Elucidating the chemical evolution of various functional groups in polycyclic aromatic hydrocarbons (PAH) and soot aids in understanding soot formation chemistry. In this work, the chemical evolution of various functional groups, including aromatic CH, aliphatic CH, C=O, COH and COC bonds, was experimentally investigated online, rather than with offline diagnostics. Oxidation was performed in a jet-stirred reactor (JSR), fueled with benzene/C₂H₂/air/N₂ and benzene/phenol/C₂H₂/N₂ for a temperature range of 600-1400 K. Kinetic modelling, including ab initio quantum chemistry calculations, reaction rate coefficient calculations and JSR simulations, were conducted to interpret the experimental data and the evolutionary chemistry of the various functional groups. Results show that the formation of functional groups on PAH and oxygenated PAH (OPAH) are highly sensitive to temperature. Aliphatic CH bonds survive mainly in the form of CCH₂C, CCH₂CH₂C or CCH functional groups above 1200 K, and exist in the CHCH₂ functional group below 1000 K. For the OPAH, the COC functional group presents stronger thermal stability than COH and C=O functional groups. Simulation results indicate that HACA-like pathway (hydrogen abstraction carbon addition), in which C₂H₂ attacks the O atom, followed by cyclization and H-atom elimination reactions, qualitatively describe the formation of OPAH with the CO-C functional group at different temperatures. The addition reaction involving PAH radical and C₂H₄ / C₂H₃ captures the evolution of PAH with the CHCH₂ functional group, but fails to explain the formation of CCH₂C and CCH₂CH₂C functional groups.

阐明多环芳烃（PAH）和烟灰中各种官能团的化学演变有助于理解烟灰形成化学。在这项工作中，在线（而非离线诊断）通过实验研究了包括芳香族C H，脂肪族C H，C = O，C OH和C O C键在内的各种官能团的化学演化。在600-1400 K的温度范围内，在装有苯/ C ₂ H ₂ /空气/ N ₂和苯/苯酚/ C ₂ H ₂ / N ₂的喷气搅拌反应器（JSR）中进行氧化。动力学模型，包括从头算起进行了量子化学计算，反应速率系数计算和JSR模拟，以解释实验数据和各个官能团的演化化学。结果表明，PAH和氧化PAH（OPAH）上官能团的形成对温度高度敏感。脂肪族的C H键生存主要在C的形式CH ₂ C，C CH ₂ CH ₂ C或C的CH中存在CH官能团以上1200 K，和CH ₂官能团低于1000 K.对于月鱼属中，C Ò C官能团比C具有更强的热稳定性OH和C ＝ O官能团。模拟结果表明，类似HACA的途径（夺氢碳添加），其中C ₂ H ₂攻击O原子，然后发生环化和H原子消除反应，定性地描述了具有不同C OC官能团的OPAH的形成。温度。涉及PAH自由基和C ₂ H ₄ / C ₂ H ₃的加成反应捕获了具有CH CH ₂官能团的PAH的演化，但是不能解释C CH ₂ C和C CH ₂ CH ₂ C官能团的形成。