Atmospheric chemistry of CF3OCF2CF2H and CF3OC(CF3)2H: reaction with Cl atoms and OH radicals, degradation mechanism, global warming potentials, and empirical relationship between k(OH) and k(Cl) for organic compounds

Using FTIR smog chamber techniques, k(Cl + CF3OCF2CF2H) = (2.70 +/- 0.52) x 10(-16), k(OH + CF3OCF2CF2H) = (2.26 +/- 0.18) x 10(-15), k(Cl + CF3OC(CF3)2H) = (1.58 +/- 0.27) x 10(-18) and k(OH + CF3OC(CF3)2H) = (3.26 +/- 0.95) x 10(-16) cm3 molecule(-1) s(-1) were measured. The atmospheric lifetimes of CF3OCF2CF2H and CF3OC(CF3)2H are estimated to be 27 and 216 years, respectively. Chlorine atom initiated oxidation of CF3OCF2CF2H in 700 Torr of air in the presence of NO(x) gives CF3OC(O)F in a molar yield of 36 +/- 5% and COF2 in a molar yield of 174 +/- 9%, whereas oxidation of CF3OC(CF3)2H gives CF3OC(O)CF3 and COF2 in molar yields that are indistinguishable from 100%. Quantitative infrared spectra were recorded and used to estimate global warming potentials of 3690 and 8230 (100 year time horizon, relative to CO2) for CF3OCF2CF2H and CF3OC(CF3)2H, respectively. All experiments were performed in 700 Torr of N2/O2 diluent at 296 +/- 2 K. An empirical relationship can be used to estimate the preexponential factor, which can be combined with k(298 K) to give the temperature dependence of reactions of OH radicals with organic compounds proceeding via H-atom abstraction: log(A/n) = (0.239 +/- 0.027) log(k(OH)/n) - (8.69 +/- 0.372), k(OH) is the rate constant at 298 K and n is the number of H atoms. The rates of H-atom abstraction by OH radicals and Cl atoms at 298 K from organic compounds are related by the expression log(k(OH)) = (0.412 +/- 0.049) log(k(Cl)) - (8.16 +/- 0.72). The utility of these expressions and the atmospheric chemistry of the title hydrofluoroethers are discussed.     

Atmospheric chemistry of CF3CH2CH2OH: kinetics, mechanisms and products of Cl atom and OH radical initiated oxidation in the presence and absence of NOX

Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with CF(3)CH(2)C(O)H and CF(3)CH(2)CH(2)OH in 700 Torr of N(2) or air diluent at 296 +/- 2 K. The rate constants determined were k(Cl+CF(3)CH(2)C(O)H) = (1.81 +/- 0.27) x 10(-11), k(OH+CF(3)CH(2)C(O)H) = (2.57 +/- 0.44) x 10(-12), k(Cl+CF(3)CH(2)CH(2)OH) = (1.59 +/- 0.20) x 10(-11), and k(OH+CF(3)CH(2)CH(2)OH) = (6.91 +/- 0.91) x 10(-13) cm(3) molecule(-1) s(-1). Product studies of the chlorine initiated oxidation of CF(3)CH(2)CH(2)OH in the absence of NO show the sole primary product to be CF(3)CH(2)C(O)H. Product studies of the chlorine initiated oxidation of CF(3)CH(2)CH(2)OH in the presence of NO show the primary products to be CF(3)CH(2)C(O)H (81%), HC(O)OH (10%), and CF(3)C(O)H. Product studies of the chlorine initiated oxidation of CF(3)CH(2)C(O)H in the absence of NO show the primary products to be CF(3)C(O)H (76%), CF(3)CH(2)C(O)OH (14%), and CF(3)CH(2)C(O)OOH (< or =10%). As part of this work, an upper limit of k(O(3)+CF(3)CH(2)CH(2)OH) < 2 x 10(-21) cm(3) molecule(-1) s(-1) was established. Results are discussed with respect to the atmospheric chemistry of fluorinated alcohols.     

Atmospheric chemistry of the Z and E isomers of CF3CF=CHF; kinetics, mechanisms, and products of gas-phase reactions with Cl atoms, OH radicals, and O3

Smog chamber/FTIR techniques were used to study the atmospheric chemistry of the Z and E isomers of CF3CF=CHF, which we refer to as CF3CF=CHF(Z) and CF3CF=CHF(E). The rate constants k(Cl + CF3CF=CHF(Z)) = (4.36 +/- 0.48) x 10-11, k(OH + CF3CF=CHF(Z)) = (1.22 +/- 0.14) x 10-12, and k(O3 + CF3CF=CHF(Z)) = (1.45 +/- 0.15) x 10-21 cm3 molecule-1 s-1 were determined for the Z isomer of CF3CF=CHF in 700 Torr air diluent at 296 +/- 2 K. The rate constants k(Cl + CF3CF=CHF(E)) = (5.00 +/- 0.56) x 10-11, k(OH + CF3CF=CHF(E)) = (2.15 +/- 0.23) x 10-12, and k(O3 + CF3CF=CHF(E)) = (1.98 +/- 0.15) x 10-20 cm3 molecule-1 s-1 were determined for the E isomer of CF3CF=CHF in 700 Torr air diluent at 296 +/- 2 K. Both the Cl-atom and OH-radical-initiated atmospheric oxidation of CF3CF=CHF give CF3C(O)F and HC(O)F in molar yields indistinguishable from 100% for both the Z and E isomer. CF3CF=CHF(Z) has an atmospheric lifetime of approximately 18 days and a global warming potential (100 year time horizon) of approximately 6. CF3CF=CHF(E) has an atmospheric lifetime of approximately 10 days and a global warming potential (100 year time horizon) of approximately 3. CF3CF=CHF has a negligible global warming potential and will not make any significant contribution to radiative forcing of climate change.     

