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Title: Ion-molecule reactions and thermal decomposition of ions in N/sub 2/-O/sub 2/-alkane (C/sub 2/-C/sub 8/) mixtures studied by time-resolved atmospheric pressure ionization mass spectrometry

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100316a025· OSTI ID:7148537
;

The experiments were carried out at temperatures ranging from 236 to 569 K. The O/sub 2//sup +/ ion reacted with n-alkane (C/sub n/H/sub 2n+2/ via fast nondissociative and dissociative charge-transfer channels, its proportion depending on temperature. The nondissociative product C/sub n/H/sub 2n + 2/sup +/ subsequently reacted with O/sub 2/ via a slow H atom transfer path, producing alkyl ions. With increasing temperature the alkane ions C//sub n/H/sub 2n + 2//sup +/ (m= 4,5,6) reacted with O/sub 2/ via a slow H atoms transfer path, producing olefinic ions and alkanes. The product olefinic ions C/sub m/H/sub 2m/sup +/ ( m = 4, 5, 6) reacted with O/sub 2/ via a slow H atom transfer path, producing alkenyl ions C//sub m/H/sub 2m-1//sup +/. The C/sub 8/H/sub 17//sup +/ decomposed thermally forming fragment alkyl ions and olefins. The fragment alkyl ions reacted with n-C/sub 8/H/sub 18/ reproducing C/sub 8/H/sub 17//sup +/, thus leading to a chain mechanism in n-C/sub 4/H/sub 18/ decomposition. The equilibrium reaction, C/sub 2/H/sub 5/ + C/sub 2/H/sub 6/ ..-->.. C/sub 4/H/sub 11//sup +/, and the subsequent dissociative rearrangement reactions, C/sub 4/H/sub 11//sup +/ ..-->.. C/sub 4/H/sub 9//sup +/ + H/sub 2/ were studied. The reactions of NO/sup +/ and NOO/sup +/, both minor products of the irradiation of N/sub 2/O/sub 2/ mixtures, with alkanes were also studied. The rate constants of the ion-molecule reactions and the unimolecular thermal decomposition reactions and the equilibrium constant were measured.

Research Organization:
Univ. of Tokyo, Ibaraki-ken (Japan)
OSTI ID:
7148537
Journal Information:
J. Phys. Chem.; (United States), Vol. 92:5
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
54 ENVIRONMENTAL SCIENCES
ALKANES
CHEMICAL REACTIONS
ION-MOLECULE COLLISIONS
NITROGEN IONS
OXYGEN IONS
EXPERIMENTAL DATA
MASS SPECTRA
MEDIUM TEMPERATURE
CHARGED PARTICLES
COLLISIONS
DATA
HYDROCARBONS
INFORMATION
ION COLLISIONS
IONS
MOLECULE COLLISIONS
NUMERICAL DATA
ORGANIC COMPOUNDS
SPECTRA
400201* - Chemical & Physicochemical Properties
500100 - Environment
Atmospheric- Basic Studies- (-1989)