissociation. T1 values of THF after hydrate dissociation were consistently smaller than
those before hydrate formation and never returned to original values. It was proposed that this
difference in T1 after hydrate dissociation indicates that the THF-D2O solution is more
microscopically homogeneous than before hydrate formation. In viscosity experiments, a
Champion Technologies hydrate rocking cell (CTHRC) was used to probe the residual viscosity
phenomenon after Green Canyon (GC) gas hydrate as well as THF hydrate dissociation. The
residual viscosity reported in the literature was observed after GC hydrate dissociation but not
after THF hydrate dissociation. Because GC hydrate behavior involves significant amounts of
gas mass transfer while THF hydrate does not, one might conclude that the residual viscosity
observed after GC hydrate dissociation was likely caused by the supersaturated gas concentration
and its general effect on solvent viscosity, not necessarily by a clathrate water structure lingering
from the solid.

1. Introduction ate experimental techniques capable of probing dynamic

Gas hydrates, also known as clathrate hydrates, are
nonstoichiometric crystalline compounds composed of
cooperative hydrogen-bonded water molecules forming
nanoscale cage-like structures, which accommodate
smaller guest molecules in nearly spherical cavities.
Depending on the size and the composition of the guest
molecules, gas hydrates usually form in at least three
types of crystal structures, I, II, and H.1 It has been
widely recognized that gas hydrates are significant
factors in flow assurance,2 global warming,3 and seafloor
stability4 and are a potential energy supply.5 Gas
hydrates have also been proposed for use in gas separa-
tion,6 transportation, and storage.7
Since the first discovery that water forms clathrate
hydrate with chloride in 1810 by Sir Humphrey Davy,
about 200 years of research has been devoted to
understanding hydrate phenomenon. This continuous
effort has well-established the thermodynamic, physical,
and structural properties of gas hydrates and discovered
a rich collection of hydrate formers. However, clathrate
hydrate formation and decomposition mechanisms and
kinetics are still far from clear due to a lack of appropri-
* To whom correspondence should be addressed. W.G.C:
phone, (713) 348-4900; fax, (713) 348-5478; e-mail, wgchap@
rice.edu. W.H.: phone, (806) 742-3573; fax, (806) 742-3502;
e-mail, Waylon.House@ttu.edu.
†
Rice University.
‡
Texas Tech University.
10.1021/ie050464b CCC: $30.25 © 2005 American Chemical Society
Published on Web 08/09/2005
structural information on the molecular level. The
actual formation and dissociation mechanisms have
important impacts on all hydrate applications. Clarifi-
cation of the formation mechanism is especially impor-
tant for designing kinetic inhibitors or antiagglomerant
hydrate inhibitors that are expected to intervene with
the hydrate formation process on the molecular scale.
Current hypotheses1 about hydrate formation and
dissociation involve hydrate precursor and postcursor
structures. The hypothesis states that, prior to hydrate
formation, water molecules form individual clathrate
cages (hydrate precursors) around the dissolved guest
molecules with one guest molecule inside each cage.
Under favorable conditions, these cages will agglomer-
ate and form solid clathrate hydrate. The hypothesis
also suggests that, upon melting, the solid hydrate
phase dissolves into hydrate cage clusters. Those clus-
ters, also known as residual structures or postcursors,
persist in the liquid phase over a long period of time
provided the temperature stays within certain limits.8
To understand hydrate formation and dissociation
mechanisms, many researchers have studied hydrates
with a particular emphasis on the precursor and post-
cursor hypotheses. Molecular simulations generated
voluminous numerical data on the elemental molecular
detail of hydrophobic hydration processes, which is
important for evaluating the precursor hypothesis. A
vigorous debate continues on whether hydrophobic
solutes structure the water molecules around them. One
7374 Ind. Eng. Chem. Res., Vol. 44, No. 19, 2005
view argues that nonpolar solutes enhance the order of
the hydrogen-bonding network and create structured
hydration shells around them.9-20 On the other hand,
some simulation results showed no indication of en-
hanced structure around hydrophobic solutes.21,22 Even
though computer simulation studies have reached con-
flicting conclusions on whether nonpolar solutes struc-
ture water network around them, they all seem to agree
that long-lived clathrate cages in solution do not exist.
