New particle formation from the reactions of ozone with indene and styrene.

This work reports the experimental study of the ozonolysis of indene in the presence of SO2 and the reaction conditions leading to the formation of secondary aerosols. The reactions have been carried out in a Teflon chamber filled with synthetic air mixtures at atmospheric pressure and room temperature. As in the case of styrene, SO2 plays a key role in the oxidation of the Criegee intermediates and enhances the formation of particulate matter. Thus, for the ozonolysis of indene, nucleation was observed for reacted indene concentrations above (4.5 ± 0.8) × 1011 molecule cm-3 in the absence of SO2 while new particle formation was observed for concentrations one order of magnitude lower, (3 ± 1) × 1010 molecule cm-3, in the presence of SO2. Within the detection limit of the system, SO2 concentrations remained constant during the experiments. The formation of secondary aerosols in the smog chamber was inhibited by H2O and so the potential formation of secondary aerosols under atmospheric conditions depends on the concentration of SO2 and relative humidity. Computational calculations have been performed for the ozonolysis of both indene and styrene in the presence of SO2 and water to identify the reaction channels and species responsible for new particle formation. The release of SO3 and its subsequent conversion into H2SO4 from the reaction of the Criegee intermediate H2COO in the ozonolysis of styrene makes this aromatic have a high potential of aerosol formation in the atmosphere. On the other hand, quantitative conversion of SO2 into SO3 does not occur following the ozonolysis of indene.

Photolysis study of fluorinated ketones under natural sunlight conditions.

UV-visible absorption cross-sections are reported for CF3C(O)CH3, CF3C(O)CH2CH3, and CH3CH2C(O)CH(CH3)2. The photolysis rate constants of CF3C(O)CH3, CF3C(O)CH2CH3, and CF3CF2C(O)CF(CF3)2 were measured from smog-chamber experiments carried out in a 400 L Teflon-bag reactor under sunlight irradiation. Actinic radiation profiles from the "Tropospheric Ultraviolet and Visible Radiation Model" were used to obtain quantum efficiencies of photolysis: 0.34 ± 0.08, 0.24 ± 0.06, and (4.4 ± 0.6) × 10(-2) for CF3C(O)CH3, CF3C(O)CH2CH3, and CF3CF2C(O)CF(CF3)2, respectively. These values correspond to wavelength ranges of 295-345 nm (for CF3C(O)CH3 and CF3C(O)CH2CH3) and 295-360 nm (for CF3CF2C(O)CF(CF3)2). The photolysis rate constants change significantly with the seasons, with the yearly averages being (2.3 ± 0.7) × 10(-6), (1.8 ± 0.6) × 10(-6), and (2.1 ± 0.8) × 10(-6) s(-1) for CF3C(O)CH3, CF3C(O)CH2CH3, and CF3CF2C(O)CF(CF3)2, respectively. Photolysis processes are fast and responsible for the short gas-phase lifetimes of the studied ketones, which are 5.1 ± 2.2, 6.5 ± 2.5 and 5.5 ± 1.5 days. The radiative forcing efficiencies are provided to assess the contribution of emissions of these gases to climate change. As a result of the short atmospheric lifetimes, their global warming potentials are negligible. Theoretical calculations involving ground and excited states justify the higher photolysis quantum efficiencies of CF3C(O)CH3 and CF3C(O)CH2CH3 compared to CF3CF2C(O)CF(CF3)2, which shows increased photolysis rate constants in the absence of O2.

Atmospheric chemistry and environmental assessment of inhalational fluroxene.

