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The Development of Clathrate Hydrate Science

Christopher I. Ratcliffe*

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ABSTRACT: Clathrate hydrates are extremely important in the

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area of energy and fuels as both potential hydrocarbon resources

and nuisances or hazards in the oil and gas industry. They are
ubiquitous in nature, occurring in many places on Earth and
probably many more extraterrestrial bodies. They have potential
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for the storage and transport of hydrocarbons, as a storage medium

for hydrogen for fuel cells, and for cold energy storage. Other
possible applications include CO2 sequestration, desalination, gas
separations and isolation of unstable species. This review will cover
the development of the science of clathrate hydrates over its
roughly 200 year history and is framed initially around several
milestones, which are then placed in the context of discoveries and
new techniques in other areas that made them possible.

1. INTRODUCTION molecules, Figure 1. As in ice, each water oxygen atom is

Today we know a great deal about clathrate hydrates,1−8 but it involved in a roughly tetrahedral arrangement of four hydrogen
has taken over two centuries to reach this state of knowledge. So bonds. They can contain mixtures of guests, and in many cases
how did we get here? In this review I will highlight how the the guests in the large cages require small guests in the small
discoveries of clathrate hydrate science unfolded, with sections
on what I consider to be some of the most important milestones.
I will place these milestones (MS) in the context of discoveries
and new techniques in other areas of science that helped make
them possible. Then, I will follow these with some more general
sections of interest. Unfortunately, it is impossible to cover all
aspects of clathrate hydrate research in detail in a short review,
but I will endeavor to mention most topics and direct readers to
further reading. In particular, I recommend a new two-volume
treatise, edited by Ripmeester and Alavi,8 that focuses largely on
the molecular science of clathrate hydrates.
John Ripmeester has played a very prominent role in the
Figure 1. X-ray diffraction structural details of two crystals of natural
scientific investigations of clathrate hydrates since his arrival in
gas hydrates recovered from offshore Vancouver Island. (Left)
Don Davidson’s group at the National Research Council of Methane (CH4) molecules in small (512) and large (51262) face-sharing
Canada (NRC) in 1972, as will be evident from many of the cages of str.I clathrate hydrate. (Right) Methane in a small (512) cage
references given. Additionally, it has been just 35 years since the and both ethane (C2H6) and propane (C3H8) in large (51264) cages of
publication of the discovery of structure H,9 and since it was str.II clathrate hydrate. The frameworks show oxygen atoms of water
John who first recognized that he was synthesizing hydrates with connected by hydrogen bonds. (notation: 51262 indicates a cage with 12
guests too large for structure II, it seems appropriate to give it pentagonal faces and 2 hexagonal faces). Reproduced from ref 10 with
special attention in this review. permission from John Wiley and Sons, copyright 2007.

2. WHAT ARE CLATHRATE HYDRATES? Special Issue: 2022 Pioneers in Energy Research: John
Clathrate hydrates are nonstoichiometric solid solution Ripmeester
materials that have an ice-like appearance. Their structures Received: May 25, 2022
consist of a scaffolding of water molecules held together by Revised: July 26, 2022
hydrogen bonds, forming a space-filling framework of face- Published: August 11, 2022
sharing small and large cages, some or all of which contain guest

© 2022 American Chemical Society https://doi.org/10.1021/acs.energyfuels.2c01723

10412 Energy Fuels 2022, 36, 10412−10429
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cages for overall stability. There are three main classes of
canonical clathrate hydrates, which have come to be known over
the years as structures I, II, and H (str.I, str.II, and str.H,
respectively). These classes have progressively larger cages as
well as small cages, of which the pentagonal dodecahedral (512)
cage is common to all three. A more formal classification
suggests these would be better named as CS-I, CS-II and HS-III
(chapter three of ref 8), but here we will stay with the familiar
notation abbreviated to str.I, str.II, and str.H.
3. MS1: FIRST DISCOVERY (THE STARTING POINT)
Clathrate hydrates were probably first produced in the late 18th
century. There are reports of solids formed in the presence of
water or moisture from gases such as sulfur dioxide and chlorine
that from the descriptions given were undoubtedly hydrates.
It was Davy in 1810 who made the crucial step of recognizing
that chlorine formed a solid compound with water11 and that
this could explain previous misguided claims that chlorine was
solid at temperatures near and above 0 °C. He also coined the
term gas hydrate. Note that the molecular natures of Cl2 and
H2O were not yet known. Faraday later determined a
composition of 1:10 chlorine/water, acknowledging that the
amount of chlorine might be underestimated.12
Through the following decades, many more gas hydrates were
made, including CO2, hydrocarbons, and halogenated organics,
and their compositions were studied. At the time, all chemical
compounds were thought to require whole numbers of atoms;
therefore, when hydration numbers were determined they were
usually rounded to whole numbers. Double hydrates were
discovered, then hydrates of liquids, and the need for help gases
for some hydrate formers was recognized.
4. MS2: PHASE EQUILIBRIA
The next major steps followed Cailletet’s development in 1878
of an apparatus to allow high-pressure and low-temperature
studies.13 This technical advance greatly helped the inves-
tigation of the temperature and pressure conditions under which
hydrates were stable. Cailletet, de Forcrand, and Villard, among
others, measured dissociation pressures versus temperature, but
Roozeboom applied the Gibbs phase rule and set about mapping
the equilibrium lines between the various possible phases and
thus obtained phase diagrams14 The determination of phase
equilibria gained great importance much later in the oil and gas
industry.
Also of note during the later 19th and early 20th centuries, Le
Chatelier showed that the Clausius−Clapeyron equation could
be applied to the variation of the dissociation pressure of
hydrates with temperature and from this established a link to the
hydrate composition.15 Using calorimetry, de Forcrand
measured a heat of dissociation from which he concluded that
most of the heat came from the change of the state of the
water.16
Villard found that many small molecules had similar hydration
numbers very close to six and suggested that all hydrates had the
composition M(H2O)6 (so-called Villard’s rule).17 This did not
go unchallenged, but the notion of a molecular structure for gas
hydrates with six waters weakly bound to the guest in an
octahedral formation was still prevalent in the 1920s.
This historical period has been extensively reviewed in
chapters one and two of ref 8.
pubs.acs.org/EF Review
5. MS3: DETERMINATION OF CRYSTAL STRUCTURES
Of all the leaps in clathrate hydrate science, probably the most
significant was the first determination of crystal structures, as
this finally showed the true forms of these intriguing materials.
Again, this followed advances in scientific knowledge and
technology: Laue18 observed X-ray diffraction by crystals in
1912, 17 years after the discovery of X-rays by Roentgen,19 and
in the following year the first X-ray crystal structures of the
simple crystals of diamond and alkali halides were published by
the Braggs.20,21 Methods of data collection and analysis
improved over the years. In particular, the introduction of the
Patterson function in 1934 to solve the phase problem and
determine interatomic distances was a major step,22,23 but it was
still a difficult proposition to solve complex structures.
In 1949, von Stackelberg published his work on single-crystal
X-ray data of several small-molecule hydrates, which he found to
be cubic with a cell constant of about 12 Å.24 He proposed a new
kind of structure involving a framework of hydrogen-bonded
water molecules that created cages occupied by guest molecules.
This was a definite departure from the traditional molecular view
of hydrates as guests coordinated by six waters. This new model
had some problems, however, in that the O−H···O bond lengths
of 2.4 Å were very short and the O−O−O angles ranged
between 60° and 145°.
At about the same time, Claussen had realized that a
pentagonal dodecahedron (512) of water molecules would have
O−O−O angles between adjacent hydrogen bonds very close to
the ideal tetrahedral angle, similar to the angles in ice. In 1951,
he then constructed a ball and stick model based on a diamond-
like lattice of dodecahedra in which the spaces had the form of
hexakaidecahedral cages (51264).25 In essence, he had produced
a model of what we now know as structure II.
Later in 1951, von Stackelberg and Muller26 reported that X-
ray diffraction results showed there were in fact two types of
cubic hydrate crystals with unit cell parameters of about 12 and
17.2 Å. The latter, which occurred for larger guests (CHCl3,
CH2Cl2, and C2H5Cl), belonged to the space group O7h-Fd3m.
