Mendeleev Commun.

, 1999, 9(5), 209–210

Clathrate hydrates of hydrogen and neon

Yuri A. Dyadin,* Eduard G. Larionov, Andrei Yu. Manakov, Fridrich V. Zhurko, Evgeny Ya. Aladko,
Tamara V. Mikina and Vladislav Yu. Komarov
Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russian Federation.
Fax: +7 3832 34 4489; e-mail: clat@che.nsk.su

At pressures up to 15 kbar, hydrogen and neon were found to form classical clathrate hydrate structures, whereas argon and
krypton, already known as polyhedral clathrate formers, can also form hydrates based on the ice II framework at high pressures.

Small hydrophobic molecules (including monoatomic molecules)

are known to form clathrate hydrates; these molecules can be 80 H2–H 2O system, this work
subdivided into two different groups. The smallest molecules, H2–H 2O system, ref. 9
hydrogen, helium and neon, all of linear dimensions less than Ne–H 2O system, this work
3.5 Å , constitute a group that can be incorporated into the small 60
cavities in the lattices of ices Ih, Ic and II, thus forming solid
solutions or clathrates very similar to the original ice frame-
works.1– 3 Thus, they are not known to form clathrates based 40
on polyhedral structures. The second group includes substances blg

T/° C
with larger molecular dimensions of 3.8 to 9.2 Å . These do alg
20 i6I
not dissolve in ice frameworks, but form polyhedral clathrate hlg
structures, the best known of which are classical cubic struc-
tures I and II (CS-I and CS-II), and a hexagonal structure H 0
(HS-III).4,5
A study of phase diagrams of the (Ar, Kr, Xe)–H 2O systems i5I metastable continuations of the curves
at pressures up to 15 kbar showed6– 8 that these gases can –2 0 i1hI i 3I
form classical clathrate hydrates, which are stable in a wide
temperature and pressure range. However, in argon and krypton 0 4 8 12 16
systems at pressures above 9.6 and 13.4 kbar, respectively, we P/kbar
found new hydrate phases, which are quite dense judging from
the fact that their decomposition temperatures rapidly increase Figure 1 Decomposition curves of hydrates formed in the water–hydrogen
and water–ne on systems. Melting curves of ices (inl) are given for
with pressure. This high-density packing is impossible in the comparison: (a) solid solutions of gases in ice Ih, (b) hydrates of the
case of typical clathrate structures where a single guest molecule respective gases based on the ice II crystal framework, (h) classical
occupies one cavity in a hydrate framework.† clathrate hydrate phase, (l) liquid phase, (g) fluid phase.
Here, we report the results of studying phase equilibria in the
neon–water an d hydrogen– water systems. All of the experiments curves to decomposition of the classical hydrogen and neon
were carried out by differential thermal analysis in an excess of clathrates. Figure 2 shows the decomposition curves of hydrate
gas. The approximate gas– water molar ratio was 6:1, while the phases in the (Ar, Kr, Xe)–H 2O systems6– 8 and those of the
ratio between the components in classical clathrates and ice II systems under discussion. It is evident that in the systems with
structures when every cavity was occupied by one guest molecule hard noble gases the decomposition curves of classical structure
was inverse. The temperature was measured with a Chromel– hydrates (solid lines) are top-shaped, and their sizes regularly
Alumel thermocouple, and the pressure, with a Manganin decrease from xenon to argon hydrate, i.e., with a decrease in
manometer. The experimental technique was described in detail the guest molecule radius. The hydrogen and neon systems are
elsewhere.6– 8 adequately described by this scheme. Kuhs et al.11 showed that
The results are shown in Figure 1. In both cases, the initial every two nitrogen molecules can occupy a large cavity in CS-I
portions of the curves (lines aIg) represent decomposition of and CS-II. This is even more true of the equilibrium in the case
solid solutions of the gases in ice Ih. 1 In our case, this manifests of hydrogen and neon molecules.12 The presence of more than
itself in a slight increase in the decomposition temperature of one guest molecules in a cavity, and slow diffusion of hydrogen
the solid solution as compared to the ice melting curve. The and neon molecules in the already formed solid compound can
final portion of the curve (line bIg) in the hydrogen-containing result in rather slow establishment of equilibrium in the case of
system corresponds to decomposition of the hydrogen hydrate classical hydrate formation.
H2·6H2O with the ice II framework.3,9 Note that in both portions Figure 2 shows that in all of the systems (except for the
of the P– T curves the equilibrium was established rapidly (in xenon system), in addition to the group discussed above, there
about 20 min), and the results were well reproducible. is a group characterised by similar curves, which go up steeply
The most complicated and interesting behaviour is observed with increasing pressure (dashed lines). An X-ray study of the
in the pressure ranges from 1.0 to 3.6 kbar for hydrogen and compounds formed in the water– hydrogen system showed that
from 1.9 to 3.7 kbar for neon systems (lines hlg). In both cases, this curve branch corresponds to decomposition of a hydrate
the equilibria were attained very slowly (in several hours or phase based on the ice II framework. Similar decomposition
longer). It is reasonable to suppose that, really, equilibrium curves for the systems strongly suggest that, at pressures above
states were not achieved in some experiments. The results can 4 kbar in the neon system, 9.6 kbar in the argon system, and
be reproduced only with a high excess of gas. We assign these 13.4 kbar in the krypton system, hydrates based on the ice II
structure are formed. For argon and krypton molecules to be
† It is reasonable to consider the above hydrates as belonging to the arranged in ice II channel cavities, a slight elongation of
same group because, provided that all the cavities are occupied by the hydrogen bonds is required, which is quite realistic. Let us
same guest, their packing coefficients k6,10 are similar. For instance, for recall that, when the self-clathrate ice VII is formed (two ice Ic
the CS-I xenon hydrate, k = 0.584; for the hypothetical xenon hydrates frameworks penetrate into each other) at pressures above 20 kbar,
of other structures, they vary from 0.55 to 0.58, i.e., they are appreciably the hydrogen bond length increases from 2.76 to 2.96 Å .13
lower than in the case with the densest packing (k = 0.74). Therefore, the
effect of pressure on them should be very similar.
Thus, classical clathrate hydrates are formed in aqueous neon,

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 Mendeleev Commun., 1999, 9(5), 209–210

References

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Figure 2 Decomposition curves of hydrates formed in the (Xe, Kr, Ar, H2, Proceedings of the 2nd International Conference on Natural Gas
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given for comparison.

hydrogen, argon, krypton and xenon systems. Their stability

decreases in the order from xenon to neon. In the first four
systems, hydrates are formed on the basis of ice II, and the
larger the guest molecules, the higher the pressure required for
their formation. A xenon molecule appears to be too bulky to be
arranged in an ice II framework cavity, and the CS-I hydrate
remains stable at pressures at least up to 15 kbar.

We are grateful to Professor J. A. Ripmeester and Professor

V. I. Kosjakov for helpful discussions and valuable comments.
We also express our gratitude to N. V. Udachina for translating
this article into English. This work was supported by the
Presidium of the Siberian Branch of the Russian Academy of
Sciences (grant no. 97-18) and by the Russian Foundation for
Basic Research (grant no. 97-03-33521a). Received: 22nd January 1999; Com. 99/1432

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