title: Novel CFCs-substitutes recommended by EPA (hydrofluorocarbon-245fa and hydrofluoroether-7100): ion chemistry in air plasma and reactions with atmospheric ions.
abstract: The ion chemistry of the title compounds, a nonafluorobutyl methyl ether and a hydrofluoropropane, is elucidated by a combination of studies using atmospheric pressure ionization mass spectrometry and triple quadrupole mass spectrometry. In the positive ion mode, the hydrofluoroether readily forms an [M - F]+ ion, attributable to hydronium ion induced dehydrofluorination, the product of which can be further hydrated to give a protonated hydrofluoroester. By contrast, the hydrofluoropropane does not react with the hydronium ion but rather gives hydrofluoroalkenylium cations via H atom and F atom abstraction by the dioxygen radical cation. In the negative ion mode, the fluorobutyl methyl ether undergoes dissociative electron capture with O2-*, O2-*(H2O), O3-*, and NO2- to generate the fluorobutoxy anion, which can dissociate by CF2[doublebond]O loss to give the perfluorocarbanion when the precursor ions are internally excited. The hydrofluoropropane reacts readily with common atmospheric anions to form molecular complexes with F-, O2-*, and O3-* and the strongly H-bonded species, O2-*(HF) and F-(HF). Interestingly, isomeric pentafluoropropanes form in the reaction with O2-*, either O2-*(HF) or F-(HF), depending on the specific pattern of the fluoro substitution.
authors.affiliation: INTM del CNR-Sezione di Padova, Dipartimento di Scienze Chimiche, Università di Padova, Padova, Italy.
authors.forename: Ester
authors.initials: E
authors.lastname: Marotta
authors.forename: Cristina
authors.initials: C
authors.lastname: Paradisi
authors.forename: R Graham
authors.initials: RG
authors.lastname: Cooks
mesh_terms: D000388:Air / Q000032:analysis*; D000393:Air Pollutants / Q000737:chemistry*; D017402:Chlorofluorocarbons; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D007477:Ions; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D014481:United States; D014484:United States Environmental Protection Agency
chemical_list: D000393:Air Pollutants; D017402:Chlorofluorocarbons; D006845:Hydrocarbons, Fluorinated; D007477:Ions