Atmospheric chemistry of hydrofluoroethers: Reaction of a series of hydrofluoroethers with OH radicals and Cl atoms, atmospheric lifetimes, and global warming potentials

The kinetics of the OH radical and Cl atom reactions with nine fluorinated ethers have been studied by the relative rate method at 298 K and 1013 hPa using gas chromatography-mass spectroscopy (GC-MS) detection: k(OH + CH3CH2OCF3) = (1.55 +/- 0.25) x 10(-13), k(OH + CF3CH2OCH3) = (5.7 +/- 0.8) x 10(-13),k(OH + CF3CH2OCHF2) = (9.1 +/- 1.1) x 10(-15), k(OH + CF3CHFOCHF2) = (6.5 +/- 0.8) x 10(-15), k(OH + CHF2CHFOCF3) = (6.8 +/- 1.1) x 10(-15), k(OH + CF3CHFOCF3) < 1 x 10(-15), k(OH + CF3CHFCF2OCHF2) = (1.69 +/- 0.26) x 10(-14), k(OH + CF3CHFCF2OCH2CH3) = (1.47 +/- 0.13) x 10(-13), k(OH + CF3CF2CF2OCHFCF3) < 1 x 10(-15), k(Cl + CH3CH2OCF3) = (2.2 +/- 0.8) x 10(-12), k(Cl + CF3CH2OCH3) = (1.8 +/- 0.9) x 10(-11), k(Cl + CF3CH2OCHF2) = (1.5 +/- 0.4) x 10(-14), k(Cl + CF3CHFOCHF2) = (1.1 +/- 1.9) x 10(-15), k(Cl + CHF2CHFOCF3) = (1.2 +/- 2.0) x 10(-15), k(Cl + CF3CHFOCF3) < 3 x 10(-15), k(Cl + CF3CHFCF2OCHF2) < 6 x 10(-16), k(Cl + CF3CHFCF2OCH2CH3) = (3.1 +/- 1.1) x 10(-12), and k(Cl + CF3CF2CF2OCHFCF3) < 3 x 10(-15) cm3 molecule(-1) s(-1). The error limits include three standard deviations (3 sigma) from the statistical data analyses, as well as the errors in the rate coefficients of the reference compounds that are used. Infrared absorption cross sections and estimates of the trophospheric lifetimes and the global warming potentials of the fluorinated ethers are presented. The atmospheric degradation of the compounds is discussed.     

Kinetics and mechanisms of CF3CHFOCH3, CF3CHFOC(O)H, and FC(O)OCH3 reactions with OH radicals

The kinetics and mechanism of oxidation of CF3CHFOCH3 was studied using an 11.5-dm3 environmental reaction chamber. OH radicals were produced by UV photolysis of an O3-H2O-He mixture at an initial pressure of 200 Torr in the chamber. The rate constant of the reaction of CF3CHFOCH3 with OH radicals (k1) was determined to be (1.77 +/- 0.69) x 10(-12) exp[(-720 +/- 110)/T] cm3 molecule(-1)(s-1) by means of a relative rate method at 253-328 K. The mechanism of the reaction was investigated by FT-IR spectroscopy at 298 K. CF3CHFOC(O)H, FC(O)OCH3, and COF2 were determined to be the major products. The branching ratio (k1a/k1b) for the reactions CF3CHFOCH3 + OH --> CF3CHFOCH2* + H2O (k1a) and CF3CHFOCH3 + OH --> CF3CF*OCH3 + H2O (k1b) was estimated to be 4.2:1 at 298 K from the yields of CF3CHFOC(O)H, FC(O)OCH3, and COF2. The rate constants of the reactions of CF3CHFOC(O)H (k2) and FC(O)OCH3 (k3) with OH radicals were determined to be (9.14 +/- 2.78) x 10(-13) exp[(-1190 +/- 90)/T] and (2.10 +/- 0.65) x 10(-13) exp[(-630 +/- 90)/T] cm3 molecule(-1)(s-1), respectively, by means of a relative rate method at 253-328 K. The rate constants at 298 K were as follows: k1 = (1.56 +/- 0.06) x 10-13, k2 = (1.67 +/- 0.05) x 10-14, and k3 = (2.53 +/- 0.07) x 10-14 cm3 molecule(-1)(s-1). The tropospheric lifetimes of CF3CHFOCH3, CF3CHFOC(O)H, and FC(O)OCH3 with respect to reaction with OH radicals were estimated to be 0.29, 3.2, and 1.8 years, respectively.     

Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4): hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation

Smog chamber/Fourier transform infrared (FTIR) techniques were used to measure k(Cl+C(x)F(2x+1)CH(OH)(2)) (x = 1, 3, 4) = (5.84 +/- 0.92) x 10(-13) and k(OH+C(x)F(2x+1)CH(OH)(2)) = (1.22 +/- 0.26) x 10(-13) cm(3) molecule(-1) s(-1) in 700 Torr of N(2) or air at 296 +/- 2 K. The Cl initiated oxidation of CF(3)CH(OH)(2) in 700 Torr of air gave CF(3)COOH in a molar yield of 101 +/- 6%. IR spectra of C(x)F(2x+1)CH(OH)(2) (x = 1, 3, 4) were recorded and are presented. An upper limit of k(CF(3)CHO+H(2)O) < 2 x 10(-23) cm(3) molecule(-1) s(-1) was established for the gas-phase hydration of CF(3)CHO. Bubbling CF(3)CHO/air mixtures through liquid water led to >80% conversion of CF(3)CHO into the hydrate within the approximately 2 s taken for passage through the bubbler. These results suggest that OH radical initiated oxidation of C(x)F(2x+1)CH(OH)(2) hydrates could be a significant source of perfluorinated carboxylic acids in the environment.     

Atmospheric chemistry of CF3CH=CH2 and C4F9CH=CH2: products of the gas-phase reactions with Cl atoms and OH radicals

FTIR-smog chamber techniques were used to study the products of the Cl atom and OH radical initiated oxidation of CF3CH=CH2 in 700 Torr of N2/O2, diluent at 296 K. The Cl atom initiated oxidation of CF3CH=CH2 in 700 Torr of air in the absence of NOx gives CF3C(O)CH2Cl and CF3CHO in yields of 70+/-5% and 6.2+/-0.5%, respectively. Reaction with Cl atoms proceeds via addition to the >C=C< double bond (74+/-4% to the terminal and 26+/-4% to the central carbon atom) and leads to the formation of CF3CH(O)CH2Cl and CF3CHClCH2O radicals. Reaction with O2 and decomposition via C-C bond scission are competing loss mechanisms for CF3CH(O)CH2Cl radicals, kO2/kdiss=(3.8+/-1.8)x10(-18) cm3 molecule-1. The atmospheric fate of CF3CHClCH2O radicals is reaction with O2 to give CF3CHClCHO. The OH radical initiated oxidation of CxF2x+1CH=CH2 (x=1 and 4) in 700 Torr of air in the presence of NOx gives CxF2x+1CHO in a yield of 88+/-9%. Reaction with OH radicals proceeds via addition to the >C=C< double bond leading to the formation of CxF2x+1C(O)HCH2OH and CxF2x+1CHOHCH2O radicals. Decomposition via C-C bond scission is the sole fate of CxF2x+1CH(O)CH2OH and CxF2x+1CH(OH)CH2O radicals. As part of this work a rate constant of k(Cl+CF3C(O)CH2Cl)=(5.63+/-0.66)x10(-14) cm3 molecule-1 s-1 was determined. The results are discussed with respect to previous literature data and the possibility that the atmospheric oxidation of CxF2x+1CH=CH2 contributes to the observed burden of perfluorocarboxylic acids, CxF2x+1COOH, in remote locations.     

Atmospheric chemistry of propionaldehyde: kinetics and mechanisms of reactions with OH radicals and Cl atoms, UV spectrum, and self-reaction kinetics of CH3CH2C(O)O2 radicals at 298 K

The kinetics and mechanism of the reactions of Cl atoms and OH radicals with CH3CH2CHO were investigated at room temperature using two complementary techniques: flash photolysis/UV absorption and continuous photolysis/FTIR smog chamber. Reaction with Cl atoms proceeds predominantly by abstraction of the aldehydic hydrogen atom to form acyl radicals. FTIR measurements indicated that the acyl forming channel accounts for (88 +/- 5)%, while UV measurements indicated that the acyl forming channel accounts for (88 +/- 3)%. Relative rate methods were used to measure: k(Cl + CH3CH2CHO) = (1.20 +/- 0.23) x 10(-10); k(OH + CH3CH2CHO) = (1.82 +/- 0.23) x 10(-11); and k(Cl + CH3CH2C(O)Cl) = (1.64 +/- 0.22) x 10(-12) cm3 molecule(-1) s(-1). The UV spectrum of CH3CH2C(O)O2, rate constant for self-reaction, and rate constant for cross-reaction with CH3CH2O2 were determined: sigma(207 nm) = (6.71 +/- 0.19) x 10(-18) cm2 molecule(-1), k(CH3CH2C(O)O2 + CH3CH2C(O)O2) = (1.68 +/- 0.08) x 10(-11), and k(CH3CH2C(O)O2 + CH3CH2O2) = (1.20 +/- 0.06) x 10(-11) cm3 molecule(-1) s(-1), where quoted uncertainties only represent 2sigma statistical errors. The infrared spectrum of C2H5C(O)O2NO2 was recorded, and products of the Cl-initiated oxidation of CH3CH2CHO in the presence of O2 with, and without, NO(x) were identified. Results are discussed with respect to the atmospheric chemistry of propionaldehyde.     