Smog chamber/gas chromatography techniques are used to investigate the atmospheric degradation of fluroxene, an anesthetic, through oxidation with OH and Cl radicals at 298 K and under atmospheric pressure of N2 or air. The measured rate constants (k) are: k(fluroxene+OH(.) )=(2.96±0.61)×10(-11) and k(fluroxene+Cl(.) )=(1.62±0.19)×10(-10) cm(3) molecule(-1) s(-1) . The only product detected after the oxidation of fluroxene with OH radicals is 2,2,2-trifluoroethyl formate (79 % and 83 % molar yield in the absence and presence of NOx, respectively). However, after oxidation with Cl radicals, the detected products are 2,2,2-trifluoroethyl formate (78 %), 2,2,2-trifluoroethyl-1-chloroacetate (5 %), and chloroacetaldehyde (4 %), in the absence of NOx, and 2,2,2-trifluoroethyl formate (93 %), 2,2,2-trifluoroethyl-1-chloroacetate (6 %), and chloroacetaldehyde (5 %), in the presence of NOx. The results indicate that, both in the absence and presence of NOx, the main fate of fluroxene is the addition of the oxidant to the double bond and, once the alkoxy radical is formed, the main decomposition pathway is by means of degradation. Moreover, it is expected that 2,2,2-trifluoroethyl formate is the only oxidation product able to actively contribute to climate change. To successfully assess the contribution of fluroxene to global warming, we measure the infrared spectra of fluroxene and 2,2,2-trifluoroethyl formate, and calculate the radiative efficiencies (REs) to be 0.27 and 0.28 W m(-2) ppbv(-1) , respectively. In addition, the cumulative effect owing to the formation of 2,2,2-trifluoroethyl formate is investigated, and the direct, indirect, and net global-warming potentials are calculated by using the REs and lifetimes of fluroxene and 2,2,2-trifluoroethyl formate.

The role of tropospheric ice surfaces in the elimination of the CFC substitute, trifluoroethanol.

This work provides uptake results of CF(3)CH(2)OH on ice over the temperature range 203-223 K using a coated wall flow tube coupled to mass spectrometric detection. For experiments over pure ice, the adsorption was fully reversible and the data could be described in terms of the Langmuir isotherm for the range of concentrations and temperatures studied. For this temperature range, ΔH°(ads) = -46 ± 16 kJ mol(-1) was obtained (error is 2σ + 5%). For experiments on doped ice with nitric acid over the temperature range 203-223 K, the number of adsorbed molecules was slightly lower than over pure ice. At temperatures above 231 K, the extent of the reversible uptake of CF(3)CH(2)OH is enhanced in the presence of nitric acid due to coexistence of a liquid solution phase. Under such conditions the obtained solubility data follow Henry's law. Although pure ice and acid doped water surfaces do not permanently scavenge CF(3)CH(2)OH, the partitioning of CF(3)CH(2)OH between the gas phase and aqueous condensed phases may play a role as reservoirs or as a means of transport in the troposphere.

Radiative efficiencies for fluorinated esters: indirect global warming potentials of hydrofluoroethers.

Density Functional Theory (DFT) has been used with an empirically-derived correction for the wavenumbers of vibrational band positions to predict the infrared spectra of several fluorinated esters (FESs). Radiative efficiencies (REs) were then determined using the method of Pinnock et al. and these were used with atmospheric lifetimes from the literature to determine the direct global warming potentials of FESs. FESs, in particular fluoroalkylacetates, alkylfluoroacetates and fluoroalkylformates, are potential greenhouse gases and their likely long atmospheric lifetimes and relatively large REs, compared to their parent HFEs, make them active contributors to global warming. Here, we use the concept of indirect global warming potential (indirect GWP) to assess the contribution to the warming of several commonly used HFEs emitted from the Earth's surface, explicitly taking into account that these HFEs will be converted into the corresponding FESs in the troposphere. The indirect GWP can be calculated using the radiative efficiencies and lifetimes of the HFE and its degradation FES products. We found that the GWPs of those studied HFEs which have the smallest direct GWP can be increased by 100-1600% when taking account of the cumulative effect due to the secondary FESs formed during HFE atmospheric oxidation. This effect may be particularly important for non-segregated HFEs and some segregated HFEs, which may contribute significantly more to global warming than can be concluded from examination of their direct GWPs.

Atmospheric chemistry of C4F9OC2H5 (HFE-7200), C4F9OCH3 (HFE-7100), C3F7OCH3 (HFE-7000) and C3F7CH2OH: temperature dependence of the kinetics of their reactions with OH radicals, atmospheric lifetimes and global warming potentials.

