Study of the reactions of oxygen atoms with carbonothioicdichloride,carbonothioicdifluoride, and tetrafluoro-1,3-dithietane

The reactions of ground-state oxygen atoms with carbonothioicdichloride, carbonothioicdifluoride, and tetrafluoro-1,3-dithietane have been studied in a crossed molecular jet reactor in order to determine the initial reaction products and in a fast-flow reactor in order to determine their overall rate constants at temperatures between 250 and 500 K. These rate constants are??(O + C₂CS) =(3.09 ± 0.54) × 10^?11 exp(+115 ± 106 cal/mol/RT),??(O + F₂CS) = (1.22 ± 0.19) × 10^?11 exp(-747 ± 95 cal/mol/RT), and??(O + F₄C₂S₂) = (2.36 ± 0.52) × 10^?11 exp(-1700 ± 128 cal/mol/RT) cm³/molec˙sec. The detected reaction products and their rate constants indicate that the primary reaction mechanism is the electrophilic addition of the oxygen atom to the sulfur atom contained in the reactant molecule to form an energy-rich adduct which then decomposes by C-S bond cleavage.     

Kinetics of hydroxyl radical reactions with formaldehyde and 1,3,5-trioxane between 290 and 600 K

Absolute rate constants are measured for the reactions: OH + CH₂O, over the temperature range 296–576 K and for OH + 1,3,5-trioxane over the range 292–597 K. The technique employed is laser photolysis of H₂O₂ or HNO₃ to produce OH, and laser-induced fluorescence to directly monitor the relative OH concentration. The results fit the following Arrhenius equations: k (CH₂O) = (1.66 ± 0.20) × 10^?11 exp[?(170 ± 80)/RT] cm³ s^?1 and k(1,3,5-trioxane) = (1.36 ± 0.20) × 10^?11 exp[?(460 ± 100)/RT] cm³ s^?1. The transition-state theory is employed to model the OH + CH₂O reaction and extrapolate into the combustion regime. The calculated result covering 300 to 2500 K can be represented by the equation: k(CH₂O) = 1.2 × 10^?18 T^2.46 exp(970/RT) cm³ s^?1. An estimate of 91 ± 2 kcal/mol is obtained for the first C? H bond in 1,3,5-trioxane by using a correlation of C? H bond strength with measured activation energies.     

Relative rate constants for reactions of HFC 152a, 143, 143a, 134a,and HCFC 124 with F or Cl atoms and for CF2CH3, CF2HCH2, and CF3CFH radicals with F2, Cl2, and O2

Relative rate experiments using UV photolysis of F₂ or Cl₂ have been used to determine rate constant ratios for several hydrofluorocarbon (HFC) reactions with Cl or F atoms and for HFC alkyl radicals with molecular halogens. For mixtures with F₂ present, dark reactions are, also, observed which are attributed to thermal dissociation of the F₂ to form F atoms. At 296 K, the rate of reaction (1a) [CF₂HCH₃ + F → CF₂CH₃ + HF] relative to (1b) [CF₂HCH₃ + F → CF₂HCH₂ + HF] is k_1a/k_1b = 0.73 (±0.13) and is independent of T (= 262–348 K). At 296 K, the ratio of reaction (2a) [CF₂HCH₂F + F → products] to that of (k_1a + k_1b) is (k_1a + k_1b)/k_2a = 2.7 (±0.4), and for reaction (2b) [CF₃CH₃ + F → products] (k_1a + k_1b)/k_2b = 22 ± 12. The temperature dependence (263–365 K) of the rate constant of reaction (3) [CF₃CFH₂ + Cl → products] relative to reaction (4) [CF₃CFClH + Cl → products] is k₃/k₄(±10%) = 1.55 exp(?300 K/T). For the alkyl radicals formed from HFC 152a (CF₂HCH₂ and CF₂CH₃) and from HFC 134a (CF₃CFH), rate constants for the reactions with F₂ and Cl₂ were measured relative to their reactions with O₂. The rate constant of reaction (5cl) [CF₂CH₃ + Cl₂ → CF₂ClCH₃ + Cl] relative to (5o) [CF₂CH₃ + O₂ → CF₂(O₂)CH₃] is k_5cl/k_5o(±15%) = 0.3 exp(200 K/T). For reaction (5f) [CF₂CH₃ + F₂ → CF₃CH₃ + F], k_5f/k_5o(±35%) = 0.23. The ratio for reaction (6f) [CF₂HCH₂ + F₂ → CF₂HCH₂F + F] relative to (6o) [CF₂HCH₂ + O₂ → CF₂HCH₂O₂] is k_6f/k_6o(±40%) = 1.23 exp(?730 K/T). The rate constant ratio for reaction (8cl) [CF₃CFH + Cl₂ → CF₃CFClH + Cl] relative to reaction (8o) [CF₃CFH + O₂ → CF₃CFHO₂] is k_8cl/k_8o(±18%) = 0.16 exp(?940 K/T). For reaction (8f) [CF₃CFH + F₂ → CF₃CF₂H + F], k_8f/k_8o(±35%) = 0.6 exp(?860 K/T). © 1993 John Wiley & Sons, Inc.     

