title: Modeling the photochemical transformation of nitrobenzene under conditions relevant to sunlit surface waters: Reaction pathways and formation of intermediates.
abstract: Nitrobenzene (NB) would undergo photodegradation in sunlit surface waters, mainly by direct photolysis and triplet-sensitized oxidation, with a secondary role of the *OH reaction. Its photochemical half-life time would range from a few days to a couple of months under fair-weather summertime irradiation, depending on water chemistry and depth. NB phototransformation gives phenol and the three nitrophenol isomers, in different yields depending on the considered pathway. The minor *OH role in degradation would make NB unsuitable as *OH probe in irradiated natural water samples, but the selectivity towards *OH could be increased by monitoring the formation of phenol from NB+*OH. The relevant reaction would proceed through ipso-addition of *OH on the carbon atom bearing the nitro-group, forming a pre-reactive complex that would evolve into a transition state (and then into a radical addition intermediate) with very low activation energy barrier.
authors.affiliation: Università degli Studi di Torino, Dipartimento di Chimica, Via P.Giuria 5, 10125, Torino, Italy. Electronic address: davide.vione@unito.it.
authors.forename: Davide
authors.initials: D
authors.lastname: Vione
authors.affiliation: Università degli Studi di Torino, Dipartimento di Chimica, Via P.Giuria 5, 10125, Torino, Italy.
authors.forename: Elisa
authors.initials: E
authors.lastname: De Laurentiis
authors.affiliation: Università degli Studi di Torino, Dipartimento di Chimica, Via P.Giuria 5, 10125, Torino, Italy.
authors.forename: Silvia
authors.initials: S
authors.lastname: Berto
authors.affiliation: Università degli Studi di Torino, Dipartimento di Chimica, Via P.Giuria 5, 10125, Torino, Italy.
authors.forename: Claudio
authors.initials: C
authors.lastname: Minero
authors.affiliation: Yildiz Technical University, Department of Chemistry, 34220, Istanbul, Turkey.
authors.forename: Arzu
authors.initials: A
authors.lastname: Hatipoglu
authors.affiliation: Yildiz Technical University, Department of Chemistry, 34220, Istanbul, Turkey.
authors.forename: Zekiye
authors.initials: Z
authors.lastname: Cinar
mesh_terms: D006207:Half-Life; D017665:Hydroxyl Radical / Q000737:chemistry; D008956:Models, Chemical; D009578:Nitrobenzenes / Q000528:radiation effects*; D010782:Photolysis; D014874:Water Pollutants, Chemical / Q000528:radiation effects*
chemical_list: D009578:Nitrobenzenes; D014874:Water Pollutants, Chemical; D017665:Hydroxyl Radical; C036077:nitrobenzene
keywords: COSMO; DFT calculation; Hydroxyl radical; Nitrobenzene; Photo-oxidative degradation