Vacuum-Ultraviolet Photochemistry. II. Solid- and Gas-Phase Photolysis of Methane—Water Systems
The photolysis of the methane hydrate (CH4·6H2O) at −195°C at 1470 and 1236 Å has been investigated. Mixtures of methane and water in the gas phase have also been photolyzed at 1470, at 1236 Å, and in the region 1450–1850 Å. In both gas- and solid-phase photolysis, CO and CO2 are formed at 1470 and...
| Published in: | The Journal of Chemical Physics |
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| Main Authors: | , , |
| Format: | Article in Journal/Newspaper |
| Language: | English |
| Published: |
AIP Publishing
1965
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| Subjects: | |
| Online Access: | http://dx.doi.org/10.1063/1.1697148 https://pubs.aip.org/aip/jcp/article-pdf/43/7/2490/11262724/2490_1_online.pdf |
| Summary: | The photolysis of the methane hydrate (CH4·6H2O) at −195°C at 1470 and 1236 Å has been investigated. Mixtures of methane and water in the gas phase have also been photolyzed at 1470, at 1236 Å, and in the region 1450–1850 Å. In both gas- and solid-phase photolysis, CO and CO2 are formed at 1470 and 1236 Å. CO2 is formed from CO, probably by the reaction OH+CO→CO2+H, which is shown to occur readily in the solid at −196°C. In the photolysis of CH4·6H2O at −196°C, the hydrogen produced is mainly from the methane. Ethane is formed as well, and the product ratio CO2/C2H6 is a linear function of the ratio of the reactants H2O/CH4. Formation of CO2 and C2H6 by competitive reactions of CH2 with H2O and CH4 is suggested. Similarity of results at 1236 Å to those at 1470 Å suggests that CH2 is present in both systems. Since photodecomposition of CH4 is negligible at 1470 Å, the production of CH2 at this wavelength is attributed to the occurrence of O+CH4→CH2+H2O with oxygen atoms being formed in photolysis of water. |
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