Competing esterification and oligomerization reactions of typical long-chain alcohols to secondary organic aerosol formation.
J Environ Sci (China)
; 126: 103-112, 2023 Apr.
Article
em En
| MEDLINE
| ID: mdl-36503740
ABSTRACT
Organosulfate (OSA) nanoparticles, as secondary organic aerosol (SOA) compositions, are ubiquitous in urban and rural environments. Hence, we systemically investigated the mechanisms 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 calculations. 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 contribute SOA formation via esterification rather than oligomerization because OSA/OSI produced by esterification engages in nanoparticle growth through enhancing hygroscopicity.
Palavras-chave
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Álcoois
/
Álcoois Graxos
Idioma:
En
Revista:
J Environ Sci (China)
Assunto da revista:
SAUDE AMBIENTAL
Ano de publicação:
2023
Tipo de documento:
Article