They determined its structure and some physical structural
parameters from the X-ray data, which confirmed the basic
correctness of Claussen’s model The unit cell contained 16
pentagonal dodecahedra and 8 hexakaidecahedra. They had not
quite finished refining the structures of the 12 Å crystals, which
formed with smaller guests Cl2, SO2, CH3SH, H2S, CH3Br, and
CH3Cl.
The last four months of 1951 saw the independent submission
of three papers, all of which converged on the crystal structure of
what we now call structure I: (1) Claussen27 found that he could
construct a body-centered cubic arrangement of pentagonal
dodecahedra in which the spaces could be formed by several
adjoining tetrakaidecahedral cages. (2) Muller and von
Stackelberg28 finally solved the structure of the 12 Å unit cell
crystals from their X-ray data in space group Pm3n, obtaining
reasonable O−H···O lengths of 2.81 Å and O−O−O angles
ranging from 104° to 124°. The unit cell contained two
pentagonal dodecahedra and six tetrakaidecahedra. (3) Pauling
and Marsh29 developed a hydrate model similar to Claussen’s
that was based on pentagonal dodecahedral structures they had
found while investigating intermetallic compounds. To test their
model, they obtained X-ray data of Cl2 hydrate and refined it to
the same Pm3n structure. Their analysis also considered possible
models for the disordering of Cl2 within the large cage.
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In short, Claussen’s insight about the pentagonal dodecahe-
dron led him to plausible models for the two cubic hydrate
structures, and the X-ray results provided experimental proof
and structural parameters. This was an impressive achievement,
especially considering that it was accomplished without the aid
of computers.
The importance of these results cannot be overstated�it was
finally possible to see the true form of these materials and gain a
much greater understanding of their behavior. First, it was clear
that the hydrates were clathrates, namely, cage compounds
where the host and guest interact only through weak forces.
Second, it became obvious from the unit cell contents that the
stoichiometry could vary depending on the cage occupancy.
str.I: (512 )2 ·(512 62)6 ·46H 2O or (D)2 ·(T )6 ·46H 2O
where D = 512 and T = 512 62
str.II: (512 )16 ·(512 6 4)8 ·136H 2O or (D)16 ·(H )8 ·136H 2O
where H = 512 64
Third, guest size was important in determining which
structure formed. Larger guests that were too large for the
51262 cage of str.I might fit into the 51264 cage of str.II.
No further structural studies were performed until 1965, by
which time the technical aspects of X-ray diffraction and data
collection and refinement had improved and greater detail was
possible. McMullan et al. obtained precise coordinates for the
framework O atoms of str.I ethylene oxide (EO) hydrate30 and
str.II H2S/tetrahydrofuran (THF) hydrate.31 The electron
density of the guests was distributed because of disordering
over equivalent symmetry positions within the cages. While the
structural data really do not allow a distinction between static
and dynamic disorder, the authors suggested that EO was a
hindered axial rotor and THF was a free rotor, thus hinting at
another aspect of guests in cages, which is discussed below in
section 9. It was also found that H2S filled 46% of the small cages
in the str.II hydrate. In the 1960s and 1970s, Jeffrey also studied
numerous amine and ionic hydrates with different structures.4 In
1977 and 1990, single-crystal neutron diffraction studies of str.I
EO/D2O hydrate32 and str.II Xe/CCl4/D2O hydrate, respec-
tively,33 showed conclusively that the D2O molecules were
disordered, with 0.5D atoms at two positions in each hydrogen
bond.
In the years following 1965, many more new hydrates were
discovered and characterized by various techniques, including
powder diffraction, dielectric, NMR, calorimetric, and phase
equilibrium studies. For a long time it was thought that all guests
small enough to fit into the str.I large cage would form that
structure and that str.II only formed with guests too large for
str.I. In 1984, that picture changed.
6. MS4: THE SMALLEST GUESTS
The discovery that the very smallest guests formed str.II was
serendipitous. John Tse was about to use incoherent inelastic
neutron scattering (IINS) to look at the lattice mode region of
the vibrational spectrum of the str.I methane hydrate to verify
some of his conclusions from MD calculations. He needed a
reference str.I material with a guest that had a much lower
incoherent scattering cross-section than the four hydrogens of
CH4, and for this he chose the monatomic guest krypton.
Immediately before the IINS experiment, a powder neutron
diffraction pattern was obtained to verify the integrity of the
sample. It was then surprising to find that the pattern did not fit
pubs.acs.org/EF Review
that expected for str.I, but it did fit str.II.34 Following this initial
revelation, several other small guests were found to form str.II
using powder diffraction, including H2, He, Ne, Ar, Kr, O2, N2,
NO, and CO.35−41 The first studies of CO produced only str.I,
but more recently it was shown that str.I was converted to str.II
over time at higher pressures.41
Some of these hydrates had been produced much earlier
before structures were known, such as Ar by Villard 1896,42 Kr
by de Forcrand 1923,43 and N2 and O2 by van Cleef 1960.44 In
1999, Dyadin et al. also showed the existence of str.II hydrates of
H2, He, and Ne at high pressures from phase equilibrium
measurements up to 15 kbar, i.e., before diffraction confirmed
their structures.45
The greater stability of str.II for these smallest guests derives
from a preference for small cages of which there are more in str.II
than str.I, a feature already suggested in 1982 by Holder and
Manganiello46 based on thermodynamic modeling.
Perhaps not too surprisingly, multiple occupancy of cages,
especially the large cage, is also possible for small guests, as seen
by diffraction for H2, He, Ne, CO, N2, and O235−37,41,47 and by
Raman spectroscopy for H2.48,49
7. FURTHER DIFFRACTION STUDIES
Continuing with the general theme of diffraction studies,
increases in computing power and more recently CCD detectors
have led to much improved single-crystal X-ray studies, with
better definition of guest positions and orientations and even
framework H atom positions. Since the 1990s, the emphasis has
been on
(a) New structures, such as hexagonal str.H with a new large
cage (discussed in section 11), tetragonal Br2 hydrate with
its 51263 cage and variable composition,50 trigonal
dimethyl ether hydrate with an unusual cage structure
and two new cage types,51 a xenon str.HS-I metastable
phase produced at high pressure and quench-recovered at
77 K.52
(b) Guest disorder, such as in str.I CO2 hydrate53 str.I
trimethylene oxide (TMO) hydrate.54
(c) Determining cage occupancies and compositions, such as
for CO2 hydrate53 and single crystals of str.I and str.II
found in recovered samples of natural gas hydrates
(Figure 1).10
(d) Hydrogen bonding and halogen bonding interactions
between the guest and the host; for example, O atoms on
guests show shorter-than-van der Waals contacts with
water O atoms,55 and Cl2 and Br2 show very significant
decreases in contact distances and distortions of
cages.56,57
The structure of str.I trimethylene oxide (TMO) hydrate was
interesting because the TMO showed two preferred orientations
in the large cage, each of which was disordered over eight
symmetry positions. In this complex situation, a range of
possible guest orientations were found to be possible, all of
which were of very similar quality when fit to the data. However,
by combining diffraction data with NMR data, which restricted
the range of orientations, it was possible to find a good result
consistent with both techniques.54 The TMO was oriented with
its electric dipole axis close to the symmetry axis of the cage. This
was of interest since, unique among all known hydrates, str.I
TMO has a dipole-ordering transition at ∼105 K.58−61
Powder diffraction of both X-rays and neutrons has also
become a powerful tool for hydrate studies. From the 1980s
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onward it has been used extensively to establish the hydrate
structural type. The method first proposed by Rietveld in 196762
for refining structures from powder data has been developed
further over the years, and structural details can be determined
with more recent maximum entropy and direct-space methods.
