Reaction of O2 with the hydrogen atom in water up to 350 degrees C |
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Authors: | Janik Ireneusz Bartels David M Marin Timothy W Jonah Charles D |
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Institution: | Notre Dame Radiation Laboratory, Notre Dame, Indiana 46556, USA. |
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Abstract: | The reaction of the H* atom with O2, giving the hydroperoxyl HO2* radical, has been investigated in pressurized water up to 350 degrees C using pulse radiolysis and deep-UV transient absorption spectroscopy. The reaction rate behavior is highly non-Arrhenius, with near diffusion-limited behavior at room temperature, increasing to a near constant limiting value of approximately 5 x 10(10) M(-1) s(-1) above 250 degrees C. The high-temperature rate constant is in near-perfect agreement with experimental extrapolations and ab initio calculations of the gas-phase high-pressure limiting rate. As part of the study, reaction of the OH* radical with H2 has been reevaluated at 350 degrees C, giving a rate constant of (6.0 +/- 0.5) x 10(8) M(-1) s(-1). The mechanism of the H* atom reaction with the HO2* radical is also investigated and discussed. |
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