title: Oxidation mechanisms of CF2Br2 and CH2Br2 induced by air nonthermal plasma.
abstract: Oxidation mechanisms in air nonthermal plasma (NTP) at room temperature and atmospheric pressure were investigated in a corona reactor energized by +dc, -dc, or +pulsed high voltage.. The two bromomethanes CF(2)Br(2) and CH(2)Br(2) were chosen as model organic pollutants because of their very different reactivities with OH radicals. Thus, they served as useful mechanistic probes: they respond differently to the presence of humidity in the air and give different products. By FT-IR analysis of the postdischarge gas the following products were detected and quantified: CO(2) and CO in the case of CH(2)Br(2), CO(2) and F(2)C ═ O in the case of CF(2)Br(2). F(2)C ═ O is a long-lived oxidation intermediate due to its low reactivity with atmospheric radicals. It is however removed from the NTP processed gas by passage through a water scrubber resulting in hydrolysis to CO(2) and HF. Other noncarbon containing products of the discharge were also monitored by FT-IR analysis, including HNO(3) and N(2)O. Ozone, an important product of air NTP, was never detected in experiments with CF(2)Br(2) and CH(2)Br(2) because of the highly efficient ozone depleting cycles catalyzed by BrOx species formed from the bromomethanes. It is concluded that, regardless of the type of corona applied, CF(2)Br(2) reacts in air NTP via a common intermediate, the CF(2)Br radical. The possible reactions leading to this radical are discussed, including, for -dc activation, charge exchange with O(2)(-), a species detected by APCI mass spectrometry.
authors.affiliation: Department of Chemical Sciences, Università di Padova, via Marzolo 1, 35131 Padova, Italy.
authors.forename: Milko
authors.initials: M
authors.lastname: Schiorlin
authors.forename: Ester
authors.initials: E
authors.lastname: Marotta
authors.forename: Marta
authors.initials: M
authors.lastname: Dal Molin
authors.forename: Cristina
authors.initials: C
authors.lastname: Paradisi
mesh_terms: D000388:Air; D000393:Air Pollutants / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry; D002248:Carbon Monoxide / Q000737:chemistry; D005617:Chlorofluorocarbons, Methane / Q000737:chemistry*; D006842:Hydrocarbons, Brominated / Q000737:chemistry*; D009609:Nitrous Oxide / Q000737:chemistry; D010084:Oxidation-Reduction; D017550:Spectroscopy, Fourier Transform Infrared; D013464:Sulfuric Acids / Q000737:chemistry
chemical_list: D000393:Air Pollutants; D005617:Chlorofluorocarbons, Methane; D006842:Hydrocarbons, Brominated; D013464:Sulfuric Acids; D002245:Carbon Dioxide; D002248:Carbon Monoxide; C048813:potassium peroxymonosulfuric acid; D009609:Nitrous Oxide; C027947:methylene bromide