Chen Guangliang, Huang Mingqiang, Gao Guangzhen, Liu Xingqiang, Hu Changjin, Zhao Weixiong, Gu Xuejun, Zhang Weijun
Fujian Provincial Key Laboratory of Modern Analytical Science and Separation Technology, College of Chemistry & Chemical Engineering and Environment, Minnan Normal University Zhangzhou 363000 China
College of Physics and Electronic Engineering, Jiangsu Normal University Xuzhou 221116 China.
RSC Adv. 2025 Sep 3;15(38):31651-31663. doi: 10.1039/d5ra03441h. eCollection 2025 Aug 29.
Nitrous acid (HONO) is a vital pollutant gas and the nitrogen-containing organic compounds (NOCs) produced by its reaction are the main components of aerosols. The reaction mechanisms and kinetics of HONO and the simplest aromatic Criegee intermediate (PhCHOO) are investigated by density functional theory and transition state theory in this study. The results demonstrate that cycloaddition of HONO and PhCHOO to form heteroozonide with the highest activation energy and smallest rate constant does not easily occur. Pathways of oxygen atom transfer and cycloaddition can form HNO and benzoic acid. Meanwhile, the hydrogen atom transfer pathway results in the generation of phenyl hydroperoxide methyl nitrite (Ph-HPMN), which has the lowest activation energy, dominating the reaction between HONO and PhCHOO with a rate constant (5.68 × 10 cm per molecule per s) close to that with OH radicals (4.83 × 10 cm per molecule per s). These results provide a theoretical reference for clarifying the mechanism of generation of NOCs formed from ozonolysis of styrene and other olefin compounds in the presence of HONO.
亚硝酸（HONO）是一种重要的污染气体，其反应产生的含氮有机化合物（NOCs）是气溶胶的主要成分。本研究采用密度泛函理论和过渡态理论研究了HONO与最简单的芳香族克里吉中间体（PhCHOO）的反应机理和动力学。结果表明，HONO与PhCHOO环加成形成具有最高活化能和最小速率常数的杂过氧化物的反应不易发生。氧原子转移和环加成途径可生成HNO和苯甲酸。同时，氢原子转移途径导致生成苯基氢过氧化物亚硝酸甲酯（Ph-HPMN），其活化能最低，主导了HONO与PhCHOO之间的反应，速率常数（5.68×10每分子每秒厘米）接近与OH自由基反应的速率常数（4.83×10每分子每秒厘米）。这些结果为阐明在HONO存在下苯乙烯和其他烯烃化合物臭氧分解形成NOCs的生成机理提供了理论参考。