High-temperature pyrolysis of acetaldehyde

High-temperature (>1000°K) pyrolysis of acetaldehyde (～1% in an atmosphere of pure nitrogen) was examined in a turbulent flow reactor which permits accurate determination of the spatial distribution of the stable species. Results show that the products in order of decreasing importance are CO, CH₄, H₂, C₂H₆, and C₂H₄. Rates of formation were consistent with the Rice–Herzfeld mechanism by including reactions to explain C₂H₄ formation and the possible presence of ketene. A steady-state treatment of the complete mechanism indicates that the overall reaction order decreases from \documentclass{article}\pagestyle{empty}\begin{document}$ \frac{3}{2} $\end{document} to 1, which is supported by the new experimental data. Using earlier low-temperature results, the rate constant for the reaction CH₃CHO → CH₃ + CHO (1) was found as k₁=10^15.85±0.21 exp (?81,775±1000/RT) sec^?1. Also, data for the ratio of rate constants for reactions CH₃CHO + CH₃ → CH₄ + CH₃CO (4) and 2CH₃ → C₂H₆(6) were fitted to the empirical expression k₄/k₆^1/2=10^?13.89±0.03T^6.1 exp(?1720±70/RT) (cm³/mole·sec)^1/2 and causes for the curvature are discussed. The noncatalytic effect of oxygen on acetaldehyde pyrolysis at high temperature is explained.     

Kinetics and mechanism of atmospheric reactions of partially fluorinated alcohols

Gas-phase reactions typical of the Earth’s atmosphere have been studied for a number of partially fluorinated alcohols (PFAs). The rate constants of the reactions of CF₃CH₂OH, CH₂FCH₂OH, and CHF₂CH₂OH with fluorine atoms have been determined by the relative measurement method. The rate constant for CF₃CH₂OH has been measured in the temperature range 258–358 K (k = (3.4 ± 2.0) × 10¹³exp(?E/RT) cm³ mol^?1 s^?1, where E = ?(1.5 ± 1.3) kJ/mol). The rate constants for CH₂FCH₂OH and CHF₂CH₂OH have been determined at room temperature to be (8.3 ± 2.9) × 10¹³ (T = 295 K) and (6.4 ± 0.6) × 10¹³ (T = 296 K) cm³ mol^?1 s^?1, respectively. The rate constants of the reactions between dioxygen and primary radicals resulting from PFA + F reactions have been determined by the relative measurement method. The reaction between O₂ and the radicals of the general formula C₂H₂F₃O (CF₃CH₂? and CF₃?HOH) have been investigated in the temperature range 258–358 K to obtain k = (3.8 ± 2.0) × 10⁸exp(?E/RT) cm³ mol^?1 s^?1, where E = ?(10.2 ± 1.5) kJ/mol. For the reaction between O₂ and the radicals of the general formula C₂H₄FO (? HFCH₂O, CH₂F?HOH, and CH₂FCH₂?) at T = 258–358 K, k = (1.3 ± 0.6) × 10¹¹exp(?E/RT) cm³ mol^?1 s^?1, where E = ?(5.3 ± 1.4) kJ/mol. The rate constant of the reaction between O₂ and the radicals with the general formula C₂H₃F₂O (?F₂CH₂O, CHF₂?HOH, and CHF₂CH₂?) at T = 300 K is k = 1.32 × 10¹¹ cm³ mol^?1 s^?1. For the reaction between NO and the primary radicals with the general formula C₂H₂F₃O (CF₃CH₂? and CF₃?HOH), which result from the reaction CF₃CH₂OH + F, the rate constant at 298 K is k = 9.7 × 10⁹ cm³ mol^?1 s^?1. The experiments were carried out in a flow reactor, and the reaction mixture was analyzed mass-spectrometrically. A mechanism based on the results of our studies and on the literature data has been suggested for the atmospheric degradation of PFAs.     