This is especially useful for studies at high pressure, for example,
the discovery that str.I Xe hydrate will transform to str.H at high
pressure63 and that this phase forms a new metastable hexagonal
structure HS-I with 512, 51262, and 51263 cages when quench-
recovered at 77 K and atmospheric pressure.52 Other examples
of high-pressure studies include H2 str.II hydrate,35 str.H CH4
hydrate,64 and str.H Kr hydrates.65
8. MS5: THERMODYNAMICS
The determination of the crystal structures in 1951 made the
next ground-breaking development in clathrate hydrate science
possible, namely, the solid-solution statistical thermodynamic
model presented in 1959 by van der Waals and Plateeuw66 (see
references 6 and 67 and chapter seven of ref 8 for detailed
reviews of this topic).
The basic model assumes a fixed water framework of cages
that can be treated separately from the guest molecules, which
are “dissolved” in the cages. Depending on the temperature and
pressure conditions, the guests can have variable concentrations.
The model assumes cages are singly occupied, guest−guest
interactions are negligible, and the lattice is independent of the
guest (i.e., the guest does not cause distortions).
By assuming a potential for the cage−guest interaction and
evaluating the partition functions, thermodynamic parameters
can be obtained. Initially, van der Waals and Plateeuw used a
Lennard−Jones−Devonshire potential, but the Kihara potential
is more commonly used. These can then be used to calculate
dissociation pressures under various conditions, e.g., refs 68 and
69.
A very useful equation derived from the model that applies
when the gas, hydrate, and ice are in equilibrium is
o began low-frequency dielectric absorption studies of clathrate
= RT i[ni ln(1 i)] / N
o
where Δμ is the chemical potential of the empty lattice relative
to that of ice, ni is the number of cages of type i and occupancy θi
in the unit cell, and N is the number of waters in the unit cell.
The empty hydrate lattice is unstable with respect to ice, but
once a minimum level of cage filling is achieved, as described by
this equation, the structure becomes stable.
In the case of str.I with 2 small cages, 6 large cages, and 46
water molecules in the unit cell, this equation becomes
o
(str.I) = RT[ln(1 S) + 3ln(1 L)] /23
Similarly for str.II,
o
(str.II) = RT[2ln(1
S) + ln(1 L)] /17
The cage occupancy is also related to the Langmuir isotherm,
e.g., for a small cage, θS = CSP/(1 + CSP), where CS is the
Langmuir constant for the guest in the small cage and P is the
pressure.
Values for θS, θL, and Δμo(str.I) can be obtained if the
hydration number n = 23/(θS + 3θL) and the cage occupancy
ratio θS/θL are determined for a sample prepared under three-
phase gas/hydrate/ice equilibrium conditions. This was done
for the str.I Xe hydrate using calorimetry to determine the
composition and 129Xe NMR to determine θS/θL from the
intensities of the resonances for Xe in the small and large cages,70
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Review
from which Δμo(str.I) = 1297 ± 110 J mol−1. Similarly, a value of
Δμo(str.II) = 1068 J mol−1 was estimated for the str.II Kr
hydrate from calorimetry and molecular dynamics calcula-
tions.71 θS/θL values have been determined from solid-state
NMR of various nuclei for a number of guests in str.I, and good
estimates of hydration numbers were obtained, using the value
of Δμo(str.I).72
The van der Waals and Plateeuw model has been extended to
more complicated situations, e.g., str.H73,74 and str.II with
double-cage occupancy.75 In spite of the limitations imposed by
its assumptions, the model has proved remarkably useful and has
provided a framework for further developments to try to
overcome its shortcomings. The model has been extremely
important for the oil and gas industries for predicting
dissociation pressures under various conditions.
Incidentally, empty hydrate lattices were assumed to be
hypothetical entities, as they needed the guest molecules for
stability. However, Falenty et al.37 found a way to obtain the
empty str.II lattice by pumping on str.II neon hydrate at 142 K
for 5 days. Neon is small enough that it can slowly diffuse
through the lattice. The empty lattice becomes unstable above
∼145 K.
9. MS6: DYNAMICS AND DISORDER
The next major development in clathrate hydrate science was
the discovery of dynamics of both guest and water molecules,
since these began to give more insights about the interactions
between the guest and the host and how these affect hydrate
properties.
Guest disorder in clathrate hydrates was first noted in
Pauling’s structural study of Cl2 hydrate,29 and the two-site
disorder of the water protons in the hydrogen bonds was
assumed to be the same as that in ice. The two-site disorder in ice
was verified in 1949 by neutron diffraction of D2O ice.76
However, the structural studies do not distinguish between static
and dynamic disorder. Then, in 1962, Don Davidson at NRC
hydrates. The first studies down to 77 K indicated the
reorientation of the water dipoles in EO, acetone, and THF
hydrates, with activation energies considerably less than that in
ice.77−80 The reorientation of guest molecule dipoles was later
found when studies were performed at temperatures well below
77 K.81 The NRC group then began to probe the dynamics with
solid=state NMR,82 which also enabled studies of guests without
dipoles. The early NMR studies made use of 1H and 19F, since
these were the most sensitive and abundant nuclei accessible at
the magnetic fields available then. Details of the dynamics of the
host and the guest were determined by analyzing line shape
second moments (M2), which gave details about structure and
motional models, and spin−lattice relaxation time (T1)
measurements, which gave rates and barrier heights. Using
these techniques, a large amount of data on the dynamics of
hydrates of str.I and str.II was obtained by Davidson, Garg,
Gough and Ripmeester throughout the course of the 1970s and
beyond. In the process, many new hydrate-forming guests were
found. The major discoveries from this period can be
summarized as follows, with reference to reviews (ref 1, ref 83,
and chapter 12 of ref 8):
9.1. Water Dynamics. Water reorientation at rates that are
amenable to detection by dielectric loss or NMR experiments is
affected by the nature of the guest and occurs above ∼180 K for
the fastest cases (higher temperatures for the slower cases). For
guests that have an O atom, e.g., ethers and ketones,
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reorientational correlation times (τ) are shorter and activation
energies (Ea) lower than those for guests without O atoms (see
Table 1 and chapter 12 of ref 8). In all cases, the reorientation is
more rapid than that in ice Ih.
Table 1. Ranges of Correlation Times and Activation
Energies for the Reorientation of Water Molecules in str.I
and str.II Clathrate Hydrates and Ice Ih Determined by
Dielectric and 1H NMR Studies
τ at 233.2 K (s) Ea (kJ mol−1) refs
guests without O 60−780 43.9−51.4 84−86
guests with O 0.03−5.4 24.2−38.0 84, 85, 87
ice Ih 1420 55.2 84, 88
The translational diffusion of water in hydrates was also found
to be more rapid than that in ice Ih; the Ea value for both str.I EO
and str.II THF hydrates was 50.2 kJ mol−1,89,90 considerably less
than the value of 58.2 kJ mol−1 for ice Ih.91
It was suggested that the more rapid reorientation of water for
O-bearing guests was due to the injection of Bjerrum defects into
the water framework by transient hydrogen bonds between the
guest O atom and a water H atom.1 Concrete evidence for this
hydrogen bonding has come much more recently from
crystallography and MD simulations (see section 12).
The H disorder of the water molecules changes from dynamic
to static as the reorientation freezes out at lower temperatures,
creating a distribution of different cage configurations92−94 (see
Figure 2). This has consequences for the guest dynamics.
Figure 2. H disorder of water molecules in a 51262 cage. (Left) Static
disorder showing three of the many different cage configurations.
(Right) Under rapid dynamic disorder, all cages appear to be identical,
with two 1/2 H atoms along each bond. Reprinted from ref 94 with
permission from Springer Nature Customer Service Centre GmbH,
copyright 1999.
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9.2. Guest Dynamics. Guest reorientation is much more
rapid than that for the water and occurs down to very low
temperatures, in some cases even below liquid helium
temperatures,83 e.g., H2S and CH4.
