The pyrolysis of ethane in the presence of nitric oxide
作者:
Joseph Esser,
Keith J. Laidler,
期刊:
International Journal of Chemical Kinetics
(WILEY Available online 1970)
卷期:
Volume 2,
issue 1
页码: 37-61
ISSN:0538-8066
年代: 1970
DOI:10.1002/kin.550020105
出版商: John Wiley&Sons, Inc.
数据来源: WILEY
摘要:
AbstractThe kinetics of the ethane pyrolysis have been studied at temperatures from 550 to 596°C and with 0 to 62% of added nitric oxide. The rates of production of various products were studied by gas chromatography; ethylene, hydrogen, methane, nitrogen, water, nitrous oxide and acetonitrile were found as primary products, with hydrogen cyanide, carbon monoxide, acetaldehyde,n‐butane, 1‐butene,cis‐ andtrans‐2‐butene and 1,3‐butadiene as secondary products. For all the primary products the orders with respect to C2H6and NO were determined, as were the activation energies at two different percentages of NO (15.7 and 45.5%).Nitric oxide was found to be rapidly consumed with a finite initial rate, and the rate of production of H2O was close to that of C2H4at higher nitric oxide pressures.A mechanism is proposed which gives good agreement with all of the observed results. Its main features are: (1) Initiation takes place mainly by the unimolecular dissociation of ethane; there is no evidence for or against the process NO + C2H6→ HNO + C2H5; (2) NO scavenges ethyl radicals to form acetaldoxime which decomposes, and in this way the breakdown of C2H5is hastened; (3) termination takes place mainly by the unimolecular decomposition of acetaldoxime to give inactive products. Some of the relevant rate parameters are evaluated. Reactions are proposed to account for the formation of the secondary pro
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