The atmospheric chemistry of several gases used in industrial applications, C(4)F(9)OC(2)H(5) (HFE-7200), C(4)F(9)OCH(3) (HFE-7100), C(3)F(7)OCH(3) (HFE-7000) and C(3)F(7)CH(2)OH, has been studied. The discharge flow technique coupled with mass-spectrometric detection has been used to study the kinetics of their reactions with OH radicals as a function of temperature. The infrared spectra of the compounds have also been measured. The following Arrhenius expressions for the reactions were determined (in units of cm(3) molecule(-1) s(-1)): k(OH + HFE-7200) = (6.9(-1.7)(+2.3)) x 10(-11) exp(-(2030 +/- 190)/T); k(OH + HFE-7100) = (2.8(-1.5)(+3.2)) x 10(-11) exp(-(2200 +/- 490)/T); k(OH + HFE-7000) = (2.0(-0.7)(+1.2)) x 10(-11) exp(-(2130 +/- 290)/T); and k(OH + C(3)F(7)CH(2)OH) = (1.4(-0.2)(+0.3)) x 10(-11) exp(-(1460 +/- 120)/T). From the infrared spectra, radiative forcing efficiencies were determined and compared with earlier estimates in the literature. These were combined with the kinetic data to estimate 100-year time horizon global warming potentials relative to CO(2) of 69, 337, 499 and 36 for HFE-7200, HFE-7100, HFE-7000 and CF(3)CF(2)CF(2)CH(2)OH, respectively.

Secondary organic aerosol formation from styrene photolysis and photooxidation with hydroxyl radicals.

The formation of secondary organic aerosol (SOA) generated by irradiating styrene in the presence and/or absence of OH, NOx, H2O vapour and seed aerosol has been investigated for the first time. Experiments were conducted in a smog chamber at 298 K and atmospheric pressure. Styrene decay was measured by gas chromatography with a mass spectrometric detector (GC-MS), and the temporal evolution of the aerosol was monitored using a fast mobility particle sizer (FMPS). The SOA yield increases as the initial styrene concentration increases, leading to yields ranging from 1.8% to 3.5% for styrene photolysis, and from 2.4% to 5.0% for its photooxidation. In both cases, the organic aerosol formation can be expressed by a one-product gas/particle partitioning absorption model. The particle number concentration, mass and yield decrease in the presence of NOx and seed aerosol but increase at higher relative humidity (RH). The gas phase and SOA composition were analysed offline using a filter/denuder sampling system simultaneously collecting gas- and particle-phase products. Benzaldehyde was confirmed as the main gas-phase product of the reaction. However, although products in the particle phase were detected, they could not be identified. Moreover, the aqueous filter extracts were analysed using UV-Visible spectrophotometry to determine differences in the optical properties of SOA produced in the presence and absence of NOx. The results from this work may be used to discuss the implications of atmospheric SOA generation from styrene degradation.

Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms.

BACKGROUND, AIM, AND SCOPE: The adverse environmental impacts of chlorinated hydrocarbons on the Earth's ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C-F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF(3)CF(2)CF(2)OCH(3)) (1) and its isomer CF(3)CF(2)CF(2)CH(2)OH (2). MATERIALS AND METHODS: Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube-mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266-333 and 298-353 K for reactions of HFE-7000 and CF(3)CF(2)CF(2)CH(2)OH, respectively. RESULTS: The measured room temperature rate constants were k(Cl+CF(3)CF(2)CF(2)OCH(3)) = (1.24 +/- 0.28) x 10(-13) cm(3) molecule(-1) s(-1)and k(Cl+CF(3)CF(2)CF(2)CH(2)OH) = (8.35 +/- 1.63) x 10(-13) cm(3) molecule(-1) s(-1) (errors are 2sigma + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k (1)(266-333 K) = (6.1 +/- 3.8) x 10(-13)exp[-(445 +/- 186)/T] cm(3) molecule(-1) s(-1) and k (2)(298-353 K) = (1.9 +/- 0.7) x 10(-12)exp[-(244 +/- 125)/T] cm(3) molecule(-1) s(-1) (errors are 2sigma). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 +/- 0.38 and 0.97 +/- 0.16 (errors are 2sigma) were obtained for CF(3)CF(2)CF(2)OCH(3) and CF(3)CF(2)CF(2)CH(2)OH, respectively. DISCUSSION: The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k (1) and k (2), HFE-7000 is significantly less reactive than its isomer C(3)F(7)CH(2)OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of -CF(2)- in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of -CF(2)- without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C(3)H(7)CH(2)OH, respectively. CONCLUSIONS: The studied CFCs' substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, tau (Cl) values as low as 2.5 and 0.4 years for HFE-7000 and C(3)H(7)CH(2)OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF(3)CF(2)CF(2)OCH(3), significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. RECOMMENDATIONS AND PERSPECTIVES: The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure-reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.

Cyclooctane tropospheric degradation initiated by reaction with C1 atoms.