A kinetic and mechanistic study of the reactions of OH radicals and Cl atoms with 3,3,3-trifluoropropanol under atmospheric conditions

Product distribution studies of the OH radical and Cl atom initiated oxidation of CF3CH2CH2OH in air at 1 atm and 298 +/- 5 K have been carried out in laboratory and outdoor atmospheric simulation chambers in the presence and absence of NOx. The results show that CF3CH2CHO is the only primary product and that the aldehyde is fairly rapidly removed from the system. In the absence of NOx the major degradation product of CF3CH2CHO is CF3CHO, and the combined yields of the two aldehydes formed from CF3CH2CH2OH are close to unity (0.95 +/- 0.05). In the presence of NOx small amounts of CF3CH2C(O)O2NO2 were also observed (<15%). At longer reaction times CF3CHO is removed from the system to give mainly CF2O. The laser photolysis-laser induced fluorescence technique was used to determine values of k(OH + CF3CH2CH2OH) = (0.89 +/- 0.03) x 10(-12) and k(OH + CF3CH2CHO) = (2.96 +/- 0.04) x 10(-12) cm3 molecule(-1) s(-1). A relative rate method has been employed to measure the rate coefficients k(OH + CF3CH2CH2OH) = (1.08 +/- 0.05) x 10(-12), k(OH + C6F13CH2CH2OH) = (0.79 +/- 0.08) x 10(-12), k(Cl + CF3CH2CH2OH) = (22.4 +/- 0.4) x 10(-12), and k(Cl + CF3CH2CHO) = (25.7 +/- 0.4) x 10(-12) cm3 molecule(-1) s(-1). The results from this investigation are discussed in terms of the possible importance of emissions of fluorinated alcohols as a source of fluorinated carboxylic acids in the environment.     

Atmospheric chemistry of a model biodiesel fuel, CH3C(O)O(CH2)2OC(O)CH3: kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation in the presence and absence of NOx

Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with ethylene glycol diacetate, CH3C(O)O(CH2)2OC(O)CH3, in 700 Torr of N2/O2 diluent at 296 K. The rate constants measured were k(Cl + CH3C(O)O(CH2)2OC(O)CH3) = (5.7 +/- 1.1) x 10(-12) and k(OH + CH3C(O)O(CH2)2OC(O)CH3) = (2.36 +/- 0.34) x 10(-12) cm3 molecule-1 s-1. Product studies of the Cl atom initiated oxidation of ethylene glycol diacetate in the absence of NO in 700 Torr of O2/N2 diluent at 296 K show the primary products to be CH3C(O)OC(O)CH2OC(O)CH3, CH3C(O)OC(O)H, and CH3C(O)OH. Product studies of the Cl atom initiated oxidation of ethylene glycol diacetate in the presence of NO in 700 Torr of O2/N2 diluent at 296 K show the primary products to be CH3C(O)OC(O)H and CH3C(O)OH. The CH3C(O)OCH2O* radical is formed during the Cl atom initiated oxidation of ethylene glycol diacetate, and two loss mechanisms were identified: reaction with O2 to give CH3C(O)OC(O)H and alpha-ester rearrangement to give CH3C(O)OH and HC(O) radicals. The reaction of CH3C(O)OCH2O2* with NO gives chemically activated CH3C(O)OCH2O* radicals which are more likely to undergo decomposition via the alpha-ester rearrangement than CH3C(O)OCH2O* radicals produced in the peroxy radical self-reaction.     

Kinetics of the reactions of Cl*(2P(1/2)) and Cl(2P(3/2)) atoms with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH at 295 K

The title reactions were studied using laser flash photolysis/laser-induced-fluorescence (FP-LIF) techniques. The two spin-orbit states, Cl*(2P(1/2)) and Cl(2P(3/2)), were detected using LIF at 135.2 and 134.7 nm, respectively. Measured reaction rate constants were as follows (units of cm3 molecule(-1) s(-1)): k(Cl(2P(3/2))+CH3OH) = (5.35 +/- 0.24) x 10(-11), k(Cl(2P(3/2))+C2H5OH) = (9.50 +/- 0.85) x 10(-11), k(Cl(2P(3/2))+n-C3H7OH) = (1.71 +/- 0.11) x 10(-10), and k(Cl(2P(3/2))+i-C3H7OH) = (9.11 +/- 0.60) x 10(-11). Measured rate constants for total removal of Cl*(2P(1/2)) in collisions with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH were (1.95 +/- 0.13) x 10(-10), (2.48 +/- 0.18) x 10(-10), (3.13 +/- 0.18) x 10(-10), and (2.84 +/- 0.16) x 10(-10), respectively; quoted errors are two-standard deviations. Although spin-orbit excited Cl*(2P(1/2)) atoms have 2.52 kcal/mol more energy than Cl(2P(3/2)), the rates of chemical reaction of Cl*(2P(1/2)) with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH are only 60-90% of the corresponding Cl(2P(3/2)) atom reactions. Under ambient conditions spin-orbit excited Cl* atoms are responsible for 0.5%, 0.5%, 0.4%, and 0.7% of the observed reactivity of thermalized Cl atoms toward CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH, respectively.     

