Underappreciated and Complex Role of Nitrous Acid in Aromatic Nitration under Mild Environmental Conditions: The Case of Activated Methoxyphenols
Journal article, 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.

Nitrogen oxides

Activation energy



Quantum chemistry


Aromatic compounds


Earth (planet)


Ana Kroflič

National Institute of Chemistry

Matej Hus

Chalmers, Physics, Chemical Physics

National Institute of Chemistry

M. Grilc

National Institute of Chemistry

Leipzig University

Irena Grgić

National Institute of Chemistry

Environmental Science & Technology

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

Vol. 52 23 13756-13765

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Other Chemistry Topics

Theoretical Chemistry

Organic Chemistry



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