Competing esterification and oligomerization reactions of typical long-chain alcohols to secondary organic aerosol formation

Organosulfate (OSA) nanoparticles, as secondary organic aerosol (SOA) compositions, are ubiquitous in urban and rural environments. Hence, we systemically investigated the mech-anisms and kinetics of aqueous-phase reactions of 1-butanol/1-decanol (BOL/DOL) and their roles in the formation of OSA nanoparticles by using quantum chemical and kinetic calcula-tions. The mechanism results show that the aqueous-phase reactions of BOL/DOL start from initial protonation at alcoholic OH-groups to form carbenium ions (CBs), which engage in the subsequent esterification or oligomerization reactions to form OSAs/organosulfites (OSIs) or dimers. The kinetic results reveal that dehydration to form CBs for BOL and DOL reaction systems is the rate-limiting step. Subsequently, about 18% of CBs occur via oligomerization to dimers, which are difficult to further oligomerize because all reactive sites are occupied. The rate constant of BOL reaction system is one order of magnitude larger than that of DOL reaction system, implying that relative short-chain alcohols are more prone to contribute OSAs/OSIs than long-chain alcohols. Our results reveal that typical long-chain alcohols con-tribute SOA formation via esterification rather than oligomerization because OSA/OSI pro-duced by esterification engages in nanoparticle growth through enhancing hygroscopicity. (c) 2022 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.

Automated summary

This study systematically investigated the mechanisms and kinetics of the aqueous-phase reactions of 1-butanol/1-decanol and their roles in the formation of organosulfate (OSA) nanoparticles. It was found that the reactions start from protonation of hydroxyl groups followed by esterification or oligomerization reactions, leading to the formation of OSA nanoparticles. Short-chain alcohols contribute more to the formation of OSA nanoparticles compared to long-chain alcohols. Additionally, long-chain alcohols participate in nanoparticle growth through esterification.