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 · Thu Mar 10 04:00:00 EST 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100316a025· OSTI ID:7148537

Matsuoka, S; Ikezoe, Y

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), Journal Name: J. Phys. Chem.; (United States) Vol. 92:5; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

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