Mechanical and kinetic study on gas-phase formation of dinitro-naphthalene from 1- and 2-nitronaphthalene. (August 2016)

• Record Type: Journal Article
• Authors: Huang, Zixiao; Zhang, Qingzhu; Wang, Wenxing
• Is Part Of: Chemosphere. Volume 156(2016)
• Page Start: 101
• Page End: 110
• Publication Date: 2016-08
• Subjects: Dinitro-naphthalene -- Formation -- Gas phase -- Reaction mechanism -- Rate constants; Pollution -- Periodicals; Pollution -- Physiological effect -- Periodicals; Environmental sciences -- Periodicals; Atmospheric chemistry -- Periodicals; 551.511
• DOI: 10.1016/j.chemosphere.2016.04.108
• Languages: English
• ISSNs: 0045-6535

Abstract

Abstract: Nitrated polycyclic aromatic hydrocarbons have received an increasing number of considerations because of their higher mutagens than parent PAHs. In this paper, the formation of dinitro-naphthalene was investigated mechanistically using 1- and 2-nitronaphthalene as precursors with the aid of high-accuracy quantum chemistry calculation. The geometrical parameters, as well as vibrational frequencies, were calculated at the BB1K/6-31+G(d, p) level. Water molecule plays an important role in the formation of dinitro-naphthalene. The rate constants were deduced by canonical variational transition-state theory with small curvature tunneling contribution over the temperature range of 273–333 K. Meanwhile, the Arrhenius formulas were fitted for the OH addition of both 1- and 2-nitronaphthalene. The calculated overall rate constants for 1-nitronaphthalene and 2-nitronaphthalene at 298 K and 1 atm are 7.43 × 10 −13 and 7.48 × 10 −13 cm 3 molecule −1 s −1, respectively. The rate constants of NO3 addition to 1-nitronaphthalene and 2-nitronaphthalene by RRKM method at 298 K and 1 atm are 3.55 × 10 −15 and 3.47 × 10 −15 cm 3 molecule −1 s −1, respectively. This study provides a comprehensive investigation of the formation process of dinitro-naphthalenes, initiated by OH and NO3 radicals and should facilitate to illuminate its atmospheric source. Oxygen may probably be competitive with the second NO2 addition step when the concentration of NO2 is at low level. Highlights: Formation of dinitro-naphthalene via both OH and NO3 were investigated firstly. Water molecule plays an important role during the formation of dinitro-naphthalene. The overall rate constants were calculated for 1- and 2-nitronaphthalene at 298 K. The Arrhenius formulas were fitted for the OH addition.