The orientation of hydrogen bonds in the hydration shell
is qualitatively the same as in hydrate clathrate cages,
but the organization of the hydrogen bonds is less
ordered and the number of water molecules involved in
each hydration shell is also different from that in a
clathrate hydrate cage. Experimental work has also
been carried out to probe the water structures around
dissolved nonpolar solutes. Data seem to agree with
those from computer simulation; that is, only loosely
organized hydration cages form around hydrophobic
solutes, with no evidence of regular clathrate cages in
solution.23-27
The fact that no regular clathrate cages have been
experimentally confirmed in the water phase before
hydrate formation indicates that the actual hydrate
formation process may be much more complicated than
the hypothesis suggests. Studies of molecular hydrate
formation mechanisms present great experimental chal-
lenges due to the low equilibrium concentrations of
gases in water and the high pressures required. Experi-
ments usually require specially designed sample cells
and high sensitivity instruments capable of providing
structural information on a molecular scale.
NMR T1 measurement has been shown to be a
powerful technique in studying microdynamic behavior
of liquids28 and providing local molecular-level struc-
tural information surrounding the NMR responding
guest molecules. THF and water form structure II
hydrate at ∼4.5 °C under ambient pressure. It is a good
model system to study clathrate hydrate mechanisms
because its formation conditions are mild and THF is
miscible with water at the conditions of interest. In this
work, proton T1 of THF in D2O was measured as the
sample was cooled from room temperature to hydrate
formation conditions. This allowed us to monitor the
structural change of the hydration shells around THF
molecules as a function of temperature and provided an
opportunity to examine whether hydrate precursors
form under hydrate conditions.
The residual structure dissociation hypothesis is not
as widely studied as the hydrate precursor hypothesis.
It has been observed that re-formation of gas hydrates
from this “hydrate melt” requires less subcooling and
less induction time. This phenomenon is called the
memory effect. Vysniauskas and Bishnoi29 proposed that
it is the existence of residual clathrate structure in
water after hydrate dissociation that is responsible for
the memory effect.
More recently, Sloan et al.30 discovered that the
viscosity of water after methane hydrate dissociation
is initially higher than that before hydrate formation
under the same pressure and temperature. The viscosity
returns to normal only after a long period of time. This
macroscopic residual viscosity phenomenon is argued
as evidence of residual structure, i.e., clathrate ag-
gregates remaining in water after gas molecules are
released.31 However, it is well-known that the diffusion
rate of methane in water is very small. After hydrate
Figure 1. Schematic of the Champion Technologies hydrate
rocking cell apparatus.
dissociation, it is very likely there is still a large amount
of methane dissolved in water solution due to mass
transfer rate limitations. Since dissolved methane struc-
tures the hydrogen-bonding network in water,32 water
supersaturated with methane will have a higher viscos-
ity than water simply saturated with methane under
the same pressure and temperature. Therefore, it is not
clear whether the observed residual viscosity is caused
by remnant clathrate structures or an excess amount
of dissolved methane.
To eliminate the complication of mass transfer phe-
nomenon on the experimental results mentioned above
and obtain a better understanding of the residual
hydrate structure hypothesis, in this work we chose to
study the possibility of residual viscosity after THF
hydrate dissociation. THF is miscible with water at the
concentration of solid THF hydrate;33,34 thus, experi-
ments can be performed at constant concentration
before, during, and after hydrate formation. Stangret
and Gampe35 recently demonstrated that the hydropho-
bic hydration of THF definitely dominates the hydro-
philic one at low THF concentrations. This is the case
at hydrate composition THF:H2O ) 1:17 (molar), so
water-THF hydrogen bonds are not very important for
the fluid structure of dilute solutions. Therefore, in
terms of water structure change, THF is not far from
other nonpolar solutes.