Kinetic study of the reactions of Cl atoms with CF3CH2CH2OH, CF3CF2CH2OH, CHF2CF2CH2OH, and CF3CHFCF2CH2OH

The reaction kinetics of chlorine atoms with a series of partially fluorinated straight-chain alcohols, CF(3)CH(2)CH(2)OH (1), CF(3)CF(2)CH(2)OH (2), CHF(2)CF(2)CH(2)OH (3), and CF(3)CHFCF(2)CH(2)OH (4), were studied in the gas phase over the temperature range of 273-363 K by using very low-pressure reactor mass spectrometry. The absolute rate coefficients were given by the expressions (in cm(3) molecule(-1) s(-1)): k(1) = (4.42 +/- 0.48) x 10(-11) exp(-255 +/- 20/T); k(1)(303) = (1.90 +/- 0.17) x 10(-11), k(2) = (2.23 +/- 0.31) x 10(-11) exp(-1065 +/- 106/ T); k(2)(303) = (6.78 +/- 0.63) x 10(-13), k(3) = (8.51 +/- 0.62) x 10(-12) exp(-681 +/- 72/T); k(3)(303) = (9.00 +/- 0.82) x 10(-13) and k(4) = (6.18 +/- 0.84) x 10(-12) exp(-736 +/- 42/T); k(4)(303) = (5.36 +/- 0.51) x 10(-13). The quoted 2sigma uncertainties include the systematic errors. All title reactions proceed via a hydrogen atom metathesis mechanism leading to HCl. Moreover, the oxidation of the primarily produced radicals was investigated, and the end products were the corresponding aldehydes (R(F)-CHO; R(F) = -CH(2)CF(3), -CF(2)CF(3), -CF(2)CHF(2), and -CF(2)CHFCF(3)), providing a strong experimental indication that the primary reactions proceed mainly via the abstraction of a methylenic hydrogen adjacent to a hydroxyl group. Finally, the bond strengths and ionization potentials for the title compounds were determined by density functional theory calculations, which also suggest that the alpha-methylenic hydrogen is mainly under abstraction by Cl atoms. The correlation of room-temperature rate coefficients with ionization potentials for a set of 27 molecules, comprising fluorinated C2-C5 ethers and C2-C4 alcohols, is good with an average deviation of a factor of 2, and is given by the expression log(k) (in cm(3) molecule(-1) s(-1)) = (5.8 +/- 1.4) - (1.56 +/- 0.13) x (ionization potential (in eV)).     

CF3CF=CH2 and (Z)-CF3CF=CHF: temperature dependent OH rate coefficients and global warming potentials

Rate coefficients over the temperature range 206-380 K are reported for the gas-phase reaction of OH radicals with 2,3,3,3-tetrafluoropropene (CF(3)CF=CH(2)), k(1)(T), and 1,2,3,3,3-pentafluoropropene ((Z)-CF(3)CF=CHF), k(2)(T), which are major components in proposed substitutes for HFC-134a (CF(3)CFH(2)) in mobile air-conditioning units. Rate coefficients were measured under pseudo-first-order conditions in OH using pulsed-laser photolysis to produce OH and laser-induced fluorescence to detect it. Rate coefficients were found to be independent of pressure between 25 and 600 Torr (He, N(2)). For CF(3)CF=CH(2), the rate coefficients, within the measurement uncertainty, are given by the Arrhenius expression k(1)(T)=(1.26+/-0.11) x 10(-12) exp[(-35+/-10)/T] cm(3) molecule(-1) s(-1) where k(1)(296 K)=(1.12+/-0.09) x 10(-12) cm(3) molecule(-1) s(-1). For (Z)-CF(3)CF=CHF, the rate coefficients are given by the non-Arrhenius expression k(2)(T)=(1.6+/-0.2) x 10(-18)T(2) exp[(655+/-50)/T] cm(3) molecule(-1) s(-1) where k(2)(296 K)=(1.29+/-0.06) x 10(-12) cm(3) molecule(-1) s(-1). Over the temperature range most relevant to the atmosphere, 200-300 K, the Arrhenius expression k(2)(T)=(7.30+/-0.7) x 10(-13) exp[(165+/-20)/T] cm(3) molecule(-1) s(-1) reproduces the measured rate coefficients very well and can be used in atmospheric model calculations. The quoted uncertainties in the rate coefficients are 2sigma (95% confidence interval) and include estimated systematic errors. The global warming potentials for CF(3)CF=CH(2) and (Z)-CF(3)CF=CHF were calculated to be <4.4 and <3.6, respectively, for the 100 year time horizon using infrared absorption cross sections measured in this work, and atmospheric lifetimes of 12 and 10 days that are based solely on OH reactive loss.     

