Journal of Physical Chemistry B, Vol.118, No.47, 13371-13377, 2014
Experimental Study on the Effect of Ammonia on the Phase Behavior of Tetrahydrofuran Clathrates
Clathrate hydrates, ice-like crystalline compounds in which small guest molecules are enclosed inside cages formed by tetrahedrally hydrogen-bonded water molecules, are naturally abundant on Earth and are generally expected to exist on icy celestial bodies. A prototypical example is Saturns moon Titan, where dissociation of methane clathrates, a major crustal component, could contribute significantly to the replenishment of atmospheric methane. Ammonia is an important clathrate inhibiting agent that may be present (potentially at high concentrations) in Titans interior. In this study, low-temperature Raman experiments are conducted to examine the dissociation point of tetrahydrofuran clathrates, an ambient-pressure analogue of methane clathrates, over a wide range of ammonia concentrations from 0 to 25 wt %. A phase diagram for the H2O-THF-NH-3 system is generated, showing two main results: (i) ammonia lowers the dissociation point of clathrate hydrates to a similar extent compared to the melting of water ice and (ii) THF clathrate exhibits a liquidus-like behavior in the presence of ammonia, with a eutectic temperature of about 203.6 K. As temperatures higher than this estimated eutectic are anticipated within Titans icy crust, these results imply that partial dissociation of clathrates can occur readily and may contribute to outgassing from the interior.