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THE RADIOLYSIS OF CYCLOHEXANE: IV. BINARY MIXTURES IN THE VAPOR PHASE

 

作者: J. M. Ramaradhya,   G. R. Freeman,  

 

期刊: Canadian Journal of Chemistry  (NRC Available online 1961)
卷期: Volume 39, issue 9  

页码: 1769-1775

 

ISSN:0008-4042

 

年代: 1961

 

DOI:10.1139/v61-232

 

出版商: NRC Research Press

 

数据来源: NRC

 

摘要:

The variation of the hydrogen yield with the composition of binary gaseous mixtures containing cyclohexane and benzene, cyclohexene, or propylene is qualitatively similar to that in the liquid phase.The quantitative experimental data were tested against several possible reaction mechanisms and two mechanisms gave straight-line plots.One mechanism involved scavenging of hydrogen atoms. The values of the kinetic parameters derived from this mechanism might not be unreasonable in the mixtures of cyclohexane with cyclohexene or propylene. The values for benzene, however, seem less likely.The second mechanism involved the transfer of energy (excitation or ionization) from cyclohexane to the second substance. The values of the ratio of the rate constants,k7/k6, of the reactionsis about 103times greater in the gas than in the liquid phase. Consideration of possible detailed mechanisms of reactions [6] and [7] indicates that this difference is reasonable if C6H12** is a positive ion rather than an excited molecule.

 

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