GOAL, SCOPE AND BACKGROUND: Within the non-methane hydrocarbons, alkanes constitute the largest fraction of the anthropogenic emissions of volatile organic compounds. For the case of cyclic alkanes, tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, C1 atom reaction rate constants are generally one order of magnitude larger than those of OH. In the present work, the reaction of cyclooctane with C1 atoms has been studied within the temperature range of 279-333 K. METHODS: The kinetic study has been carried out using the fast flow tube technique coupled to mass spectrometry detection. The reaction has been studied under low pressure conditions, p=1 Torr, with helium as the carrier gas. RESULTS: The measured room temperature rate constant is very high, k=(2.63+/-0.54)x10-10 cm(3)molecule(-1)s(-1), around 20 times larger than that for the corresponding OH reaction. We also report the results of the rate coefficients obtained at different temperatures: k = (3.5+/-1.2)x 10(-10) exp[(-79+/-110)/T] cm(3) molecule(-1) s(-1) within the range of 279-333 K. This reaction shows an activation energy value close to zero. DISCUSSION: Quantitative formation of HCl has been observed, confirming the mechanism through H-atom abstraction. The reactivity of cyclic alkanes towards Cl atoms is clearly dependent on the number of CH2 groups in the molecule, as is shown by the increase in the rate constant when the length of the organic chain increases. This increase is very high for the small cyclic alkanes and it seems that the reactions are approaching the collision-controlled limit for cyclohexane and cyclooctane. Conclusions. These results show that gas-phase reaction with Cl in marine or coastal areas is an efficient sink (competing with the gas phase, OH initiated degradation) for the Earth's emissions of cyclooctane, with a Cl-based lifetime ranging from 11 to 2000 hours, depending on the location and time of day. RECOMMENDATIONS AND PERSPECTIVES: Cl and OH fast reactions with cyclooctane are expected to define the lifetime of cyclooctane emissions to the atmosphere. The degradation of cyclooctane occurs in a short period of time and consequently (under conditions of low atmospheric mass transport), close to the emission sources enabling a significant contribution to local effects, like the formation of photochemical smog.

Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO 2) in a coastal rural area in the southwest of Iberian Peninsula.

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX = NO2 + O3), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station "El Arenosillo" was used. The observed daily cycles of NO x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO x -independent 'regional' contribution (i.e. the O3 background), and a linearly NO x -dependent 'local' contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO2 increases with the increase in NO x concentration during the day. The higher proportion of NO2 observed at night must be due to the conversion of NO to NO2 by the NO + O3 reaction. With regards to the source of the local NO x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO + O2 = 2NO2, at high-NO x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO2, J NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.

Behaviour and variability of local and regional oxidant levels (OX = O3 + NO2) measured in a polluted area in central-southern of Iberian Peninsula.

The purpose of this work is to contribute to the understanding of the photochemical air pollution in central-southern of the Iberian Peninsula, analysing the behaviour and variability of oxidant levels (OX = O(3) + NO(2)), measured in a polluted area with the highest concentration of heavy industry in central Spain. A detailed air pollution database was observed from two monitoring stations. The data period used was 2008 and 2009, around 210,000 data, selected for its pollution and meteorological statistics, which are very representative of the region. Data were collected every 15 min, however hourly values were used to analyse the seasonal and daily ozone, NO, NO(2) and OX cycles. The variation of OX concentrations with NO(x) is investigated, for the first time, in the centre of the Iberian Peninsula. The concentration of OX was calculated using the sum of a NO(x)-independent 'regional' contribution (i.e. the O(3) background), and a linearly NO(x)-dependent 'local' contribution. Monthly dependence of regional and local OX concentration was observed to determine when the maximum values may be expected. The variation of OX concentrations with levels of NO(x) was also measured, in order to pinpoint the atmospheric sources of OX in the polluted areas. The ratios [NO(2)]/[OX] and [NO(2)]/[NO(x)] vs. [NO(x)] were analysed to find the fraction of OX in the form of NO(2), and the possible source of the local NO(x)-dependent contribution, respectively. The progressive increase of the ratio [NO(2)]/[OX] with [NO(x)] observed shows a greater proportion of OX in the form of NO(2) as the level of NO( x ) increases. The higher measured values in the ratio [NO(2)]/[NO(x)] should not be attributed to NO(x) emissions by vehicles; they could be explained by industrial emission, termolecular reactions or formaldehyde and HONO directly emitted by vehicles exhausts. We also estimate the rate of NO(2) photolysis, J (NO(2)) = 0.18-0.64 min(-1), a key atmospheric reaction that influence O(3) production and then the regional air quality. The first surface plot study of annual variation of the daily mean oxidant levels, obtained for this polluted area may be used to improve the atmospheric photochemical dynamic in this region of the Iberian Peninsula where there are undeniable air quality problems.

