Читать книгу Clathrate Hydrates - Группа авторов - Страница 22

It is just over 200 years ago in 1810 that a gas hydrate, frozen from a solution of gas in water, was first recognized as a new kind of material. This places the discovery of gas hydrates in the period when the fundamentals of modern chemistry, e.g. Joseph Proust's law of definite proportions and John Dalton's atomic theory, were being formulated. Although the study of gas hydrates ran parallel to the development of chemistry, and indeed work on gas hydrates contributed significantly to the first applications of classical chemical thermodynamics, these substances presented peculiarities not found in the usual chemical compounds. Despite the best efforts of some of the most eminent chemists and physicists of the time, the nature of the interactions between the constituents of gas hydrates, the non‐integer ratios of their constituting atoms/molecules, and their apparent compositional variations eluded explanation until the 1950s.

Often clathrate hydrates have been designated as “laboratory curiosities,” which leaves little appreciation of the fact that the early science of clathrate hydrates is closely linked to the discovery and characterization of weak intermolecular forces. Neither covalent nor ionic, nevertheless such forces are able to control the assembly of complex structures. The work on clathrate hydrates presaged the field of supramolecular chemistry – that is, “chemistry beyond the molecule.” Today, it is known that multiple weak interactions, e.g. van der Waals forces, hydrogen bonding, and halogen bonding, play a major role in the construction of complex materials in chemistry, biology, and materials science. This burgeoning field was duly recognized by the award of the 1987 Nobel Prize in Chemistry to Jean‐Marie Lehn, Donald J. Cram, and Charles J. Pederson.

The first ∼150 years of clathrate hydrate science is presented following the order in which these materials revealed themselves to the scientific community. In writing this chapter on the research that shaped the early scientific knowledge of clathrate hydrates, we acknowledge as major resources W. Schröder's “The History of Gas Hydrates” [1] and Donald Davidson's notes on the history of clathrate hydrates which he had started to compile into a manuscript chapter shortly before his death in 1986 [2].