Combustion and pyrolysis reactions of alkylated polycyclic aromatic compounds: The decomposition of 13C methylarenes in relation to diesel engine emissions

The thermal decomposition of methylarenes labelled with 13C in the methyl group was investigated. This was conducted using both a direct injection diesel engine and a pyrolysis flow cell connected to a GC-MS. 2-[13C]methylnaphthalene and 9-[13C]methylphenanthrene were synthesized by means of the Corey-House coupling reaction and their identity and purity confirmed by mass spectrometry and NMR. GC-MS analysis of the aromatic fraction separated from the extract of the exhaust particulate collected from the engine operated with n-hexadecane doped with the labelled methylnaphthalene showed that the 13C was not redistributed among the methyl groups of higher PAH. However, with 9-[13C]methylphenanthrene in the fuel a significant amount was retained in the particulate, even though the principal in-cylinder reaction was dealkylation. Pyrolytic reactions of the 13C-labelled methyl arenes were studied in a micro-pyrolysis-GC-MS-apparatus and confirmed dealkylation as the predominant reaction. The detailed chemical mechanism of the pyrolysis was explained by a scheme involving two alternative radical transfer reactions.