Thermodynamic Stability Boundaries and Structures of Methane + Monohalogenated Cyclopentane Mixed Hydrates

Thermodynamic stability boundaries of the mixed hydrate composed of methane and fluorocyclopentane, chlorocyclopentane, or bromocyclopentane were investigated in a temperature range of (274.17 to 306.19) K and pressures up to 9.93 MPa under the four-phase (hydrate, aqueous, monohalogenated cyclopentane-rich liquid, and gas phases) equilibrium conditions. Also, the crystal structure of the methane + chlorocyclopentane hydrate was determined by means of powder X-ray diffractometry. The each boundary is laid at a pressure lower and a temperature higher than that of the simple methane hydrate. Especially, the methane + fluorocyclopentane hydrate system has the lowest equilibrium pressure among three mixed hydrate systems investigated in the present study. The powder X-ray diffraction patterns reveal that a guest species larger than chrolocyclopentane and smaller than bromocyclopentane is at the border between structure-II and structure-H hydrate formers.