Reactions of coal with discharge-generated (excited) nitrogen species |
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Authors: | Seiji Nishida Norbert Berkowitz |
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Affiliation: | Fuel Sciences Division, Research Council of Alberta, 11315-87th Avenue, Edmonton 7, Alberta, Canada |
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Abstract: | Reaction between coal and nitrogen in a discharge furnishes hydrogen cyanide and smaller amounts of cyanogen, as well as some carbon monoxide and carbon dioxide; the cumulative yields of hydrogen cyanide and cyanogen depend upon rank. The apparent activation energies for formation of hydrogen cyanide and cyanogen are in the order of 2–4 kcal mol?1 but increase sharply to ≈13–14 kcal mol?1 at ≈200 °C (possibly coincident with incipient thermal decomposition of the coal). The cyanogen/hydrogen cyanide ratio increases with rank, and also depends upon the reaction temperature — falling with increasing temperature up to ≈200 °C, and thereafter rising progressively. Rate measurements and i.r. spectral changes accompanying the reaction suggest that hydrogen cyanide is mainly formed from non-aromatic carbon-hydrogen configurations in the coal, and that cyanogen derives for the most part from aromatic carbon — though some can also be generated from non-aromatic CH in competition with formation of hydrogen cyanide. |
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