All guests show effects that can be accounted for by a
distribution of correlation times as a consequence of the
multiplicity of cage configurations arising from the static H atom
disorder in the cage walls, which in turn implies a distribution of
interaction potentials.92−94
Because of their internal symmetry, spherical-top guest
molecules such as CH4 and SF6 exhibit pseudo-isotropic
reorientation in all types of cages even when the water motion
is frozen. Nonspherical molecules show anisotropic motion in all
cages in the lower temperature (LT-) regime where the water
motion is frozen. However, in the higher temperature (HT-)
regime, where the water motion is rapid and the cages take on
their average crystallographic symmetry, nonspherical guests
show pseudo-isotropic reorientation in spherical cages, i.e., str.I
small and str.II large cages, but their motion is still anisotropic in
nonspherical cages. Therefore, the shape of nonspherical cages,
defined by the crystal symmetry, clearly affects the range of
orientation of the guest.
The mean activation energies determined for guest
reorientation are very much smaller than those for water and
range from about 0.2 to 8.8 kJ mol−1.83,95−97 There is not much
difference in the range between str.I and str.II or between guests
with and without oxygen atoms in str.II. However, there is a
trend of Ea increasing with the guest size. Spherical tops are all at
the lower end of the range, below 3.2 kJ mol−1.95 It also appears
that the presence of an electric dipole has very little influence, as
the activation energies for p-dioxane97 and 1,3-dioxane83 with
zero and 2.06 D dipole moments are quite similar at Ea = 7.19
and 8.28 kJ mol−1. respectively.
A new era of NMR began in the later 1970s with the advent of
superconducting cryomagnets with higher magnetic fields,
which allowed many lower-frequency nuclei to be studied.
The increasing capabilities of computers also allowed the
development of Fourier transform pulse NMR at this time, and
the techniques of magic angle spinning (MAS) and polarization
transfer by cross-polarization (CP) from 1H further advanced
the possibilities.
These new capabilities made it possible to study the dynamics
of guest molecules in more detail using the quadrupolar doublet
lineshapes of 2H and chemical shift anisotropy (csa) lineshapes
of nuclei such as 13C, 31P, and 77Se.72,98 With a knowledge of the
line shape for the molecule when completely static (usually
obtained from the pure-solid guest material), the line narrowing
caused by dynamic averaging in a hydrate cage yields
information about the orientations visited by the molecule
during the course of its motion.
Once again one must distinguish between the temperature
regions where the water reorientation is fast (HT-regime) or
frozen (LT-regime). In the HT-regime, the cages of a particular
type are all equivalent and have their crystallographic symmetry.
Consequently, the guest lineshapes have clear features
corresponding to a single dynamically averaged csa or
quadrupole coupling. In cases where the guest occupies both
small and large cages of str.I, the lineshapes for guests in the
spherical small cages show complete averaging to an isotropic
line and thus can be distinguished from the guests in the
nonspherical cages, which retain an incompletely averaged
anisotropic line (this can be used to obtain θS/θL cage
occupancy ratios and thus calculate hydration numbers using
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the van der Waals and Plateeuw model, as described earlier72).
Upon cooling the system to the LT-regime, the effects are
dramatic, as the lines broaden and their features become
obscured due to the distribution of slightly different cages
(review Figure 2 again). Figure 3 illustrates this for str.I CO2
Figure 3. 13C NMR static lineshapes of CO2 in its str.I hydrate at 170
and 238 K. The dashed line shows the spectrum of the bulk CO2 solid at
77 K where there is no motion. Reproduced from ref 53. Copyright
2011 American Chemical Society.
hydrate.53,99,100 The 13C spectrum at 238 K is in the HT-regime,
which displays well-defined features characteristic of an axially
symmetric csa pattern that is reversed in sign and about 1/3 the
width of the line shape for a completely static CO2 molecule.
The 170 K line shape is in the LT-regime, where the
characteristic csa features are lost and the spectrum is
significantly broader.
The 238 K line shape can be analyzed to give more specific
details of the motion. Firstly, it shows that CO2 is reorienting
about the str.I large-cage axis and at orientations that are close to
the equatorial plane of the cage. A simple model would have the
molecule reorienting at a fixed angle of 21.3° with respect to the
plane, but it is also possible to fit the results with a model that has
a distribution of small angles relative to the plane. The latter
seems more reasonable in light of MD simulations discussed in
section 10. Analyzing the 170 K spectrum is more problematic,
as it is in effect a convolution of lineshapes averaged to different
extents because of the distribution of cage potentials in the LT-
regime; however, one possible model has the molecule librating
in a cone rather than reorienting about the cage axis with a
Gaussian distribution of librational amplitudes.53,99
In the HT-regime, the crystal symmetry dictates that the guest
must sample several equivalent positions within each cage.
Therefore, given a particular orientation, the dynamic averaging
over the equivalent sites can be calculated and compared with an
experimental line shape. This can be used to help guide the
refinement of the positions of guests in a hydrate crystal
structure to determine a solution that is compatible with both
the NMR line shape and the X-ray diffraction data, as was done
for the str.I TMO hydrate54 mentioned in section 7.
More recently, evidence for the transport of guests between
cages has been found from NMR experiments in a few special
instances: (a) H2 molecules in str.II hydrates are small enough to
pass through six-rings of cages fairly readily, less so through five-
rings, and thus show exchange between large cages but not
between small cages.101,102 (b) 13C and 2H NMR lineshapes of
CO2 and CD3F in their str.II hydrates, with THF in the large
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cage, show the expected anisotropic motion at temperatures a
little above 200 K, but then the lines collapse to isotropic at
higher temperatures. Since the small cage of str.II is not
spherical, the lineshapes must be anisotropic if the guest is
confined to the cage. The guests must therefore be able to
exchange between adjacent small cages, and the dynamic
averaging over the new orientations removes the residual
anisotropy. This requires a vacancy in an adjacent cage, and
since the molecules are too large to pass through the five-rings,
this requires the formation of vacancies in the water lattice,
apparently due to hydrogen bonding between the THF and
water.103,104 )c) In the str.H hydrate of CH4/CH3F/t-butyl-
methyl ether, the coalescence of pairs of lines in the 13C MAS
spectra corresponds to the two small guests in the two types of
small cage, indicating exchange between these cages that again
requires water vacancies due to hydrogen bonding with the
ether.104
10. MS7: COMPUTATIONAL STUDIES
The advent and ever increasing power and speed of computers
has enabled the burgeoning field of computational chemistry.
Simulations can yield many parameters for comparison with
experiments but perhaps more importantly can give insights into
aspects of observed behavior that would otherwise remain
obscure. Monte Carlo (MC) and molecular dynamics (MD)
simulations have found useful applications in many areas of
clathrate hydrate science, including determining guest-water
interaction terms for use in the van der Waals and Plateeuw
model, e.g., the first MC calculations in 1972;105 testing the
limits of the van der Waals and Plateeuw model;106,107
determining thermodynamic parameters;108,109 studying hy-
drate decomposition, nucleation, and phase transitions;110,111
determining lattice dynamics and phonon density of
states;112−114 determining mechanical properties such as
compressibility and high-pressure phases (see chapter 15 of
ref 8);115116 determining the relative stabilities of different
structures;117 investigating effects of hydrogen and halogen
bonding between the guest and the host;118−120 analyzing
anomalous thermal conductivity (below); and investigating
guest dynamics (below). The references given above are
examples and are by no means exhaustive for every topic, and
much other work can be found in recent reviews121−123,
including chapters 8 and 15 of ref 8). In this section, just two
topics will be discussed in more detail.