Kinetic and product study of the gas-phase reactions of OH radicals, NO(3) radicals, and O(3) with (C(2)H(5)O)(2)P(S)CH(3) and (C(2)H(5)O)(3)PS

Rate constants for the reactions of OH radicals and NO3 radicals with O,O-diethyl methylphosphonothioate [(C(2)H(5)O)(2)P(S)CH(3); DEMPT] and O,O,O-triethyl phosphorothioate [(C(2)H(5)O)(3)PS; TEPT] have been measured using relative rate methods at atmospheric pressure of air over the temperature range 296-348 K for the OH radical reactions and at 296 +/- 2 K for the NO(3) radical reactions. At 296 +/- 2 K, the rate constants obtained for the OH radical reactions (in units of 10(-11) cm(3) molecule(-1) s(-1)) were 20.4 +/- 0.8 and 7.92 +/- 0.27 for DEMPT and TEPT, respectively, and those for the NO(3) radical reactions (in units of 10(-15) cm(3) molecule(-1) s(-1)) were 2.01 +/- 0.20 and 1.03 +/- 0.10, respectively. Upper limits to the rate constants for the reactions of O(3) with DEMPT and TEPT of <6 x 10(-20) cm(3) molecule(-1) s(-1) were determined in each case. Rate constants for the OH radical reactions, measured relative to k(OH + alpha-pinene) = 1.21 x 10(-11) e(436/T) cm(3) molecule(-1) s(-1), resulted in the Arrhenius expressions k(OH + DEMPT) = 1.08 x 10(-11) e(871+/-25)/T cm(3) molecule(-1) s(-1) and k(OH + TEPT) = 8.21 x 10(-13) e(1353+/-49)/T cm(3) molecule(-1) s(-1) over the temperature range 296-348 K, where the indicated errors are two least-squares standard deviations and do not include the uncertainties in the reference rate constant. Diethyl methylphosphonate was identified and quantified from the OH radical and NO(3) radical reactions with DEMPT, with formation yields of 21 +/- 4%, independent of temperature, from the OH radical reaction and 62 +/- 11% from the NO(3) radical reaction at 296 +/- 2 K. Similarly, triethyl phosphate was identified and quantified from the OH radical and NO(3) radical reactions with TEPT, with formation yields of 56 +/- 9%, independent of temperature, from the OH radical reaction and 78 +/- 15% from the NO(3) radical reaction at 296 +/- 2 K.     

Kinetics and mechanism of (CF3)2CHOCH3 reaction with OH radicals in an environmental reaction chamber

The atmospheric chemistry of (CF3)2CHOCH3, a possible HCFC/HFC alternative, was studied using a smog chamber/FT-IR technique. OH radicals were prepared by the photolysis of ozone in a 200-Torr H2O/O3/O2 gas mixture held in an 11.5-dm3 temperature-controlled chamber. The rate constant, k1, for the reaction of (CF3)2CHOCH3 with OH radicals was determined to be (1.40 +/- 0.28) x 10(-12) exp[(-550 +/- 60)/T] cm3 molecule(-1) s(-1) by means of a relative rate method at 253-328 K. The value of k1 at 298 K was (2.25 +/- 0.04) x 10(-13) cm3 molecule(-1) s(-1). The random errors are reported with +/-2 standard deviations, and potential systematic errors of 15% could increase k(1). In considering OH-radical reactions, we estimated the tropospheric lifetime of (CF3)2CHOCH3 to be 2.0 months using the rate constant at 288 K. The degradation mechanism of (CF3)2CHOCH3 initiated by OH radicals was also investigated using FT-IR spectroscopy at 298 K. Products (CF3)2CHOC(O)H, CF3C(OH)2CF3, CF3C(O)OCH3, and COF(2) were identified and quantified. The branching ratio, k1a/k1b, was estimated to be 2.1:1 for reactions (CF3)2CHOCH3 + OH --> (CF3)2CHOCH2*+ H2O (k1a) and (CF3)2CHOCH3 + OH --> (CF3)2C*OCH3 + H2O (k1b).     

Atmospheric chemistry of CF3CF═CH2 and (Z)-CF3CF═CHF: Cl and NO3 rate coefficients, Cl reaction product yields, and thermochemical calculations

Rate coefficients, k, for the gas-phase reactions of Cl atoms and NO(3) radicals with 2,3,3,3-tetrafluoropropene, CF(3)CF═CH(2) (HFO-1234yf), and 1,2,3,3,3-pentafluoropropene, (Z)-CF(3)CF═CHF (HFO-1225ye), are reported. Cl-atom rate coefficients were measured in the fall-off region as a function of temperature (220-380 K) and pressure (50-630 Torr; N(2), O(2), and synthetic air) using a relative rate method. The measured rate coefficients are well represented by the fall-off parameters k(0)(T) = 6.5 × 10(-28) (T/300)(-6.9) cm(6) molecule(-2) s(-1) and k(∞)(T) = 7.7 × 10(-11) (T/300)(-0.65) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and k(0)(T) = 3 × 10(-27) (T/300)(-6.5) cm(6) molecule(-2) s(-1) and k(∞)(T) = 4.15 × 10(-11) (T/300)(-0.5) cm(3) molecule(-1) s(-1) for (Z)-CF(3)C═CHF with F(c) = 0.6. Reaction product yields were measured in the presence of O(2) to be (98 ± 7)% for CF(3)C(O)F and (61 ± 4)% for HC(O)Cl in the CF(3)CF═CH(2) reaction and (108 ± 8)% for CF(3)C(O)F and (112 ± 8)% for HC(O)F in the (Z)-CF(3)CF═CHF reaction, where the quoted uncertainties are 2σ (95% confidence level) and include estimated systematic errors. NO(3) reaction rate coefficients were determined using absolute and relative rate methods. Absolute measurements yielded upper limits for both reactions between 233 and 353 K, while the relative rate measurements yielded k(3)(295 K) = (2.6 ± 0.25) × 10(-17) cm(3) molecule(-1) s(-1) and k(4)(295 K) = (4.2 ± 0.5) × 10(-18) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF, respectively. The Cl-atom reaction with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF leads to decreases in their atmospheric lifetimes and global warming potentials and formation of a chlorine-containing product, HC(O)Cl, for CF(3)CF═CH(2). The NO(3) reaction has been shown to have a negligible impact on the atmospheric lifetimes of CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF. The energetics for the reaction of Cl, NO(3), and OH with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF in the presence of O(2) were investigated using density functional theory (DFT).     

