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Kinetics measurements of methane oxidation in supercritcal water

Journal Article · · Journal of Physical Chemistry
DOI:https://doi.org/10.1021/jp951925h· OSTI ID:196634
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  1. Sandia National Labs., Livermore, CA (United States)
Results and analysis of the oxidation of methane in supericritical water by oxygen over a pressure range from 35 to 270 bar and a temperature range from 390 to 440{degree} are presented. Raman spectroscopy is used as an in situ diagnostic to monitor the concentration of methane, oxygen, carbon monoxide, and carbon dioxide in a constant volume reactor. Reaction orders with respect to methane and oxygen at 270 bar and at methane concentrations near 0.1 mol/L are close to two and zero, respectively. A nonmonotonic dependence of reaction rates on water concentration is observed. With temperature and initial concentrations held constant, methane consumption rates first increase with water concentration but reach a maximum near 5 mol/L. Further increases in water concentration lead to a sharp decrease in the rate of methane consumption. An existing, high-pressure elementary reaction mechanism reproduces this downturn in rates and provides insight into the reasons for this behavior. 25 refs., 7 figs., 1 tab.
OSTI ID:
196634
Journal Information:
Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 1 Vol. 100; ISSN JPCHAX; ISSN 0022-3654
Country of Publication:
United States
Language:
English