Underappreciated and Complex Role of Nitrous Acid in Aromatic Nitration under Mild Environmental Conditions: The Case of Activated Methoxyphenols
Artikel i vetenskaplig tidskrift, 2018

Many ambiguities surround the possible mechanisms of colored and toxic nitrophenols formation in natural systems. Nitration of a biologically and environmentally relevant aromatic compound, guaiacol (2-methoxyphenol), under mild aqueous-phase conditions (ambient temperatures, pH 4.5) was investigated by a temperature-dependent experimental modeling coupled to extensive ab initio calculations to obtain the activation energies of the modeled reaction pathways. The importance of dark nonradical reactions is emphasized, involving nitrous (HNO2) and peroxynitrous (HOONO) acids. Oxidation by HOONO is shown to proceed via a nonradical pathway, possibly involving the nitronium ion (NO2+) formation. Using quantum chemical calculations at the MP2/6-31++g(d,p) level, NO2 is shown capable of abstracting a hydrogen atom from the phenolic group on the aromatic ring. In a protic solvent, the corresponding aryl radical can combine with HNO2 to yield OH and, after a subsequent oxidation step, nitrated aromatic products. The demonstrated chemistry is especially important for understanding the aging of nighttime atmospheric deliquesced aerosol. The relevance should be further investigated in the atmospheric gaseous phase. The results of this study have direct implications for accurate modeling of the burden of toxic nitroaromatic pollutants, and the formation of atmospheric brown carbon and its associated influence on Earth's albedo and climate forcing.

Activation energy

Calculations

Aromatic compounds

Aromatization

Quantum chemistry

Nitrogen oxides

Earth (planet)

Nitration

atoms

Författare

Ana Kroflič

National Institute of Chemistry Ljubljana

Matej Hus

National Institute of Chemistry Ljubljana

Chalmers, Fysik, Kemisk fysik

M. Grilc

Universität Leipzig

National Institute of Chemistry Ljubljana

Irena Grgić

National Institute of Chemistry Ljubljana

Environmental Science & Technology

0013-936X (ISSN) 1520-5851 (eISSN)

Vol. 52 23 13756-13765

Ämneskategorier

Annan kemi

Teoretisk kemi

Organisk kemi

DOI

10.1021/acs.est.8b01903

Mer information

Senast uppdaterat

2019-01-17