Surface ozone comparison conducted in two rural areas in central-southern Spain.

PURPOSE: The purpose of this work is to contribute to the understanding of the photochemical air pollution analysing the levels and temporal variations of surface ozone in two rural areas situated in central-southern Spain. METHOD: The study is based on ozone hourly data recorded during the overall period between January 2008 and November 2009. The seasonal and daily ozone cycles as well as the number of exceedances of the threshold established in the European Ozone Directive have been calculated and analysed. RESULTS: This study presents the first ozone data registered at these two rural sites in the Iberian Peninsula plateau. Ozone shows a clear seasonal variation with the lowest values in January and November. High ozone concentrations are interrelated with high radiation intensities, temperature and wind directions. The information threshold defined in the European Ozone Directives was exceeded six times, while the limit for protection of human health was exceeded more than 40 times. The limits to protect the vegetation were also exceeded. CONCLUSIONS: Porzuna (near Cabañeros National Park) presents higher ozone levels than Argamasilla during the night-time and during the daytime of the summer months. Ozone levels are lower in Argamasilla probably due to fresh emissions from the close industrial area of Puertollano. The ozone exceedances of the limits defined in the Ozone Directive point out an ozone problem in this rural region.

Kinetic, mechanistic and temperature dependence study of Cl reactions with CH3OC(O)H and CH3CH2OC(O)H. Atmospheric implications.

Reactions of Cl atoms with CH(3)OC(O)H (1) and CH(3)CH(2)OC(O)H (2) have been studied using the Discharge Flow-Mass Spectrometric (DF-MS) method. The study has been carried out at 1 Torr total pressure under pseudo-first-order conditions in the temperature range 253 K to 333 K to approach the tropospheric temperature profile. The measured room temperature rate coefficients are k(1)=(1.01+/-0.15) x 10(-12) cm(3) molecule(-1) s(-1) and k(2)=(8.78+/-1.22) x 10(-12) cm(3) molecule(-1) s(-1) (errors are 2sigma) and the fitted Arrhenius expressions, k(1)=(1.7+/-1.4) x 10(-11) exp -(810+/-250)/T cm(3) molecule(-1) s(-1) and k(2)=(5.5+/-4.8) x 10(-11) exp -(556+/-268)/T cm(3) molecule(-1) s(-1) (errors are 2sigma). The reactions proceed through the abstraction of an H atom to form HCl and the corresponding radical. At 298 K and 1 Torr, yields on HCl of 0.95+/-0.09 (error is 2sigma) for reaction (1) and 0.96+/-0.11 (error is 2sigma) for reaction (2) have been measured. The tropospheric lifetimes are calculated and discussed.

Atmospheric HFEs degradation in the gas phase: reactions of HFE-7100 and HFE-7200 with Cl atoms at low temperatures.

Kinetic rate coefficients for the reactions of HFE-7100 (1) (C4F9OCH3) and HFE-7200 (2) (C4F9OC2H5) with Cl atoms have been measured using a discharge flow mass spectrometric technique (DFMS) at 1 Torr total pressure. The reactions have been studied under pseudo-first-order kinetic conditions in excess of HFEs over Cl atoms and the study has been extended from 333 down to 234 K to approach the tropospheric temperature profile. At room temperature the measured rate constants are k (1) = (1.43 +/- 0.28) x 10(-13) cm3molecule(-1)s(-1) and k (2) = (2.1 +/- 0.1) x 10(-12) cm3molecule(-1)s(-1). The Arrhenius expressions from our results are (units in cm3molecule(-1)s(-1)): k (1) = (2.3 +/- 1.4) x 10(-10) exp - (2254 +/- 177)/T(234-315 K) and k (2) = (3.7 +/- 0.5) x 10(-11) exp - (852 +/- 38)/T(234-333 K) (errors are sigma). The reactions proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.88 +/- 0.09 and 0.95 +/- 0.10 (errors are 2sigma) were obtained for HFE-7100 and HFE-7200 reactions, respectively.