Rate constants of the reactions of OH radicals with cyclopropane and cyclobutane

The kinetics of the reactions of hydroxy radicals with cyclopropane and cyclobutane has been investigated in the temperature range of 298–492 K with laser flash photolysis/resonance fluorescence technique. The temperature dependence of the rate constants is given by k₁ = (1.17 ± 0.15) × 10^?16 T^3/2 exp[?(1037 ± 87) kcal mol^?1/RT] cm³ molecule^?1 s¹ and k₂ = (5.06 ± 0.57) × 10^?16 T^3/2 exp[?(228 ± 78) kcal mol^?1/RT] cm³ molecule^?1 s^?1 for the reactions OH + cyclopropane → products (1) and OH + cyclobutane → products (2), respectively. Kinetic data available for OH + cycloalkane reactions were analyzed in terms of structure-reactivity correlations involving kinetic and energetic parameters.     

Gas‐phase reactions of Cl atoms with propane,n‐butane,and isobutane

Using the relative kinetic method, rate coefficients have been determined for the gas‐phase reactions of chlorine atoms with propane, n‐butane, and isobutane at total pressure of 100 Torr and the temperature range of 295–469 K. The Cl₂ photolysis (λ = 420 nm) was used to generate Cl atoms in the presence of ethane as the reference compound. The experiments have been carried out using GC product analysis and the following rate constant expressions (in cm³ molecule^?1 s^?1) have been derived: (7.4 ± 0.2) × 10^?11 exp [‐(70 ± 11)/ T], Cl + C₃H₈ → HCl + CH₃CH₂CH₂; (5.1 ± 0.5) × 10^?11 exp [(104 ± 32)/ T], Cl + C₃H₈ → HCl + CH₃CHCH₃; (7.3 ± 0.2) × 10^?11 exp[?(68 ± 10)/ T], Cl + n‐C₄H₁₀ → HCl + CH₃ CH₂CH₂CH₂; (9.9 ± 2.2) × 10^?11 exp[(106 ± 75)/ T], Cl + n‐C₄H₁₀ → HCl + CH₃CH₂CHCH₃; (13.0 ± 1.8) × 10^?11 exp[?(104 ± 50)/ T], Cl + i‐C₄H₁₀ → HCl + CH₃CHCH₃CH₂; (2.9 ± 0.5) × 10^?11 exp[(155 ± 58)/ T], Cl + i‐C₄H₁₀ → HCl + CH₃CCH₃CH₃ (all error bars are ± 2σ precision). These studies provide a set of reaction rate constants allowing to determine the contribution of competing hydrogen abstractions from primary, secondary, or tertiary carbon atom in alkane molecule. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 651–658, 2002     

The NO- and NO2-catalyzed decomposition of I2 in shock waves

Measurements of the NO-catalyzed dissociation of I₂ in Ar in incident shock waves were carried out in the temperature range of 700°-1520°K and at total concentrations of 5 × 10^?6-6 × 10^?5 mol/cm³, using ultraviolet-visible absorption techniques to monitor the disappearance of I₂. It was shown that the main reaction responsible for the disappearance under these conditions is I₂ + NO → INO + I, for which a rate coefficient of (2.9 ± 0.5) × 10¹³ exp[-(18.0 ± 0.6 kcal/mol)/RT] cm²/mol·sec was determined. The INO formed dissociates rapidly in a subsequent reaction. The reaction, therefore, constitutes a “chemical model” for a “thermal collisional release mechanism.” Preliminary measurements of the rate coefficient for I₂ + NO₂ → INO₂ + I are also presented. Combined with information on the reverse reactions obtained in earlier room temperature experiments, these results lead to accurate values of ΔH°_f for INO and INO₂ equal to 29.7 ± 0.5 and 15.9 ± 1 kcal/mol, respectively.     