The first MD calculation of a hydrate was performed in 1983
to study the lattice dynamics and spectrum of str.I CH4
hydrate,112 and a similar calculation for str.II Kr hydrate
followed.114
MD played a vital role in elucidating the mechanism behind
the anomalous thermal conductivity of hydrates, which was first
discovered for the THF hydrate in 1981.124 In general, the
thermal conductivity of hydrates is only about one-fifth that of
ice;125 intriguingly, however, it increases in the 100−250 K
range with the increasing temperature, 126,127 which is
completely opposite to normal crystalline behavior and is
more like a glass.128 However, below 100 K the thermal
conductivity of small molecules such as Xe and CH4 increases
with the decreasing temperature down to about 50 K before
decreasing again to the lowest temperatures. For larger
molecules such as THF and 1,3-dioxolane, in the 50−100 K
region there is little change in the thermal conductivity before it
decreases again below 50 K.127
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A resonant phonon scattering model was developed that can
explain the glass-like behavior.129 Heat transport in crystals is
mainly carried by low-frequency acoustic lattice modes
(phonons). At some point in the Brillouin zone the acoustic
modes would cross the localized rattling modes of the guest, but
because of the crystal symmetry and quantum mechanical
noncrossing rules the crossing is avoided at the point where the
acoustic modes reach frequencies similar to the rattling mode130
(see Figure 4). Energy exchange between the host and the guest
Figure 4. Schematic of avoided crossings in the Xe hydrate. In the
Brillouin zone, the acoustic lattice phonons LA and TA are dispersed
instead of following the dashed lines, as they near the rattling modes of
Xe. Reproduced from ref 130 with permission from IOP Publishing Ltd,
copyright 1994.
is then possible, which causes the interruption or dissipation of
the heat flow through the lattice. Rattling motions have been
identified using neutron scattering,131 and there is experimental
evidence for the avoided crossing.132,133 Several MD simulations
were used to calculate thermal conductivities.134−137 The results
for the CH4 hydrate were in semiquantitative agreement with
experiment. By analyzing the heat flux and local energy
correlation functions from nonequilibrium MD calculations, it
was shown that the water framework itself and the guest−host
interactions contribute to thermal transport processes. There-
fore, the lower thermal conductivity in hydrates relative to that
in ice Ih is partly due to differences in their crystal structures, but
the glass-like temperature behavior is governed by the guests and
their collisions with the host. The latter causes the dephasing of
the heat-carrying acoustic phonons of the lattice, resulting in the
localization of energy and the inhibition of heat transport (see
chapter 15 of ref 8).138−141
MD can also be used to look at the reorientational motion of a
guest within a cage. As shown in Figure 5, CO2 has been
simulated in the large cage of str.I at several temperatures.142 At
77 K, the long axis of the molecule samples many positions about
the cage symmetry axis, but it is oriented close to the equatorial
plane. As temperature increases, it is able to make greater
angular excursions from the plane. 13C NMR lineshapes were
simulated by averaging the experimental CO2 static chemical
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Figure 5. MD snapshots of CO2 orientations in a large str.I cage at 77,
150, and 238 K. The carbon atom positions are superimposed at the
center of each figure to show the distribution of O atoms. Reproduced
from ref 142 with permission from John Wiley and Sons, copyright
2008.
shift tensor over the distributions of orientations, and the results
compared very favorably with the experimental lineshapes.99
11. MS8: THE DISCOVERY OF STRUCTURE H (HS-III)
AS IT HAPPENED
The discovery of structure H9 was very important in that it
uncovered a new class of clathrate hydrate structure which, like
str.I and str.II, formed with numerous guests, many of them
hydrocarbons. Although there are structures outside these three
classes, they are typically known for only one specific guest, e.g.,
tetragonal Br2 hydrate.50 The discovery was also a good example
of the convergence of a number of techniques and ideas in
solving a problem.
In 1986, John Ripmeester was looking for new str.II guests to
try to determine the upper size limit for guests in the 51264 cage.
This involved making hydrates with help gases (H2S and Xe
being the most convenient), since these helped stabilize the
structures of the largest str.II guests. He noticed that he was still
forming solids with a few molecules that were calculated to be
too large for str.II; the expectation had been that these would not
form a hydrate. Was this a new clathrate structure? The clathrate
hydrate group at the NRC was not equipped at the time to do
low-temperature single-crystal X-ray studies, so other techni-
ques were used to determine the most probable structure.
Following the introduction of cryomagnets and Fourier
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transform pulse spectrometers for NMR in the later 1970s, solid-

state 2H NMR lineshapes were increasingly utilized to study
dynamics of molecules, and in the early 1980s 129Xe NMR was
being developed as a probe of pore spaces.3,83,143,144 A highly
polarizable electron cloud makes Xe very sensitive to its
environment. Both these new tools were brought to bear on
the new hydrates.
11.1. 2H NMR. Hydrate solids made from four deuterated
large molecules with the H2S help gas were investigated using 2H
lineshapes. Two of these had to be synthesized in-house with
deuterated CD3 groups. An isotropic 2H NMR line shape
indicated that cyclohexanone-2,6-d4 reoriented rapidly in a
pseudospherical cage, presumably the str.II large cage. In
contrast, the 2H NMR lineshapes observed for methyl-
cyclohexane-d14, t-butyl-methyl-d3 ether, and pinacolone-d3 (t-
butyl-methyl-d3 ketone) had doublet structures indicating that
these molecules reoriented anisotropically and were therefore in
large nonspherical cages, thus confirming that these hydrates
must have a new structure.9 Furthermore, the degree of line
narrowing of the CD3 groups indicated that the longest axis of
each molecule reoriented about an axis of the cage at a small tilt
angle.
11.2. 129Xe NMR. It had already been found that 129Xe NMR
gave quite distinct spectra for Xe in str.I and str.II hydrates, and
with data from other types of clathrates a linear relationship
between the increasing isotropic NMR chemical shift and the
decreasing cage size was becoming apparent.144 Furthermore,
the 129Xe csa lineshapes had been found to depend on the crystal
symmetry of each type of cage. The new hydrate of methyl-
cyclohexane with Xe as help gas revealed a unique static
spectrum, which was quite distinct from those of str.I and str.II, Figure 6. Characteristic 129Xe NMR static lineshapes for str.I, str.II, and
in the shift range corresponding to Xe in small cages. The str.H at 77 K. (Top) Pure Xe str.I. (Middle) Xe/butane str.II. (Bottom)
characteristic lineshapes of all three structural types are Xe/bicyclo[2.2.2]oct-2-ene str.H. Reproduced from ref 145. Copyright
illustrated in Figure 6, and chemical shifts are given in Table 1990 American Chemical Society.
2. 129Xe MAS resolved two lines with different intensities. These
lines overlapped in the static spectrum, but it was clear that they Table 2. Typical 129Xe NMR Isotropic Chemical Shifts (δiso)
both showed chemical shift anisotropy; therefore, both types of and Anisotropies (Δ) of Xe in the Cages of Structures I, II,
small cages were nonspherical, again providing confirmation of a and H Clathrate Hydrates
new structure.
structure cage δiso (ppm) Δ (ppm) ref
Thoughts then turned to possibilities for this new structure,
and there was one very obvious choice: clathrasils. Clathrate str.I 512 242 0 9, 145
frameworks built with silica units SiO2, clathrasils were also Xe 51262 152 21
being studied at about the same time. Two of these clathrasils, str.II 512 231 16 9, 145
melanophlogite147 and dodecasil-3C,148 were isostructural with Xe/C3H8 51264 80 0
str.I and str.II hydrates, and the 129Xe spectra of Xe in dodecasil- str.H 512 231 13.7 9, 146
3C and str.II were very similar.144 The structure of a third Xe/t-butyl-methyl-ether 435663 212.4 31.4
clathrasil, dodecasil-1H with a hexagonal unit cell and space 51268a
a
group P6/mmm, had an even larger cage together with two types No signal was seen for Xe in the large cage of str.H.
of small cages.149 Therefore, a hydrate analogue of this seemed
like a logical candidate structure for the new hydrate. Other
structures considered were some suggested earlier in Jeffrey’s match for an analog of dodecasil-1H. The final confirmation
classification of hydrates.4,150 came from a comparison of cell constants. The cubic unit cell
11.3. Powder Diffraction Studies. Neutron powder parameters of str.I and str.II hydrates are smaller by a factor of
diffraction studies performed of t-butyl-methyl ether/H2S/ 0.898 than those of their isostructural clathrasils. This reflects
D2O hydrate at 5 K and PXRD studies of methyl-cyclohexane/ the difference in the lengths of the O−H−O and Si−O−Si
H2S/H2O at 210 K were then carried out, revealing a primitive linkages in the frameworks. When this scaling factor was applied
hexagonal cell compatible with three Laue symmetries, namely, to the dodecasil-1H cell parameters, the resulting numbers were
3̅m1, 6/m, and 6/mmm. Two of these corresponded with in very close agreement with the experimental values for the new
Jeffrey’s hypothetical structural types IV and V. These could be hydrate.
eliminated, however, as it appeared unlikely that they had cages Thus, all the NMR and powder diffraction results were
large enough for some of the new guests and, as a bigger completely compatible with the new hydrate being isostructural
problem, their unit cell parameters did not compare well with with dodecasil-1H, with a space group of P6/mmm and a
the new results. The 6/mmm Laue symmetry was an obvious formula for the cage framework of (512)3·(435663)2·(51268)·
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34H2O. The large guests could fit into the new 51268 cage, and
Xe, H2S, or CH4 could fit in the two small cages (see Figure 7).
