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Ion-Molecule Reactions and Thermal Decomposition of Ions in N2-O2-Alkane (C2-C8) Mixtures Studied by Time-Resolved Atmospheric Pressure Ionization Mass
Matsuoka, Shingo,Ikezoe, Yasumasa
, p. 1126 - 1133 (2007/10/02)
The experiments were carried out at temperatures ranging from 236 to 569 K.The O2+ ion reacted with n-alkanes (CnH2n+2) via fast nondissociative and dissociative charge-transfer channels, its proportion depending on temperature.The nondissociative product CnH(2n+2)+ subsequently reacted with O2 via a slow H atom transfer path, producing alkyl ions.With increasing temperature the alkane ions CnH(2n+2)+ (n >/= 4) began to decompose thermally, producing olefinic ions and alkanes.The product olefinic ions CmH2m+ (m=4,5,6) reacted with O2 via a slow H atom transfer path, producing alkenyl ions CmH(2m-1)+.The C8H17+ decomposed thermally forming fragment alkyl ions and olefins.The fragment alkyl ions reacted with n-C8H18 reproducing C8H17+, thus leading to a chain mechanism in n-C8H18 decomposition.The equilibrium reaction, C2H5+ + C2H6 ->/+, and the subsequent dissociative rearrangement reaction, C4H11+ -> C4H9+ + H2, were studied.The reactions of NO+ and NOO+, both minor products of the irradiation of N2-O2 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.