Ozone–olefin reactions in the gas phase 1. Rate constants and activation energies

Reactions of ozone with simple olefins have been studied between 6 and 800 mtorr total pressure in a 220-m³ reactor. Rate constants for the removal of ozone by an excess of olefin in the presence of 150 mtorr oxygen were determined over the temperature range 280 to 360° K by continuous optical absorption measurements at 2537 Å. The technique was tested by measuring the rate constants k₁ and k₂ of the reactions (1) NO + O₃ → NO₂ + O₂ and (2) NO₂ + O₃ rarr; NO₃ + O₂ which are known from the literature. The results for NO, NO₂, C₂H₄, C₃H₆, 2-butene (mixture of the isomers), 1,3→butadiene, isobutene, and 1,1 -difluoro-ethylene are 1.7 × 10^{?1 4} (290°K), 3.24 × 10^?17 (289°K), 1.2 × 10^{?1 4} exp (–4.95 ± 0.20/RT), 1.1 × 10^{?1 4} exp (–3.91 ± 0.20/RT), 0.94 × 10^{?1 4} exp ( –2.28 ± 0.15/RT), 5.45 ± 10^{?1 4} exp ( –5.33 ± 0.20/RT), 1.8 ×10^?17 (283°K), and 8 × 10^?20 cm³/molecule ·s(290°K). Productformation from the ozone–propylene reaction was studied by a mass spectrometric technique. The stoichiometry of the reaction is near unity in the presence of molecular oxygen.     

Kinetics and Products of the Reactions of F2 with Br‐Atom and Br2

Reactions of F₂ molecules exhibit unusual features, manifesting in high reactivity of F₂ with respect to some closed‐shell molecules and low reactivity toward chemically active species, such as halogen and oxygen atoms. The existing data base on the reactions of F₂ being rather sparse, kinetic and mechanistic studies (preferably over a wide temperature range) are needed to better understand the nature of the specific reactivity of fluorine molecule. In the present work, reactions of F₂ with Br atoms and Br₂ have been studied for the first time in an extended temperature range using a discharge flow reactor combined with an electron impact ionization mass spectrometer. The rate constant of the reaction F₂ + Br → F +BrF (1) was determined either from kinetics of the reaction product, BrF, formation or from the kinetics of Br consumption in excess of F₂: k₁ = (4.66 ± 0.93) × 10⁻¹¹ exp(−(4584 ± 86)/T) cm³ molecule⁻¹ s⁻¹ at T = 300–940 K. The rate constant of the reaction F₂ + Br₂ → products (2), k₂ = (9.23 ± 2.68) × 10⁻¹¹ exp(−(8373 ± 194)/T) cm³ molecule⁻¹ s⁻¹, was determined in the temperature range 500–958 K by monitoring both reaction product (FBr) formation and F₂ consumption kinetics in excess of Br₂. The results of the experimental measurements of the yield of FBr (1.02 ± 0.07 at T = 960 K) combined with thermochemical calculations indicate that F+Br₂F forming channel of reaction (2) is probably the dominant one, at least, at highest temperature of the study.     

Reactions of chromium atoms with chloromethanes

The rate constants of the gas-phase reactions of the chromium atom with CC1⁴, CHC1₃, and CH₂Cl₂ were measured behind shock waves at 800–1400 K. The results are presented in the Arrhenius form (the activation energy is given in kJ/mol):k _{CCl 4} = 10^14.32±0.36exp[-(2.0±7.5)/RT],k _{CHCl 3} = 10^14.72±0.21exp[-(18.5.±4.0)/RT, andk _{CH 2 Cl 2}> = 10^14.33±0.16exp[-(24.1±3.1)/RT]cm³mol^-1s^-1.     

The kinetics of the reactions of O(3P) atoms with dimethyl ether and methanol

The kinetics of the reaction of O + CH₃OCH₃ were investigated using fast-flow apparatus equipped with ESR and mass-spectrometric detection. The concentration of O(³P) atoms to CH₃OCH₃ was varied over an unusually large range. The rate constant for reaction was found to be k = (5.0 ± 1.0) × 10¹² exp [(?2850 ± 200/RT)] cm³ mole^?1 sec^?1. The reaction O + CH₃OH was studied using ESR detection. Based on an assumed stoichiometry of two oxygen atoms consumed per molecule of CH₃OH which reacts, we obtain a value of k = (1.70 ± 0.66) × 10¹² exp [(?2,280 ± 200/RT)] cm³ mole^?1 sec^?1 for the reaction The results obtained in this study are compared with the results from other workers on these reactions. The observation of essentially equal activation energies in these two reactions is indicative of approximately equal C? H bond strengths in CH₃OCH₃ and CH₃OH. This is in agreement with recent measurements of these bond energies.     