Viscosity of the sample was monitored before hydrate
formation and after dissociation using a Champion
Technologies hydrate rocking cell (CTHRC) (Figure 1)
to detect the reported residual viscosity phenomenon.30
Since THF concentration in water is constant, if the
residual viscosity phenomenon is observed, it would be
a strong demonstration of the existence of residual
clathrate hydrate structures, i.e., postcursors.
Fleyfel et al.36 combined macroscopic hydrate experi-
ments (visual rocking cell) with microscopic hydrate
experiments (NMR) to investigate clathrate residual
structure at the point where hydrate particles become
invisible. They found that some clathrate cages might
still exist in solution after hydrates visually disappear.
In this work, to investigate the molecular evidence of
residual structure for THF hydrate, we measured T1
values of THF as a function of temperature after THF
hydrate dissociation in the NMR experiment mentioned
earlier. Results were compared with that before hydrate

Figure 2. Schematic of the NMR experimental setup.
formation to detect any difference caused by the history
of hydrate formation.
2. Experimental Section
2.1. NMR Microscopic Measurements. 2.1.1. Theo-
retical Background. Spin lattice relaxation mecha-
nisms for THF are composed of two parts, intermolecu-
lar dipole-dipole and intramolecular dipole-dipole
interactions. When the THF to D2O molar ratio is 1:17
(the same composition as in THF hydrate), most of the
THF molecules are completely surrounded by D2O
hydration shells, and intra-dipole-dipole is the main
spin relaxation mechanism. Orientational structures of
D2Os in hydration shells have direct impact on the
rotational motion of enclosed THF molecules. On the
basis of NMR theory,37 T1 is inversely proportional to
the rotational correlation time τc. τc is usually believed
to follow the Arrhenius behavior
1 takes time to rearrange into individual clathrate cages
∝ τc (1)
T1
τc ) τoeEa/RT (2)
where τo is a constant preexponential factor; Ea is the
rotational activation energy, a manifestation of hydra-
tion cage structure around THF and not sensitive to
temperature; T is the temperature in kelvin; and R is
the molar gas constant. Combining eqs 1 and 2 yields
eq 3.
d ln(1/T1) Ea
) (3)
d(1/T) R of handling pressures up to 5000 psi. The rack is
The slope of ln(1/T1) versus (1/T) gives the rotational
activation energy Ea. Therefore, by tracking the changes
in the slope of ln(1/T1) versus (1/T), we can measure Ea
and evaluate the changes in hydration shell structure
around dissolved THF molecules as a function of tem-
perature.
2.1.2. Experimental Details. T1 measurements of
THF (Aldrich, 99+%) in D2O (Cambridge Isotope Labo-
ratories, D 99.9%) at various temperatures were per-
formed on an 85-MHz Oxford horizontal 31 cm wide bore
NMR with imaging capability, using a LITZ RF Volume
Coil (with 14 cm internal diameter) from Doty Scientific,
Inc. (Figure 2). Data were acquired and processed using
Varian VNMR software and INOVA hardware systems.
An Air-Jet temperature controller blew dry and cold air
to control the sample temperature. It is capable of
controlling temperature from -40 to 100 °C with (0.1
°C stability. A glass bottle with a cap that has a Teflon
Ind. Eng. Chem. Res., Vol. 44, No. 19, 2005 7375
liner was used to contain the deoxygenated THF:D2O
) 1:17 (molar ratio) mixture. A LUXTRON fluoroptic
thermometer was mounted into the glass container
through the cap to monitor system temperature. Its
output reading resolution is 0.1 °C.
