Electron transfer and ion-pair formation during oxidation and gasification of coal. Final report, February 1982-February 1985
This report describes a research project directed towards investigating the possible or potential role of radical cations and hydroxyl adduct radicals in coal gasification. Basic knowledge relating to the reactions of radical cations and hydroxyl adducts of coal-related compounds was deduced from study of Cu(II)-catalyzed peroxydisulfate oxidations conducted in aqueous acetonitrile. Bibenzylic and related compounds, aromatic aldehydes, and alkyl- and acyl-anthracenes were observed to undergo facile side-chain fragmentation and ring oxidation reactions. Preferred reaction pathways were structure- and medium-dependent. Hydration of radical cations to form hydroxyl adduct radicals readily occurred but acid suppressed the reaction for monocyclic alkylaromatic radical cations in favor of side-chain fragmentation. Loss of benzylic protons was usually favored but cleavage of bibenzylic C-C bonds occurred when sufficiently more-stable radical and cationic fragments could be formed. Thus, the radical cations of 1,2-diarylethanes reacted by proton loss but those of 1,2-diarylethanol and 2,3-diphenyl-2,3- dimethylbutane reacted by C-C cleavage. The hydration reactions of 9-alkyl- and 9-acyl- anthracene radical cations to form hydroxyl adduct radicals were not suppressed by acid, and direct side fragmentation was not observed. The implication of these and other results to coal gasification is discussed.
- Research Organization:
- Battelle-Northwest, Richland, WA (USA). Pacific Northwest Lab.
- OSTI ID:
- 5508177
- Report Number(s):
- PB-85-204618/XAB
- Resource Relation:
- Other Information: See also PB84-198555
- Country of Publication:
- United States
- Language:
- English
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CHEMICAL REACTIONS
ELECTRON TRANSFER
ION PAIRS
COAL GASIFICATION
CATALYSIS
CATIONS
CHEMICAL BONDS
HYDROXYL RADICALS
MOLECULAR STRUCTURE
OXIDATION
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IONS
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010404* - Coal
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