High temperature pyrolysis of methane in shock waves. Rates for dissociative recombination reactions of methyl radicals and for propyne formation reaction

The pyrolysis of 2% CH₄ and 5% CH₄ diluted with Ar was studied using both a single–pulse and time–resolved spectroscopic methods over the temperature range 1400–2200 K and pressure range 2.3–3.7 atm. The rate constant expressions for dissociative recombination reactions of methyl radicals, CH₃ + CH₃ → C₂H₅ + H and CH₃ + CH₃ → C₂H₄ + H₂, and for C₃H₄ formation reaction were investigated. The simulation results required considerably lower value than that reported for CH₃ + CH₃ → C₂H₄ + H₂. Propyne formation was interpreted well by reaction C₂H₂ + CH₃ → P-C₃H₄ + H with ?? = 6.2 × ¹⁰12 exp(?17 kcal/RT) ^cm3 mol^?1 s^?1.     

The reactions of hydrogen atoms with bis(trifluoromethyl)disulfide

The reactions of hydrogen atoms produced by the mercury-photosensitized decomposition of H₂ with bis(trifluoromethyl)disulfide has been studied. The rate coefficient for the primary reaction, H + CF₃SSCF₃ → CF₃SH + CF₃S, was determined in competition with the reaction H + C₂H₄S → SH + C₂H₄ to have the value k = (3.0 ± 0.18) × 10¹⁴ exp[-(4560 ± 140)/RT] cm³ mol^?1 S^?1. The high A factor can be partially accounted for by assuming free rotation for the two CF₃ groups and the SCF₃ groups about the S—S bond in the transition state. The relatively high activation energy is attributed to inductive and orbital overlap effects. CH₃SH, H₂S, and CF₃SH all react with CF₃SSCF₃ to yield solid complexes which were not explored further.     

Thermal decomposition of propane in shock waves

The thermal decomposition of propane was studied behind reflected shock waves over the temperature range 1100–1450 K and the pressure range 1.5–2.6 atm, by both monitoring the time variations of absorption at 3.39 μm and analyzing the concentrations of the reacted gas mixtures. The rate constants of the elementary reactions were discussed from the results. The rate constant expressions, k₁ = 1.1 × 10¹⁶ exp (?84 kcal/RT) s^?1 and k₄ = 9.3 × 10¹³ exp(?8 kcal/RT) cm³ mol^?1 s^?1, of reactions C₃H₈ → CH₃ + C₂H₅ and C₃H₈ + H → n-C₃H₇ + H₂ were evaluated, respectively.     

Reaction of hydrogen atoms and O2(1Δg)

The reaction of atomic hydrogen with O₂(¹Δ_g) has been investigated as a function of temperature, using a fast discharge-flow apparatus equipped for EPR detection of free radical species. The rate constant for the overall reaction was measured as (1.46 ± 0.49) × 10^?11 exp(-4000 ± 200 cal/mol/RT) cm³/s. Evidence is presented which suggests that the reaction occurs principally via abstraction, H + O₂(¹Δ_g) → OH + O, rather than via physical quenching, H + O₂(¹Δ_g) → H + O₂(X³Σ_g^?).     

Kinetics and mechanisms for reactions of HNO with CH3 and C6H5 studied by quantum‐chemical and statistical‐theory calculations

Kinetics and mechanisms for the reactions of HNO with CH₃ and C₆H₅ have been investigated by ab initio molecular orbital (MO) and transition‐state theory (TST) and/or Rice‐Ramsperger‐Kassel‐Marcus/Master Equation (RRKM/ME) calculations. The G2M(RCC, MP2)//B3LYP/6‐31G(d) method was employed to evaluate the energetics for construction of their potential energy surfaces and prediction of reaction rate constants. The reactions R + HNO (R = CH₃ and C₆H₅) were found to proceed by two key product channels giving (1) RH + NO and (2) RNO + H, primarily by direct abstraction and indirect association/decomposition mechanisms, respectively. As both reactions initially occur barrierlessly, their rate constants were evaluated with a canonical variational approach in our TST and RRKM/ME calculations. For practical applications, the rate constants evaluated for the atmospheric‐pressure condition are represented by modified Arrhenius equations in units of cm³ mol^?1 s^?1 for the temperature range 298–2500 K: κ_1A = 1.47 × 10¹¹ T ^0.76 exp[?175/ T ], κ_2A = 8.06 × 10³ T ^2.40 exp[?3100/ T ], κ_1B = 3.78 × 10⁵ T ^2.28 exp[230/ T ], and κ_2B = 3.79 × 10⁹ T ^1.19 exp[?4800/ T ], where A and B represent CH₃ and C₆H₅ reactions, respectively. Based on the predicted rate constant at 1 atm pressure for R + HNO → RNO + H, we estimated their reverse rate constants for R + HNO production from H + RNO in units of cm³ mol^?1 s^?1: κ_?2A′ = 7.01 × 10¹⁰ T ^0.84 exp[120/ T ] and κ_?2B′ = 2.22 × 10¹⁹ T ^?1.01 exp[?9700/ T ]. The heats of formation at 0 K for CH₃NO, CH₃N(H)O, CH₃NOH, C₆H₅N(H)O, and C₆H₅NOH have been estimated to be 18.6, 18.1, 22.5, 47.2, and 50.7 kcal mol^?1 with an estimated ±1 kcal mol^?1 error. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 261–274, 2005     