Since trace amounts of oxygen may alter the T1 of
THF significantly, we deoxygenated pure D2O and THF
liquids separately in Teflon containers by periodically
flushing the gas above the liquid phase with pure
nitrogen gas while periodically shaking the sample
containers to accelerate the diffusion of oxygen from the
liquid samples. After flushing six or seven times over
about 12 h, THF and D2O were mixed on the molar basis
of 1:17. All these processes were operated within a
closed glovebox with nitrogen environment. After al-
lowing the sample to stabilize for half a day, we put the
sample into the NMR probe for T1 measurements. (The
success of deoxygenation was demonstrated by that fact
that, after deoxygenation, T1 increased about 2 s
compared to the sample without deoxygenation). T1
values were measured using the inversion recovery
technique. All samples’ 90° and 180° pulses were
calibrated before every measurement. VNMR software,
given inputs of possible minimum and maximum T1
values, automatically generates standard 180°-τ-90°
pulse sequences with various values of τ. It took 4-6
min to take a T1 data point.
The sample was cooled from room temperature (∼25
°C) to subzero temperatures with an average cooling
rate of ∼0.5 C°/h until hydrate formation occurred.
Hydrate formation was indicated by a jump in the
sample temperature. Oyama et al.38 proposed that,
during the induction period, water around dissolved CO2
before hydrate formation. To test this hypothesis, we
measured T1 as a function of time while the temperature
was kept constant in subcooling state. If the hydration
shell structures around THF experience rearrange-
ments, the T1 of THF would vary. After hydrate forma-
tion, temperature was raised to completely dissociate
the hydrate. T1 was also measured as the sample was
heated back to about 25 °C.
2.2. Viscosity Macroscopic Measurements. The
viscosity experiments for the THF (99+%, Aldrich)-
deionized (DI) water system were performed on a state-
of-the-art CTHRC, which is an apparatus with high-
pressure sapphire tubes placed on a rack. It is capable
immersed in a temperature-controlled thermal bath and
it rocks (45° from horizontal position through a com-
puter-controlled step motor. As the rack rocks, a ball
inside the tube rolls from one end to the other, and each
tube functions such as a rolling ball viscometer. The
motion of the ball is detected through two sensors
mounted on both ends of each tube. The time that the
ball takes to travel from one sensor to the other is
recorded as an indication of the fluid viscosity inside
the tube. Changes of the fluid viscosity in the tubes can
be sensitively detected by measuring the ball travel
speeds. Hydrate formation is indicated by an increase
in fluid apparent viscosity while system temperature
and pressure were kept constant. The ball was eventu-
ally immobilized by the hydrate blockage. Hydrate onset
can also be detected by visual observation of hydrate
crystal deposit on the tube’s inside wall. Ball travel time,
temperature, and pressure data are collected every
minute into a terminal computer using LabView.
7376 Ind. Eng. Chem. Res., Vol. 44, No. 19, 2005
Figure 3. T1 of THF in D2O before hydrate formation and after
hydrate dissociation, plotted as ln(1/T1/s) vs 1/T/K. The activation
energies (Ea) were calculated from the slopes.
Green Canyon (GC) gas hydrate experiments were
first performed on CTHRC to duplicate the residual
viscosity phenomenon reported in the literature30 in
order to ensure that the rocking cell we use is sensitive
enough. GC gas is composed of 87.2% (mol) CH4, 7.6%
C2H6, 3.1% C3H8, 0.8% n-C4H10, 0.5% i-C4H10, 0.2%
n-C5H12, 0.2% i-C5H12, and 0.4% N2. Every tube was first
charged with 9 mL of DI water. After the system was
purged three times with 50 psi of GC gas, 1000 psi of
GC gas was introduced into the tubes. The pressure was
kept constant at 1000 psi during the experiment. Once
charged, the cell temperature was initially raised to 30
°C to eliminate any possible preexisting extra structure
in water. The system was then lowered to 20 °C and
equilibrated for ∼2 h to establish a viscosity baseline
at this temperature. The temperature was then further
cooled to 15 °C to initiate hydrate formation. The
predicted hydrate equilibrium temperature by CSM-
HYD1 is 17.8 °C for this pressure and gas composition.
To ensure complete hydrate formation, the temperature
was lowered to 5 °C before it was raised to dissociate
the hydrate. Then the system was slowly warmed back
to 20 °C until complete hydrate dissociation occurred.
The system was equilibrated to establish the viscosity
baseline at this temperature again.