Atmospheric chemistry of isoflurane, desflurane, and sevoflurane: kinetics and mechanisms of reactions with chlorine atoms and OH radicals and global warming potentials

The smog chamber/Fourier-transform infrared spectroscopy (FTIR) technique was used to measure the rate coefficients k(Cl + CF(3)CHClOCHF(2), isoflurane) = (4.5 ± 0.8) × 10(-15), k(Cl + CF(3)CHFOCHF(2), desflurane) = (1.0 ± 0.3) × 10(-15), k(Cl + (CF(3))(2)CHOCH(2)F, sevoflurane) = (1.1 ± 0.1) × 10(-13), and k(OH + (CF(3))(2)CHOCH(2)F) = (3.5 ± 0.7) × 10(-14) cm(3) molecule(-1) in 700 Torr of N(2)/air diluent at 295 ± 2 K. An upper limit of 6 × 10(-17) cm(3) molecule(-1) was established for k(Cl + (CF(3))(2)CHOC(O)F). The laser photolysis/laser-induced fluorescence (LP/LIF) technique was employed to determine hydroxyl radical rate coefficients as a function of temperature (241-298 K): k(OH + CF(3)CHFOCHF(2)) = (7.05 ± 1.80) × 10(-13) exp[-(1551 ± 72)/T] cm(3) molecule(-1); k(296 ± 1 K) = (3.73 ± 0.08) × 10(-15) cm(3) molecule(-1), and k(OH + (CF(3))(2)CHOCH(2)F) = (9.98 ± 3.24) × 10(-13) exp[-(969 ± 82)/T] cm(3) molecule(-1); k(298 ± 1 K) = (3.94 ± 0.30) × 10(-14) cm(3) molecule(-1). The rate coefficient of k(OH + CF(3)CHClOCHF(2), 296 ± 1 K) = (1.45 ± 0.16) × 10(-14) cm(3) molecule(-1) was also determined. Chlorine atoms react with CF(3)CHFOCHF(2) via H-abstraction to give CF(3)CFOCHF(2) and CF(3)CHFOCF(2) radicals in yields of approximately 83% and 17%. The major atmospheric fate of the CF(3)C(O)FOCHF(2) alkoxy radical is decomposition via elimination of CF(3) to give FC(O)OCHF(2) and is unaffected by the method used to generate the CF(3)C(O)FOCHF(2) radicals. CF(3)CHFOCF(2) radicals add O(2) and are converted by subsequent reactions into CF(3)CHFOCF(2)O alkoxy radicals, which decompose to give COF(2) and CF(3)CHFO radicals. In 700 Torr of air 82% of CF(3)CHFO radicals undergo C-C scission to yield HC(O)F and CF(3) radicals with the remaining 18% reacting with O(2) to give CF(3)C(O)F. Atmospheric oxidation of (CF(3))(2)CHOCH(2)F gives (CF(3))(2)CHOC(O)F in a molar yield of 93 ± 6% with CF(3)C(O)CF(3) and HCOF as minor products. The IR spectra of (CF(3))(2)CHOC(O)F and FC(O)OCHF(2) are reported for the first time. The atmospheric lifetimes of CF(3)CHClOCHF(2), CF(3)CHFOCHF(2), and (CF(3))(2)CHOCH(2)F (sevoflurane) are estimated at 3.2, 14, and 1.1 years, respectively. The 100 year time horizon global warming potentials of isoflurane, desflurane, and sevoflurane are 510, 2540, and 130, respectively. The atmospheric degradation products of these anesthetics are not of environmental concern.     

Atmospheric chemistry of dimethyl phosphonate, dimethyl methylphosphonate, and dimethyl ethylphosphonate