The reaction of methoxy radicals with nitric oxide and nitrogen dioxide

By allowing dimethyl peroxide (10^?4M) to decompose in the presence of nitric oxide (4.5 × 10^?5M), nitrogen dioxide (6.5 × 10^?5M) and carbon tetrafluoride (500 Torr), it has been shown that the ratio k₂/k_2′ = 2.03 ± 0.47: CH₃O + NO → CH₃ONO (reaction 2) and CH₃O + NO₂ → CH₃ONO₂ (reaction 2′). Deviations from this value in this and previous work is ascribed to the pressure dependence of both these reactions and heterogeneity in reaction (2). In contrast no heterogeneous effects were found for reaction (2′) making it an ideal reference reaction for studying other reactions of the methoxy radical. We conclude that the ratio k₂/k_2′ is independent of temperature and from k₁ = 10^10.2±0.4M^?1 sec^?1 we calculate that k_2′ = 10^9.9±0.4M^?1 sec^?1. Both k₂ and k_2′ are pressure dependent but have reached their limiting high-pressure values in the presence of 500 Torr of carbon tetrafluoride. Preliminary results show that k₄ = 10.^9.0±0.6 10^?4.5±1.1/ΘM^?1 sec^?1 (Θ = 2.303RT kcal mole^?1) and by k₄ = 10^8.6±0.6 10^?2.4±1.1/ΘM^?1 sec^?1: CH₃O + O₂ → CH₂O + HO₂ (reaction 4) and CH₃O + t-BuH → CH₃OH + (t-Bu) (reaction 4′).     

Cyanogen pyrolysis and the CN + NO reaction behind incident shock waves

The reaction chemistry of C₂N₂? Ar and C₂N₂? NO? Ar mixtures has been investigated behind incident shock waves. Progress of the reaction was monitored by observing the cyano radical (CN) in absorption at 388.3 nm. A quantitative spectroscopic model was used to determine concentration histories of CN. From initial slopes of CN concentration during cyanogen pyrolysis, the rate constant for C₂N₂ + M → 2CN + M (1) was determined to be k₁ = (4.11 ± 1.8) × 10¹⁶ exp(?47,070 ± 1400/T) cm³/mol · s. A reaction sequence for the C₂N₂? NO system was developed, and CN profiles were computed. By comparison with experimental CN profiles the rate constant for the reaction CN + NO → NCO + N (3) was determined to be k₃ = 10^{(14.0 ± 0.3)} exp(?21,190 ± 1500/T) cm³/mol · s. In addition, the rate of the four-centered reaction CN + NO → N₂ + CO (2) was estimated to be approximately three orders of magnitude below collision frequency.     

The reaction of fluorine atoms with formyl fluoride and the CFO self-reaction at 293 K

A fast-flow apparatus with mass spectrometric detection was used to study the system F + CHFO between 2 and 3.5 mbar total pressure. The rate constant of the primary reaction was evaluated directly to yield at 298 K k₍₁₎ = (8.8 ± 1.4) * 10^?13 cm³ * molecule^?1 * s^?1. Numerical modelling was used to determine the rate constant at 298 K of the subsequent reaction CFO + CFO → CF₂O + CO: k₍₂₎ = (4.9 ± 2.0) * 10^?11 cm³ * molecule^?1 * s^?1. The possible occurrences of secondary reactions, CFO + F + M → CF₂O + M, and CFO + F₂ → CF₂O + F, can be excluded under the present conditions. © 1993 John Wiley & Sons, Inc.