Viscosities of the THF-water system were measured
in a similar fashion. DI water and THF were added in
a H2O:THF ) 17:1 molar ratio, the composition in THF
hydrate. The tubes were then sealed and heated to 30
°C to eliminate any preexisting extra structure in the
water. The system temperature was then lowered to
hydrate formation conditions. During this cooling pro-
cess, the system was allowed to equilibrate at 10 and 6
°C for about 300 min in order to establish the viscosity
baselines at these temperatures. After complete hydrate
formation, the system was warmed to dissociate the
hydrate. The system was equilibrated again at 10 and
6 °C to establish the viscosity lines.
3. Results and Discussion
3.1. NMR Results. As shown in Figure 3, the ln(1/
T1) vs 1/T slope does not change dramatically as the
sample is cooled from room temperature into the
hydrate region. This indicates that the hydration cage
structure around THF in the hydrate region before the
phase transition is not very different from that at room
temperature. The slope gives the average rotational
activation energy of 21.18 kJ/mol for THF in water
solution, which is very different from that in the solid
hydrate phase, 4.14 kJ/mol.39 Since the rotational
Figure 4. T1 of THF in D2O during induction time at -1.7 °C.
activation energy reflects local water structure around
THF, the result indicates that THF hydration shells in
the aqueous phase are dissimilar in nature from the
regular clathrate cages in the hydrate phase, even under
hydrate formation conditions. The suggested hydrate
precursors were not found and the proposed hydrate
formation hypothesis1 is not supported.
To compare with the time-dependent results reported
by Oyama et al.,38 we measured T1 as a function of time
while the temperature was kept constant under hydrate
conditions. As shown in Figure 4, T1 does not change
much with respect to time during the induction period.
This implies that the hydration shells around THF have
no dramatic structural change and they do not rear-
range themselves into regular clathrate cages during
induction time.
One interesting feature is that even though the slope
of ln(1/T1) vs 1/T does not change dramatically as
temperature goes from ∼25 °C to hydrate formation
regions, it does show a slight increase at around 8-9
°C. In this experiment, the activation energy changes
from 19.97 to 23.83 kJ/mol at ∼8.5 °C. This transition
in the slope is reproducible and it is under further
investigation.
After hydrate dissociation, even though the slope is
similar to that before hydrate formation, there is a
consistent shift of T1, which never returned to the
original value. This variation of T1 implies a structural
change of water molecules around THF due to hydrate
formation and dissociation. However, this structural
change is not caused by residual clathrate structure,
because the effect still exists above 25 °C. There are
possible microscopic heterogeneities40 in fresh THF-
D2O solution, even though THF and D2O are miscible
at all concentrations under conditions of interest. Since
THF becomes perfectly distributed as a result of hydrate
formation, subsequent dissociation would result in a
more microscopically homogeneous THF-D2O solution.
Therefore, the T1 shift is probably caused by a more
uniform distribution of THF in D2O after THF hydrate
dissociation than before hydrate formation. It was also
observed that before hydrate formation the THF-D2O
solution had a slight milky appearance and after
hydrate dissociation the solution became crystal clear.
Without external disturbance, the milky appearance can
last over 2 weeks at room temperature.
3.2. Viscosity Results. In the GC gas hydrate
viscosity experiment, shown in Figure 5, the viscosity
baseline after hydrate dissociation is obviously higher
than that before hydrate formation at temperature 20
°C and pressure 1000 psi. The residual viscosity phe-
nomenon reported in the literature30 was successfully
reproduced.

Figure 5. Residual viscosity phenomenon observed at 20 °C after Green Canyon gas hydrate dissociation. The pressure was kept constant
at 1000 psi.
Figure 6. No residual viscosity is observed at 6 and 10 °C after THF hydrate dissociation.
However, results from THF-water hydrate experi-
ments (Figure 6) do not demonstrate this residual
viscosity effect. Viscosities baselines established at 6 and
10 °C before hydrate formation are the same as those
after hydrate dissociation. Macroscopic evidence of the
residual structure is absent in this experiment. The
different results from THF and GC experiments may
be explained as follows.