Figure 7. Interconnected cages in structure H. The large 51268 cage
(left) shows t-butyl-methyl ketone (pinacolone) in one of its disordered
symmetry-equivalent positions, with a short guest−host O−O distance
of 2.96 Å (red line) indicative of a hydrogen bond. The two types of
small cages, 512 (top) and 435663 (right), contain H2S “help” molecules.
Reproduced with permission from ref 57.
In this manner, structure H appeared on the stage of hydrate
science.
In hindsight, John Ripmeester may have produced a structure
H hydrate in 1977 while studying the methyl group tunneling of
molecules isolated in clathrate hydrate cages.151 He looked at
ethyl iodide CH3CD2I in what he assumed at the time to be an
enlarged str.II hydrate−he recognized that the largest van der
Waals diameter of this molecule (7.1 Å) was longer than the
accepted free diameter of the large cage of str.II (6.6 Å).
Whether or not this guest forms str.II or str.H has not been
determined. Additionally, hydrates of three large guest
molecules with H2S synthesized by de Forcrand in 1883 were
probably str.H: CH2ClCCl3, i-C4H9Cl, and i-C4H9Br16
2
H and 129Xe NMR were then used to find a large number of
new guests that formed str.H hydrates and a few more str.II
hydrates.145 In all cases, a small help gas was necessary. The
static 129Xe NMR line shape became a very characteristic marker
for str.H. New str.H guests continue to be reported, e.g., bromo-
cyclopentane and bromocyclohexane152
It was not until 1996 that a single-crystal X-ray structure
determination provided the ultimate confirmation of the P6/
mmm structure.153 The crystal came from a sample made in a
sealed tube during the early exploration of str.H formers (2,2-
dimethylpentane/Xe/H2S/H2O). Initially the powder sample
had been stored in liquid N2, but it was later transferred to a large
freezer where it was stored at −20 °C for at least six years. Very
good quality single crystals with few defects had grown on the
tube walls during this lengthy period of annealing. It was even
possible to locate half H atoms in their disordered positions in
the O−H−O hydrogen bonds of the water framework.
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Besides the large 51268 cage, another feature of str.H that
stands out is the small 435663 cage with its four-sided faces. The
90° O−O−O angles of the four-rings are a long way from the
tetrahedral angle ideal for H-bonding coordination in water, and
although the half H atoms are positioned off the O···O edges, the
ring is clearly strained. One might question whether this makes
the water molecules in the four-rings more susceptible to bond
breaking and reorientation. This could be a question for a future
investigation.
A few more single-crystal XRD studies of str.H followed for
large guests methyl-cyclohexane,154 pinacolone,56,57 and cyclo-
octane.155 The cyclooctane hydrate is unusual in that it
transforms into a lower symmetry form below 167 K. PXRD
with direct space methods was used to obtain crystal structures
of str.H with the large guest methylcyclohexane and a mixed
str.H t-butyl-methyl ether/neohexane.156
Str.H with its ability to contain larger hydrocarbons along
with CH4 was soon of interest to the oil and gas community, and
studies of phase equilibria and kinetics of formation and
decomposition followed.73,74,157−159 The occurrence of str.H in
nature was confirmed in the early 21st century (see below).
More recently, ionic str.H hydrates have also been made: (1)
diethyl-dimethyl-ammonium hydroxide ionic str.H, where the
OH− anion substitutes one H2O in the framework and the cation
fills the 51268 cage,160 and (2) solid-solution frameworks made
from NH4F/H2O were found for all three structural classes,
where NH4+ and F− could substitute two water molecules up to
roughly 20% of the framework.161
12. HOST−GUEST INTERACTIONS
At the fundamental level, clathrate hydrates are all about host−
guest interactions, which determine their structure, stability and
properties. van der Waals forces affect all guests, and in the
absence of other interactions the structural type will in general
be determined by whether the largest guest will fit into the
largest cage in the structure, i.e., whether repulsive overlap can
be avoided between the atoms of the guest and the cage as
defined by their van der Waals radii. There are cases where the
molecule can fit, but a help gas is required in the smaller cages to
form a stable hydrate, i.e., some of the largest str.II guests and all
large str.H guests. There are some double hydrates, whose
largest guest on its own would form str.I, that form str.I or str.II
depending on the guest ratio, e.g., Kr/Xe,162 where pure Xe
would form str.I and pure Kr would form str.II. Even more
intriguing is the case of the CH4/C2H6 double hydrate, where
both guests on their own form str.I but for some ratios the
double hydrate is str.II.163,164 Note that in both cases the two
guests can fit into 512, 51262, and 51264 cages. These cases point to
the subtle interplay of the different cage−guest interactions that
contribute to the overall stability of str.I or str.II and determine
which is the more stable for different compositions. For a recent
plot and discussion of the guest size−structural type relation-
ships, see chapter three of ref 8.
Another interesting aspect of this size issue is the observation
that if the guest molecule has conformational flexibility it may
adapt a conformation that allows it to fit more easily into the
space of the cage. The lowest-energy conformation of the
molecule in the free state may be such that it would encounter
strong repulsive forces with the cage walls (put simply, too large
to fit), but a higher energy conformation may have much weaker
interactions. The higher energy of this second conformation
must be offset by the lower interaction energy. Examples include
n-butane165 and 1,2-dichloroethane,166 which have a gauche
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conformation in the str.II large cage rather than trans in the gas
phase, as well as tetrahydropyran in str.II large cages154 and large
guests in str.H.167
Hydrogen bonding is another important interaction. This has
long been thought to cause the lower-temperature reorientation
of the host water molecules in hydrates with oxygen- or
nitrogen-bearing guests by generating Bjerrum defects. Modern
crystallography has indeed found evidence of this in several
structures with O−O or N−O distances shorter than the sum of
van der Waals radii and small associated cage distortions, e.g., in
CO2 in the small cage of str.I (chapter five of ref 8), t-butyl
amine/Xe/H2S str.II, and pinacolone/H2S str.H.56 MD
simulations of these and other guests have also been used to
study the hydrogen bonding and formation of Bjerrum
defects.168−170 This is clearly an important interaction, and in
addition to its effect on the cage framework it also influences the
guest orientation. Surprisingly, methanol has been found to act
as a co-guest in small amounts in THF str.II and propane str.I
hydrates at temperatures below about 240 K.171 Here the OH
group of the methanol actually replaces a water molecule in the
small cage wall and forms a strong hydrogen bond with the water
network, distorting the cage and neighboring cages. Ammonia
too can act as a guest, even forming a str.I pure NH3 clathrate
that is stable below about 150 K. As a coguest in str.II THF, the
crystal structure shows a cage water molecule pulled toward the
NH3 that forms a hydrogen bond and breaks a bond to an
adjacent water, thus distorting the cages.172
More recently, unusual interactions between Cl2 or Br2 and
cage atoms have been discovered that may be classed as halogen
bonding. Modern X-ray techniques have allowed the determi-
nation of the positions of Cl2 and Br2 molecules in clathrate
cages.57,120 Both molecules are found in cages for which they
would be considered much too large to fit based on their van der
Waals lengths. There are Br−O contacts in 51262 cages as much
as 0.46 Å shorter than the sum of van der Waals radii; similarly,
there are Cl−O contacts in 512 cages as much as 0.37 Å shorter.
Even in the larger cages, such as Br2 in 51263 and Cl2 in 51262, the
halogens sit closer to water O atoms than the sum of van der
Waals radii. This interaction is clearly stronger than the van der
Waals forces.
