Products and mechanism of the OH-initiated photo-oxidation of perfluoro ethyl vinyl ether, C2F5OCF[double bond, length as m-dash]CF2.

The OH-initiated photo-oxidation of perfluoro ethyl vinyl ether (C2F5OCF[double bond, length as m-dash]CF2, PEVE) in air (298 K, 50 and 750 Torr total pressure) was studied in a photochemical reactor using in situ detection of PEVE and its products by Fourier transform IR absorption spectroscopy. The relative rate technique was used to derive the rate coefficient, k1, for the reaction of PEVE with OH as k1 = (2.8 ± 0.3) × 10-12 cm3 molecule-1 s-1. The photo-oxidation of PEVE in the presence of NOx at 1 bar results in formation of C2F5OCFO, FC(O)C(O)F and CF2O in molar yields of 0.50 ± 0.07, 0.46 ± 0.07 and 1.50 ± 0.22, respectively. FC(O)C(O)F and CF2O are formed partially in secondary, most likely heterogeneous processes. At a reduced pressure of 50 Torr, the product distribution is shifted towards formation of FC(O)C(O)F, indicating the important role of collisional quenching of initially formed association complexes, and enabling details of the reaction mechanism to be elucidated. An atmospheric photo-oxidation mechanism for PEVE is presented and the environmental implications of PEVE release and degradation are discussed.

Absolute and relative-rate measurement of the rate coefficient for reaction of perfluoro ethyl vinyl ether (C2F5OCF[double bond, length as m-dash]CF2) with OH.

The rate coefficient (k1) for the reaction of OH radicals with perfluoro ethyl vinyl ether (PEVE, C2F5OCF[double bond, length as m-dash]CF2) has been measured as a function of temperature (T = 207-300 K) using the technique of pulsed laser photolysis with detection of OH by laser-induced fluorescence (PLP-LIF) at pressures of 50 or 100 Torr N2 bath gas. In addition, the rate coefficient was measured at 298 K and in one atmosphere of air by the relative-rate technique with loss of PEVE and reference reactant monitored in situ by IR absorption spectroscopy. The rate coefficient has a negative temperature dependence which can be parameterized as: k1(T) = 6.0 × 10-13 exp[(480 ± 38/T)] cm3 molecule-1 s-1 and a room temperature value of k1 (298 K) = (3.0 ± 0.3) × 10-12 cm3 molecule-1 s-1. Highly accurate rate coefficients from the PLP-LIF experiments were achieved by optical on-line measurements of PEVE and by performing the measurements at two different apparatuses. The large rate coefficient and the temperature dependence indicate that the reaction proceeds via OH addition to the C[double bond, length as m-dash]C double bond, the high pressure limit already being reached at 50 Torr N2. Based on the rate coefficient and average OH levels, the atmospheric lifetime of PEVE was estimated to be a few days.

Identification of the major HOx radical pathways in an indoor air environment.

OH and HO2 profiles measured in a real environment have been compared to the results of the INCA-Indoor model to improve our understanding of indoor chemistry. Significant levels of both radicals have been measured and their profiles display similar diurnal behavior, reaching peak concentrations during direct sunlight (up to 1.6×106 and 4.0×107  cm-3 for OH and HO2 , respectively). Concentrations of O3 , NOx , volatile organic compounds (VOCs), HONO, and photolysis frequencies were constrained to the observed values. The HOx profiles are well simulated in terms of variation for both species (Pearson's coefficients: pOH =0.55, pHO2 =0.76) and concentration for OH (mean normalized bias error: MNBEOH =-30%), HO2 concentration being always underestimated (MNBEHO2 =-62%). Production and loss pathways analysis confirmed HONO photolysis role as an OH precursor (here up to 50% of the production rate). HO2 formation is linked to OH-initiated VOC oxidation. A sensitivity analysis was conducted by varying HONO, VOCs, and NO concentrations. OH, HO2 , and formaldehyde concentrations increase with HONO concentrations; OH and formaldehyde concentrations are weakly dependent on NO, whereas HO2 concentrations are strongly reduced with increasing NO. Increasing VOC concentrations decreases OH by consumption and enhances HO2 and formaldehyde.

Assessment of indoor HONO formation mechanisms based on in situ measurements and modeling.

