Guest size effects on a robust structure of semiclathrate hydrates and their thermophysical properties

The ability to tune the pore size, shape, and functionality of semiclathrate hydrates, host-guest materials formed from aqueous solutions of ionic guest materials and water, makes them attractive materials for thermal storage and gas storage applications. The flexibility of semi-clathrate hydrates and their guest-molecule-dependent reactions produce these unexpected and desirable properties. As an ionic guest, tetra-n-butylammonium cation is known for best-fit in hydrogen-bonded water structures. Few investigations have been conducted for other cations, while there are numerous candidates. Relationships between the molecular structures of ionic guest substances and their hydrate structure and relevant thermodynamic properties are yet to be understood. In this study, the semiclathrate hydrates formed with two variations of tetra-n-butylammonium chloride (N4444Cl) that are n-propyl, tri-n-butylammonium chloride (N3444Cl) and tri-n-butyl, n-pentylammonium chloride (N4445Cl) were investigated. Structure analyses found that both salts formed Jeffrey's type III tetragonal hydrate structure which is the same as that of tetra-n-butylammonium chloride hydrate, although their lattice parameters are significantly different. The present data found that this hydrate structure can cover a wide range of melting temperature compared to the other two main semiclathrate structures. The present N4445Cl hydrate is an example in which its melting temperature was adjusted to be suitable for air conditioning, i.e., ∼282 K, compared to that of the N4444Cl hydrate, the melting temperature of which is slightly too high for this purpose. The results provide insight that the thermal properties of the tetragonal P4₂/m hydrate structure can be widely tuned by ionic guests for various practical requirements.