Rate constants for the reactions of OH radicals and NO3 radicals with dimethyl phosphonate [DMHP, (CH3O)2P(O)H], dimethyl methylphosphonate [DMMP, (CH3O)2P(O)CH3], and dimethyl ethylphosphonate [DMEP, (CH3O)2P(O)C2H5] have been measured at 296 +/- 2 K and atmospheric pressure using relative rate methods. The rate constants obtained for the OH radical reactions (in units of 10(-12) cm3 molecule(-1) s(-1)) were as follows: DMHP, 4.83 +/- 0.25; DMMP, 10.4 +/- 0.6; and DMEP, 17.0 +/- 1.0, with a deuterium isotope effect of k(OH + DMMP)/k(OH + DMMP-d9) = 4.8 +/- 1.2. The rate constants obtained for the NO3 radical reactions (in units of 10(-16) cm3 molecule(-1) s(-1)) were as follows: DMHP, < 1.4; DMMP, 2.0 +/- 1.0; and DMEP, 3.4 +/- 1.4. Upper limits to the rate constants for the O3 reactions of < 8 x 10(-20) cm3 molecule(-1) s(-1) for DMHP and < 6 x 10(-20) cm3 molecule(-1) s(-1) for DMMP and DMEP were determined. Products of the reactions of OH radicals with DMHP, DMMP, and DMEP were investigated in situ using atmospheric pressure ionization mass spectrometry (API-MS) and, for the DMMP and DMEP reactions, Fourier transform infrared (FT-IR) spectroscopy. API-MS analyses showed the formation of products of molecular weight 96 and 126, attributed to CH3OP(O)(H)OH and (CH3O)2P(O)OH, respectively, from DMHP; of molecular weight 110, attributed to CH3OP(O)(CH3)OH, from DMMP; and of molecular weight 124 and 126, attributed to CH3OP(O)(C2H5)OH and (CH3O)2P(O)OH, respectively, from DMEP. FT-IR analyses showed formation (values given are % molar yields) of the following: from DMMP, CO, 54 +/- 6; CO2, 5 +/- 1 in dry air; HCHO, 3.9 +/- 0.7; HC(O)OH, < 1.4 in dry air; RONO2, approximately 4; and formate ester, approximately 8; and from DMEP, CO, 50 +/- 7; CO2, 11 +/- 4; CH3CHO, 18 +/- 8; HCHO, < 7; HC(O)OH, < 6; RONO2, < or = 5; and formate ester, 5.0 +/- 1.5. Possible reaction mechanisms are discussed.     

Atmospheric chemistry of t-CF3CH=CHCl: products and mechanisms of the gas-phase reactions with chlorine atoms and hydroxyl radicals

FTIR-smog chamber techniques were used to study the products and mechanisms of the Cl atom and OH radical initiated oxidation of trans-3,3,3-trifluoro-1-chloro-propene, t-CF(3)CH=CHCl, in 700 Torr of air or N(2)/O(2) diluent at 296 ± 2 K. The reactions of Cl atoms and OH radicals with t-CF(3)CH=CHCl occur via addition to the >C=C< double bond; chlorine atoms add 15 ± 5% at the terminal carbon and 85 ± 5% at the central carbon, OH radicals add approximately 40% at the terminal carbon and 60% at the central carbon. The major products in the Cl atom initiated oxidation of t-CF(3)CH=CHCl were CF(3)CHClCHO and CF(3)C(O)CHCl(2), minor products were CF(3)CHO, HCOCl and CF(3)COCl. The yields of CF(3)C(O)CHCl(2), CF(3)CHClCOCl and CF(3)COCl increased at the expense of CF(3)CHO, HCOCl and CF(3)CHClCHO as the O(2) partial pressure was increased over the range 10-700 Torr. Chemical activation plays a significant role in the fate of CF(3)CH(O)CHCl(2) and CF(3)CClHCHClO radicals. In addition to reaction with O(2) to yield CF(3)COCl and HO(2) the major competing fate of CF(3)CHClO is Cl elimination to give CF(3)CHO (not C-C bond scission as previously thought). As part of this study k(Cl + CF(3)C(O)CHCl(2)) = (2.3 ± 0.3) × 10(-14) and k(Cl + CF(3)CHClCHO) = (7.5 ± 2.0) × 10(-12) cm(3) molecule(-1) s(-1) were determined using relative rate techniques. Reaction with OH radicals is the major atmospheric sink for t-CF(3)CH=CHCl. Chlorine atom elimination giving the enol CF(3)CH=CHOH appears to be the sole atmospheric fate of the CF(3)CHCHClOH radicals. The yield of CF(3)COOH in the atmospheric oxidation of t-CF(3)CH=CHCl will be negligible (<2%). The results are discussed with respect to the atmospheric chemistry and environmental impact of t-CF(3)CH=CHCl.     

Atmospheric chemistry of CHF2CHO: study of the IR and UV-vis absorption cross sections, photolysis, and OH-, Cl-, and NO3-initiated oxidation

The infrared and ultraviolet-visible absorption cross sections, effective quantum yield of photolysis, and OH, Cl, and NO3 reaction rate coefficients of CHF2CHO are reported. Relative rate measurements at 298 +/- 2 K and 1013 +/- 10 hPa gave kOH = (1.8 +/- 0.4) x 10(-12) cm3 molecule(-1) s(-1) (propane as reference compound), kCl = (1.24 +/- 0.13) x 10(-11) cm3 molecule(-1) s(-1) (ethane as reference compound), and kNO3 = (5.9 +/- 1.7) x 10(-17) cm3 molecule(-1) s(-1) (trans-dichloroethene as reference compound). The photolysis of CHF2CHO has been investigated under pseudonatural tropospheric conditions in the European simulation chamber, Valencia, Spain (EUPHORE), and an effective quantum yield of photolysis equal to 0.30 +/- 0.05 over the wavelength range 290-500 nm has been extracted. The tropospheric lifetime of CHF2CHO is estimated to be around 1 day and is determined by photolysis. The observed photolysis rates of CH3CHO, CHF2CHO, and CF3CHO are discussed on the basis of results from quantum chemical calculations.