In GC hydrate experiment, after hydrate dissociation,
a large amount of hydrocarbons have to get out of the
liquid phase because the concentrations of hydrocarbon
gases in the hydrate phase are much higher than their
equilibrium concentrations in liquid water under the
same condition. The hydrocarbon gases resulting from
hydrate dissociation can come out of liquid phase by
diffusion or by forming bubbles. Since the diffusion
coefficients of hydrocarbons in water are very small, it
is much more efficient for gases to escape as bubbles.
However, from visual observation, few bubbles formed
during GC hydrate dissociation under constant pres-
sure. Therefore, gases come out of water mainly by
diffusion, which makes this process very time consum-
ing. During the time frame of viscosity measurements,
liquid water could be still highly supersaturated with
hydrocarbon gases. This would cause higher than
normal apparent water viscosity.41 THF does not have
the above problem because its concentration in the
liquid phase is the same as that in the hydrate phase
Ind. Eng. Chem. Res., Vol. 44, No. 19, 2005 7377
and it stays constant under all conditions. Since residual
viscosity was absent after THF hydrate dissociation, the
observed residual viscosity phenomenon in GC hydrate
experiment was probably caused by supersaturated
hydrocarbons in water after hydrate dissociation, not
necessarily by remaining clathrate structure in the
aqueous phase.
The fact that residual viscosity was not observed after
THF dissociation but an overall structural change
around THF was indicated by NMR results may be
caused by two reasons. First, strong mixing by the steel
ball inside the sample tube may have already made
THF-D2O microscopically homogeneous even before
hydrate formation and destroyed any possible residual
structure as soon as the hydrate melted. Second, even
though CTHRC can reproduce the residual viscosity
phenomenon for the GC hydrate experiment, it may not
be sensitive enough to detect the structural change after
THF hydrate dissociation. In any case, rocking-cell types
of apparatus30 may not be appropriate tools to measure
residual structure.
4. Conclusions
NMR and CTHRC techniques were used to investi-
gate the formation and dissociation mechanisms of THF
hydrate. In NMR experiments, T1 of THF in D2O was
measured as the sample was cooled from room temper-
7378 Ind. Eng. Chem. Res., Vol. 44, No. 19, 2005
ature to hydrate formation conditions. By calculating
the rotational activation energy of THF in D2O, it was
shown that the THF hydration shell structure in solu-
tion changes little as temperature goes from room
temperature to subzero. No indication of hydrate pre-
cursor formation was observed. During the induction
period, T1 stayed about the same as a function of time
at constant temperature, which implied that water
molecules in THF hydration shells do not undergo much
rearrangement during the induction period. These
results do not support the hydrate precursor hypothesis
in THF. After hydrate dissociation, T1s were consis-
tently smaller than that before hydrate formation,
which suggests a structural change in the solvent after
hydrate dissociation. The failure of this change to
disappear even at higher temperatures suggests it is
probably caused by a more uniform distribution of THF
in D2O after hydrate dissociation.
Using the CTHRC apparatus, a residual viscosity
effect reported in the literature was reproduced in a GC
gas hydrate experiment but not in a THF hydrate
system. After GC gas hydrate dissociation under con-
stant pressure, it would take a long time for hydrocar-
bon gases to reach their equilibrium concentrations
because of their small diffusion constants in water.
Combined with results from the THF viscosity experi-
ment, it is concluded that the residual viscosity phe-
nomenon after GC gas hydrate dissociation is probably
due more to gas supersaturation than residual clathrate
structure.
Acknowledgment
We gratefully acknowledge the financial support of
the Robert A. Welch Foundation. S.G. expresses his
gratitude to Champion Technologies Inc for giving him
access to their state-of-the-art Champion Technologies
hydrate rocking cell. The Livermore Chair and MRI-
PAC at TTU provided support for the NMR experi-
ments.
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Received for review April 18, 2005
Revised manuscript received July 7, 2005
Accepted July 12, 2005
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