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Title: Spectroscopic determination of gas-water interactions in clathrate hydrates

Abstract

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 tomore » (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/).« less

Authors:
Publication Date:
Research Org.:
Oklahoma State Univ., Stillwater (USA)
OSTI Identifier:
5585284
Resource Type:
Thesis/Dissertation
Resource Relation:
Other Information: Thesis (Ph. D.)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; ELECTRONS; CHEMICAL RADIATION EFFECTS; ETHYLENE; CLATHRATES; HEAVY WATER; ISOTOPE EFFECTS; HYDROGEN SULFIDES; OXIDES; SULFUR DIOXIDE; WATER; CRYSTAL DEFECTS; TRACER TECHNIQUES; ALKENES; CHALCOGENIDES; CHEMISTRY; CRYSTAL STRUCTURE; ELEMENTARY PARTICLES; FERMIONS; HYDROCARBONS; HYDROGEN COMPOUNDS; ISOTOPE APPLICATIONS; LEPTONS; ORGANIC COMPOUNDS; OXYGEN COMPOUNDS; RADIATION CHEMISTRY; RADIATION EFFECTS; SULFIDES; SULFUR COMPOUNDS; SULFUR OXIDES; 400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987); 400302 - Organic Chemistry- Isotope Effects- (-1987); 400600 - Radiation Chemistry

Citation Formats

Richardson, H.H. Jr. Spectroscopic determination of gas-water interactions in clathrate hydrates. United States: N. p., 1985. Web.
Richardson, H.H. Jr. Spectroscopic determination of gas-water interactions in clathrate hydrates. United States.
Richardson, H.H. Jr. Tue . "Spectroscopic determination of gas-water interactions in clathrate hydrates". United States.
@article{osti_5585284,
title = {Spectroscopic determination of gas-water interactions in clathrate hydrates},
author = {Richardson, H.H. Jr.},
abstractNote = {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/).},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1985},
month = {1}
}

Thesis/Dissertation:
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