13. GLIMPSES INTO FORMATION PROCESSES
Unfortunately, there is not room in this review to cover the topic
of the kinetics of formation and dissociation of hydrates, but the
interested reader is referred to chapter 14 of ref 8. However, we
will touch upon investigations of the microscopic processes of
hydrate formation.
One approach to observing the formation of the Xe hydrate
was to create an intimate mixture of Xe and H2O in an
amorphous state by depositing vapor onto a coldfinger at very
low temperatures and then observe the development of structure
as the sample was annealed at progressively higher temper-
atures.173 The initial amorphous mixture had a very broad,
featureless 129Xe NMR spectrum representative of a wide range
of Xe environments. By 147 K, a side feature began developing in
the same chemical shift range as that for Xe in small cages. As the
sample was still amorphous, this indicated that the Xe was
probably surrounded by a cluster of about 20 water molecules.
At 175 K another feature corresponding to a larger cluster began
to show just before the sample crystallized at about 180 K.
During the 1980s, an optical pumping method was developed
to increase the nuclear spin polarization of Xe by several orders
of magnitude over its equilibrium thermal polarization. The
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resulting immense NMR sensitivity of this hyperpolarised (HP)
Xe made it possible to observe the reaction of HP Xe gas with
powdered ice in real time by taking single 129Xe NMR scans in
rapid succession (Figure 8).174 In the very early stages of the
Figure 8. Time dependence of the hyperpolarized 129Xe NMR spectra
following the introduction of HP Xe gas at 580 mbar to powdered ice at
243 K. Reproduced from ref 174. Copyright 2001 American Chemical
Society.
reaction 0−30s, once weak signals could be detected in the small
and large cage regions of the spectrum, the ratio of large and
small cages (L/S) was roughly equal. This was taken to be a
prenucleation stage where species were self-assembling in
roughly equal numbers. From 30 to 100 s the L:S ratio rose
quickly to about 3.5, which was taken to indicate an increase in
the number of crystalline nuclei while prenucleation species
continued to form. The signals were still weak at this time but
then began to increase rapidly as the bulk hydrate formed. At
300 s the growth rate declined, and as time progressed the ratio
approached the equilibrium ratio of 4.
These two experiments give a glimpse of the microscopic
processes, and there have also been numerous simulations
probing nucleation and growth.111,175−178
It may also be relevant that metastable str.II hydrates have
been seen during the early stages of hydrate formation and
annealing,50,179 showing that different structural types can occur
under nonequilibrium conditions and perhaps hinting at the
presence of multiple prenucleation cage types in the very early
stages of formation.
14. NATURAL CLATHRATE HYDRATES
14.1. Hydrocarbon Hydrates. Natural occurrences of
clathrate hydrates were not discovered until the second half of
the 20th century, although the possibility of their presence in
conjunction with natural gas sources was contemplated in
1946.180 They were first reported to exist in the permafrost
regions of Siberia (Messoyakha gas field) in 1965. 181
Exploratory drilling in 1972 indicated the presence of hydrates
beneath the permafrost of the Mackenzie delta in Canada,182
and seismic exploration showed bottom simulating reflections
(BSRs) indicative of hydrates in marine sediments on
continental margins (reported in 1971183). The first physical
observation of a solid natural hydrate was in 1974 in samples
from the Black Sea, found 6.5 m below the sea floor at a water
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depth of 2000 m,184,185 and there have been numerous
recoveries from coring since. Marine outcrops of massive
hydrates do occur, and in 2000 a fishing boat working off
Vancouver Island brought up a large frothing mass of hydrate in
a trawl net from a depth of about 800 m.186 The hydrate stability
zone depends on having the right conditions of pressure,
temperature, and concentration for the particular gas
composition. These in turn depend on the depth, the
temperature of the overburden, the geothermal gradient, and
the gas source.187,188 Most of the hydrates from permafrost and
continental slope regions appear to be mainly methane str.I, with
small amounts of other small molecules, and the gas is of
biogenic origin.188−190 Hydrates from areas associated with oil
seeps, however, have a different composition with numerous
higher hydrocarbons as well as methane and thus are usually
str.II,191 sometimes with str.I or str.H.192 These hydrocarbons
are usually of thermogenic origin. Analyzing the gas composition
gives a good idea of the likely structural type, but definitive proof
comes from X-ray structural analysis and 13C CP/MAS NMR
spectra of recovered samples. The first comprehensive
laboratory study of a sample recovered intact (from the Gulf
of Mexico193) was carried out in 1986 by Davidson et al.191
PXRD showed only str.II, and 13C NMR gave signals from
methane as well as ethane, propane, and isobutene in both large
and small cages of str.II. In addition to these hydrocarbons, gas
analysis showed appreciable amounts of CO2, N2, and H2S along
with very small amounts of n-butane, neopentane, isopentane,
and cyclopentane; methane constituted 66% by volume. The
isotropic 13C NMR chemical shift of CH4 increases as the cage
size decreases (much like 129Xe NMR), Table 3, and thus the
CH4 region of a magic angle spinning spectrum can be used to
determine which hydrate structures are present in a sample (ref
194 and Table 11.1 of ref 8).
Table 3. Summary of 13C Isotropic Chemical Shifts (ppm) of
CH4 in Gas Hydratesa
structure cage shift range
12
str.I 5 −4.1 to −4.4
51262 −6.5 to −6.8
str.II 512 −4.3 to −4.7
51264 −8.2 to −8.3
str.H 512 −4.3 to −4.5
435663 −4.7 to −4.9
a
Relative to reference TMS at 0 ppm. Condensed from Table 11.1 of
ref 8
Although natural str.H was implied from the presence of iso-
pentane in a hydrate sample from the Gulf of Mexico in 1994,195
definite proof came in 2006 with PXRD and 13C NMR analysis
of a sample from the Cascadia Margin off Vancouver Island,
which contained seven different str.H guests192
Initial estimates of the amount of gas locked in hydrate
deposits globally were vast, as high as 3 × 1018 m3,196 which is
much greater than all other hydrocarbon resources combined,
but with time and increasing knowledge the estimates have
declined (e.g., ∼3 × 1014 m3 in 2011197) until now the estimates
of the potentially recoverable amounts of gas from hydrate
deposits stands at (15−63) × 1012 m3.198
14.2. Air Hydrates. Besides the major deposits of natural
hydrocarbon hydrates, there are also natural occurrences of air
hydrates. These have been found deep in the ice caps of
Antarctica and Greenland. The gradual disappearance of air
pubs.acs.org/EF Review
bubbles in deep Antarctic ice cores was first reported in 1968,199
but it was Miller200 who realized, based on the dissociation
pressures of N2 and O2 hydrate, that this probably indicated the
presence of air hydrates. Then, in 1982, Shoji and Langway
observed the sudden release of gas when they melted ice cores
from Greenland.201 Raman signals of the enclathrated O2 and
N2202 and X-ray diffraction from crystals203 provided the
definitive evidence. Research has continued, and very recently
argon was found in small amounts in an air hydrate.204
14.3. Extraterrestrial Hydrates. The presence of clathrate
hydrates beyond the Earth also seems highly probable but has
not yet been proven. The existence of CH4 and CO2 hydrates in
comets and interstellar grains was postulated in 1952 by
Delsemme and Swings.205 Miller later considered the likelihood
of hydrates involving H2, CH4, H2S, C2H6, C2H4, C2H2, and
CO2 being present on the outer planets and their moons where
temperature and pressure conditions were suitable206 and
suggested that CO2 hydrate existed in the polar caps of
Mars.207 Planetary scientists now suggest that clathrate hydrates
may play an important role in the surfaces and internal structures
of planetary bodies and their satellites, Consequently, knowl-
edge about various gas hydrates, and especially their high-
pressure forms,208,209 has become very important for planetary
models. Recent interest has focused on bodies visited by space
probes, e.g., methane and ethane hydrates on Saturn’s moon
Titan,210,211 and subsurface oceans capped by methane hydrate
layers have been suggested for Saturn’s moon Enceladus212 and
the dwarf planet Pluto.213 Since NH3 is thought to be abundant,
the possible involvement of this gas in mixed clathrate hydrates
on the planets and moons also should be considered.172
15. HYDRATES IN THE OIL AND GAS INDUSTRY (IN
BRIEF)
Gas hydrates are of course of great interest to and a major
concern of the oil and gas industry. They first came to attention
in 1934 when Hammerschmidt realized that hydrates rather
than ice were the culprits in pipeline blockages in cold
conditions214 and suggested using methanol as a thermody-
namic inhibitor, since it shifts the phase equilibrium line. Ever
since, a great deal of effort has been expended to understand the
conditions in which hydrates can form, both from the
engineering aspect and in the natural environment, and to find
ways to prevent hydrate formation and safe methods for clearing
hydrate blockages when they do happen using phase equilibria
knowledge, predictive software such as CSM Gem,215 both
thermodynamic (methanol and glycols)216,217 and kinetic
(polyvinyl pyrrolidone and antifreeze proteins) inhibitors, and
studies of formation and decomposition.159,218 The book by
Sloan and Koh6 and publications on flow assurance219,220 cover
many aspects of this in detail.
