13C chemical shifts of propane molecules encaged in structure II clathrate hydrate.

Experimental NMR measurements for (13)C chemical shifts of propane molecules encaged in 16-hedral cages of structure II clathrate hydrate were conducted to investigate the effects of guest-host interaction of pure propane clathrate on the (13)C chemical shifts of propane guests. Experimental (13)C NMR measurements revealed that the clathrate hydration of propane reverses the (13)C chemical shifts of methyl and methylene carbons in propane guests to gaseous propane at room temperature and atmospheric pressure or isolated propane, suggesting a change in magnetic environment around the propane guest by the clathrate hydration. Inversion of the (13)C chemical shifts of propane clathrate suggests that the deshielding effect of the water cage on the methyl carbons of the propane molecule encaged in the 16-hedral cage is greater than that on its methylene carbon.

Tetra-n-butylammonium bromide-water (1/38).

Tetra-n-butylammonium bromide forms the title semi-clathrate hydrate crystal, C16H36N+.Br-.38H2O, under atmospheric pressure. The cation and anion lie at sites with mm symmetry and seven water molecules lie at sites with m symmetry in space group Pmma. Br- anions construct a cage structure with the water molecules. Tetra-n-butylammonium cations are disordered and are located at the centre of four cages, viz. two tetrakaidecahedra and two pentakaidecahedra in ideal cage structures, while all the dodecahedral cages are empty.

Texture change of ice on anomalously preserved methane clathrate hydrate.

We used a confocal scanning microscope to observe growth and texture change of ice due to the dissociation of methane gas clathrate hydrate (CH(4) hydrate). The experiments were done under CH(4) gas atmospheric pressure and isothermal conditions between 170 and 268 K. Above 193 K, the dissociation of CH(4) hydrate resulted in many small ice particles that covered the hydrate surface. These ice particles had roughly the same shape and density between 193 and 210 K. In contrast, above 230 K the ice particles developed into a sheet of ice that covered the hydrate surface. Moreover, the measured release of CH(4) gas decreased when the sheet of ice formed at the surface of the hydrate. These findings can explain the anomalous preservation behavior of CH(4) hydrate; that is, the known increase of storage stability of CH(4) hydrate above 240 K is likely related to the formation of the ice that we observed in the experiments.

A new method for separating HFC-134a from gas mixtures using clathrate hydrate formation.

A new separation method using gas hydrate formation is proposed for separating HFC-134a from gas mixtures containing N2 and HFC-134a. The feasibility of this separation method was investigated from various points of view. First, to determine the mixed hydrate stability region, three-phase equilibria of hydrate (H), liquid water (Lw), and vapor (V) for HFC-134a + N2 + water mixtures with various HFC-134a vapor compositions were closely examined in the temperature and pressure ranges of 275-285 K and 0.1-2.7 MPa, respectively. Second, the compositions of the hydrate and vapor phases at a three-phase equilibrium state were analyzed for identical mixtures at 278.15 and 282.15 K to confirm the actual separation efficiency. Third, kinetic experiments were performed to monitor the composition change behavior of the vapor phase and to determine the time required for an equilibrium state to be reached. Furthermore, X-ray diffraction confirmed that the mixed HFC-134a + N2 hydrates were structure II. Through an overall investigation of the experimental results, it was verified that more than 99 mol % HFC-134a could be obtained from gas mixtures after hydrate formation and subsequent dissociation processes. Separation of HFC-134a using hydrate formation can be carried out at mild temperature and low-pressure ranges. No additive is needed to lower the hydrate formation pressure.