Spectroscopic determination of gas-water interactions in clathrate hydrates

Thesis/Dissertation · Tue Jan 01 04:00:00 EST 1985

OSTI ID:5585284

Richardson, Jr, H H

The technique of forming clathrate hydrates by first forming the amorphous deposits of gas-water mixture and, secondly, annealing this deposit was used to form the clathrate hydrates of ethylene oxide, hydrogen sulfide and sulfur dioxide. Once the clathrate hydrate formed as a thin film on the CsI substrate, the infrared spectrum of these hydrates could be obtained. The clathrate hydrates could be irradiated with 1.7 MeV electrons to promote high proton concentrations in the clathrate hydrate lattice at low temperatures (approx.30K) where the Bjerrum defects in the lattice are not mobile. The ring breathing model of ethylene oxide in the clathrate hydrate can be assigned. It was possible to incorporate D/sub 2/O into the hydrogen bonded lattice of the ethylene oxide clathrate hydrate by growing the clathrate hydrate epitaxially on a thin film of clathrate hydrate at 100 K. The half-life of the D/sub 2/O molecules in the ethylene oxide clathrate hydrate was only 9 minutes at 120 K. The activation energy determined from the hopping rate constant in ethylene oxide clathrate hydrate was 4.5 +/- 1.8 Kcal/mole. Irradiation of the ethylene oxide clathrate hydrate with 1.7 MeV electrons transformed some of the ethylene oxide molecules in the cages to (a) CH/sub 2/ = CH/sub 2/, (b) CH/sub 2/ = C = O, (c) CH/sub 3/-CH/sub 2/-OH, (d) CO/sub 2/, and (e) CO. A steady state concentration of coupled HOD was maintained in irradiated samples of ethylene oxide clathrate hydrates at a temperature around 80 K. The enclathrated H/sub 2/S molecule in the small cages had a different infrared spectrum (broad band complex centered at 2600 cm/sup -1/) from the H/sub 2/S molecules which had been enclathrated in the large cages (broad band complex centered at 2550 cm/sup -1/).

• Research Organization: Oklahoma State Univ., Stillwater (USA)
• OSTI ID: 5585284
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
400600 -- Radiation Chemistry
ALKENES
CHALCOGENIDES
CHEMICAL RADIATION EFFECTS
CHEMISTRY
CLATHRATES
CRYSTAL DEFECTS
CRYSTAL STRUCTURE
ELECTRONS
ELEMENTARY PARTICLES
ETHYLENE
FERMIONS
HEAVY WATER
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN SULFIDES
ISOTOPE APPLICATIONS
ISOTOPE EFFECTS
LEPTONS
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
SULFIDES
SULFUR COMPOUNDS
SULFUR DIOXIDE
SULFUR OXIDES
TRACER TECHNIQUES
WATER