The photolysis of HONO has been found to be the oxidation driver through OH formation in the indoor air measurement campaign SURFin, an extensive campaign carried out in July 2012 in a classroom in Marseille. In this study, the INCA-Indoor model is used to evaluate different HONO formation mechanisms that have been used previously in indoor air quality models. In order to avoid biases in the results due to the uncertainty in rate constants, those parameters were adjusted to fit one representative day of the SURFin campaign. Then, the mechanisms have been tested with the optimized parameters against other experiments carried out during the SURFin campaign. Based on the observations and these findings, we propose a new mechanism incorporating sorption of NO2 onto surfaces with possible saturation of these surfaces. This mechanism is able to better reproduce the experimental profiles over a large range of conditions.

Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF3OCF=CF2.

Product formation in the reaction of perfluorinated methyl vinyl ether, CF3OCF=CF2, with OH radicals is studied theoretically using the M06-2X/aug-cc-pVTZ and CCSD(T) levels of theory. The stable end-products in an oxidative atmosphere are predicted to be perfluorinated methyl formate, CF3OCFO, and fluorinated glycolaldehyde, CFOCF2OH, both with CF2O as coproduct. The prediction of glycolaldehyde as a product contrasts with experimental data, which found perfluoro glyoxal, CFOCFO, instead. The most likely explanation for this apparent disagreement is conversion of CFOCF2OH to CFOCFO, e.g. by multiple catalytic agents present in the reaction mixture, wall reactions, and/or photolysis. The formation routes for the glyoxal product proposed in earlier work appear unlikely, and are not supported by theoretical or related experimental work.

Correction: Kinetics and mechanism of the reaction of perfluoro propyl vinyl ether (PPVE, C3F7OCH[double bond, length as m-dash]CH2) with OH: assessment of its fate in the atmosphere.

Correction for 'Kinetics and mechanism of the reaction of perfluoro propyl vinyl ether (PPVE, C3F7OCH[double bond, length as m-dash]CH2) with OH: assessment of its fate in the atmosphere' by D. Amedro et al., Phys. Chem. Chem. Phys., 2015, 17, 18558-18566.

Kinetics and mechanism of the reaction of perfluoro propyl vinyl ether (PPVE, C3F7OCH=CH2) with OH: assessment of its fate in the atmosphere.

Absolute rate coefficients for the reaction between OH radicals and perfluoro propyl vinyl ether (PPVE) were obtained using the technique of pulsed laser photolysis with the detection of OH radicals by laser induced fluorescence. Rate coefficients were measured over a range of temperatures (212-298 K) and at either 50 or 200 Torr bath-gas (N2 or N2/O2). The temperature dependence of the rate coefficient is given by k1(212-298 K) = (4.88 ± 0.49) × 10(-13) exp[(564 ± 10)/T] cm(3) molecule(-1) s(-1) with a value at room temperature of (3.4 ± 0.3) × 10(-12) cm(3) molecule(-1) s(-1). No pressure dependence was observed, indicating that the reaction is at the high pressure limit under atmospheric conditions. The accuracy of the rate coefficient obtained was enhanced by on-line optical absorption measurements of PPVE at 184.95 nm using a value of σ(184.95 nm) = (5.64 ± 0.28) × 10(-18) cm(2) molecule(-1) determined in this work. An atmospheric lifetime of a few days for PPVE was calculated. Extensive quantum chemical calculations as a complement to the experimental work are presented in order to determine its probable tropospheric degradation mechanism.

Atmospheric and kinetic studies of OH and HO2 by the FAGE technique.

A new FAGE setup has recently been built at the University of Lille, France. It permits the quantification of OH and HO2 in the atmosphere with a detection limit of 3 x 105 molecules/(cm3 x min) for OH and 1 x 10(6) molecules/(cm3 x min) for HO2. Its coupling to a photolysis cell enables the measurement of the total reactivity of the hydroxyl radical in ambient air and kinetic studies in laboratory. Two configurations have been considered: one with the photolysis cell at 90 degrees to the FAGE nozzle, the other on line with the FAGE nozzle. The two configurations have been tested and validated by measuring the well known rate constants of OH with CH4, C3H8 and CO. The advantages and drawbacks of each configuration have been evaluated. The "on line" configuration limits losses and permits measurements over a larger reactivity range but is affected by OH formation from the laser beam striking the FAGE nozzle, thus limiting the ability to carry out energy dependence studies which can, in contrast, be successfully performed in the 90 degrees configuration.