Gas Hydrates: Review of Physical/Chemical Properties

An overview is provided of time-independent physical/chemical properties as related to crystal structures. The following two points are illustrated in this review:  (1) Physical and chemical properties of structure I (sI) and structure II (sII) hydrates are well-defined; measurements have begun on sH. Properties of sI and sII are determined by the molecular structures, described by three heuristics:  (i) Mechanical properties approximate those of ice, perhaps because hydrates are 85 mol % water. Yet each volume of hydrate may contain as much as 180 volumes (STP) of the hydrate-forming species. (ii) Phase equilibrium is set by the size ratio of guest molecules within host cages, and three-phase (Lw−H−V) equilibrium pressure depends exponentially upon temperature. (iii) Heats of formation are set by the hydrogen-bonded crystals and are reasonably constant within a range of guest sizes. (2) Fundamental research challenges are (a) to routinely measure the hydrate phase (via diffraction, NMR, Raman, etc.), and...