Drilling in marine environments and through hydrate beds
poses engineering problems. The Deepwater Horizon disaster
was a prime example of a major accident caused by hydrates. The
latest analysis suggests that gas hydrate plugs had formed in the
drill system some time before the accident and that the initial
explosion was caused by the sudden release of a plug.221
Additionally, some of the initial attempts to funnel and collect
the escaping gas and oil failed because hydrates formed and
blocked the funnel.
The discovery of natural gas hydrate deposits and estimates of
potentially recoverable gas were mentioned earlier. It was
thought for many years that gas production at Messoyakha in
Siberia came from gas hydrates, but this has been questioned222
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Energy & Fuels
based on accumulated evidence, and it may be that the source of
gas was just free gas beneath hydrate beds. Otherwise, there are
no other current sites producing gas from hydrates commer-
cially. However, there have been several projects over the last
two decades where test wells have been drilled to investigate
methods of gas production in both permafrost and marine
environments, such as at Mallik in the Mackenzie Delta, Canada
in 1998, 2002, 2007, and 2008;223−225 on the Alaska North
Shore, USA, in 2011 and 2012;226−228 in the Nankai Trough
offshore Honshu, Japan in 2013 and 2017;229 and in the Shenhu
area of the South China Sea in 2017, 2019, and 2020.230 The
wells produced mainly CH4, usually by depressurising, some-
times with thermal stimulation, but the 2012 Alaska test used
CO2/N2 injection to replace the CH4 with CO2. Recovery
methods have recently been reviewed.231,232 CO2 sequestration
in hydrate form is promoted as a possible medium for reducing
emissions into the atmosphere.233
16. PRACTICAL INTERESTS
Apart from the exploitation of natural hydrates as a potential fuel
source, people have been finding and proposing other uses for
hydrates almost since they were first discovered. In 1823,
Faraday decomposed chlorine hydrate in a sealed tube to obtain
liquid chlorine for the first time.234 Such uses include the
following: isolating unstable species, e.g. ClO2235 and O3;236 the
storage and transport of natural gas (there are about 160
volumes of gas for 1 volume of hydrate);237,238 gas separations,
e.g., CO2 from flue gas;239 desalination;240−242 the concen-
tration of aqueous waste materials;243 CO2 sequestration, e.g,.
by replacing CH4;244 cold energy storage (using excess
electricity in off-peak periods to produce hydrates that can
then be decomposed for air-conditioning cooling during high-
peak periods); and hydrogen storage,245,246 especially for use in
vehicles powered by fuel cells. (see chapter 16 of ref 8 for more
details)
17. FUTURE WORK
It is certain that work will continue, especially in technical and
engineering aspects, in such areas as hydrate prevention and flow
assurance, in situ hydrocarbon extraction methods, CO2
sequestration, and storage and transport of gases, all of which
have economic or environmental interest. As far as molecular
level research is concerned, a few interesting topics come to
mind.
Details of the nucleation and growth of hydrates are still
lacking, requiring new experimental probes.247 In connection
with this, the mechanism of the memory effect is still not settled.
The possibility of gas nanobubbles remaining in the liquid after
hydrate decomposition seems reasonable. Nanobubbles con-
taining several atmospheres of guest gas pressure, which are
stable for a reasonable length of time, could be centers for
nucleation. Uchida et al. have done experiments to show the
presence of ultrafine bubbles (UFBs) with micro- and nanosized
bubble distributions in decomposed hydrate solutions (of CH4,
C2H6, C3H8, and CO2 clathrate hydrates).248−251 They also
demonstrated that such liquids have higher nucleation
probabilities and lower induction times for hydrate formation
compared to those for fresh water. Additionally, UFB solutions
prepared with fresh water using a generator behave in much the
same way for enhanced hydrate formation. Very recently, Cheng
et al. also found that nanobubbles enhanced methane hydrate
nucleation.252 This all suggests that such bubbles play a role in
pubs.acs.org/EF Review
the memory effect. Whether this is the only factor is unclear, and
it would be very interesting to find probes to determine what is
happening at the molecular level.
The topic of intercage transport has barely been touched. Two
cases were mentioned earlier,103,104 and there it appears that O-
bearing guests enhanced the breaking and formation of bonds in
the cage walls through transient hydrogen bonding, causing
defect formation. There are other ways of introducing defects.
Suga253 showed that doping a small amount of KOH into
hydrates accelerated the reorientation of the water molecules
(OH− substituting into the lattice, thus creating H vacancies)
and led to a hydrogen ordering transition at very low
temperatures (at 46.6 K for acetone str.II doped with KOH at
1.8 × 10−4 mole fraction). It would be worth investigating if this
also enhanced exchange of guests between cages. There is also
potential for further work on CH3OH and NH3 inhibitors acting
as guests. These distort the water framework more strongly than
O-bearing guests through hydrogen bonding and the sub-
stitution of the hydroxyl in the framework, thereby introducing
defects.
As for possibilities for new structures, there may be other
unique structures to be found for odd-shaped molecules and
hydrogen bonding situations. One could look for more analogs
of clathrasils or zeolite structures, e.g., clathrasil DD-3R,254 and
sodalite (the latter is already known in the high-temperature
structure of the ionic semiclathrate (CH3)4NOH·5H2O255). We
might speculate whether there could be a fourth major class of
clathrate hydrate structure stabilized by guests too large for str.H
with suitable help molecules in any small cages. This might pose
problems in finding ways to bring the guest and water together,
as the potential large guest materials may be solids in their bulk
form, although str.H has formed with the volatile solids
adamantane, hexamethylethane, and hexachloro-ethane.145
Cages larger than the 51268 cage of str.H would probably also
need to have some larger rings.
18. IN CONCLUSION
I hope this short review has given the reader a good cross-section
of most aspects of the canonical clathrate hydrates, which have
had a rich history of research for over 200 years. Of course the
related topic of the structurally related semiclathrate hydrates
and ionic hydrates (including salt hydrates and acid and base
hydrates) has barely been mentioned here, and these too
provide a broad area of research. I am sure hydrates will continue
to surprise us as research continues, probably for many years to
come.
■ AUTHOR INFORMATION
Corresponding Author
Christopher I. Ratcliffe − National Research Council of
Canada, Ottawa, ON K1A 0R6, Canada; orcid.org/0000-
0002-0610-7445; Email: chris.ratcliffe@bell.net
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.2c01723
Notes
The author declares no competing financial interest.
Biography
Chris Ratcliffe received his B.Sc and Ph.D. Chemistry from Durham
University, UK. He joined the National Research Council (NRC) of
Canada in 1982, becoming Senior Research Officer and finally a
Program leader. He is currently a Volunteer Visitor at NRC. He worked
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Energy Fuels 2022, 36, 10412−10429
Energy & Fuels pubs.acs.org/EF
on clathrate hydrates throughout his career at NRC. His principal
expertise is in multinuclear solid-state NMR, and his interests
encompass molecular dynamics and disorder in solids, clathrate
hydrates, host−guest materials, nanoparticles, nanoconfined materials,
and hydrogen storage.
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