Studies of the reactions of hydroxyl radicals. I
| Autor: | D. E. Hoare |
|---|---|
| Rok vydání: | 1966 |
| Předmět: | |
| Zdroj: | Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences. 291:73-84 |
| ISSN: | 2053-9169 0080-4630 |
| DOI: | 10.1098/rspa.1966.0079 |
| Popis: | This paper describes how the homogeneous decomposition of hydrogen peroxide vapour has been successfully used as a source of hydroxyl radicals in a kinetic study of the relative rates of reaction of hydroxyl radicals with methane, carbon monoxide, formaldehyde and hydrogen peroxide. It has been found that the method is of general applicability provided subsequent reactions of radicals formed can be controlled. With hydroxyl radicals so produced from the decomposition of hydrogen peroxide, surprisingly consistent values were obtained for the relative rates of reaction of methane and carbon monoxide with hydroxyl radicals. Thus, within an accuracy of 10%, the ratios of rate constants for reaction of hydroxyl radicals with methane and carbon monoxide were found to be 3.6 at 650 $^\circ$C, 2.1 at 525 $^\circ$C and 0.85 at 400 $^\circ$C. The rates of reaction of hydroxyl radicals with formaldehyde and hydrogen peroxide were less accurately determined because of expected additional reactions. Within an accuracy of about 50% it was estimated that hydroxyl radicals reacted ten times as fast with hydrogen peroxide as with carbon monoxide at 525 $^\circ$C. At the same temperature hydroxyl radicals reacted 33$\pm$6 times as fast with formaldehyde as with methane. Data were obtainable at temperatures as low as 400 $^\circ$C even though heterogeneous decomposition of hydrogen peroxide was relatively more important at these temperatures. This was because heterogeneous decomposition of hydrogen peroxide did not cause oxidation of the other gases which were also present. A preliminary account (Hoare 1962) of this work has previously been published. |
| Databáze: | OpenAIRE |
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