1558-67-4Relevant articles and documents
Mechanism of the Ozone-Ethene Reaction in Dilute N2/O2 Mixtures Near 1-atm Pressure
Kan, Charles S.,Su, Fu,Calvert, Jack G.,Shaw, John H.
, p. 2359 - 2363 (1981)
Kinetic studies of the O3-C2H4 reaction (ppm reactant level in 700 torr of O3/N2) were made at several temperatures (9-30 deg C) by using Fourier transform-infrared methods to follow reactants and products in situ.The rate data gave the second-order rate constant for the elementary reaction O3 + C2H4 ---> ---> CH2OO* + CH2O (1); k1 (cm3molecule-1s-1)=10-13.59+/-0.27exp.The fraction of the CH2OO* species formed in eq 1 which does not fragment, but lives to react with CH2O, was found to be 0.37+/-0.02, independent of temperature (9-30 deg C).The addition of CH2O2 to CH2O leads to the transient product X, thought to be HOCH2OCHO, and this produces formic anhydride by some ill-defined path (e.g., HOCH2OCHO ---> (HCO)2O + H2 (7); or HOCH2OCHO + O2 ---> (HCO)2O + H2O2 (7a)).The first-order rate constant k7 showed an unexpected, low activation energy and preexponential factor and a sensitivity to wall conditioning and O2 pressure which suggested that reaction 7, 7a, or some similar reaction forming (HCO)2O occurs heterogeneously.
Kinetic and Product Study of the Atmospheric Photooxidation of 1,4-Dioxane and Its Main Reaction Product Ethylene Glycol Diformate
Maurer, Tobias,Hass, Heinz,Barnes, Lan,Becker, Karl H.
, p. 5032 - 5039 (1999)
A FTIR kinetic and product study of the OH-radical initiated oxidation of 1,4-dioxane (DOX) has been performed in a quartz-glass photoreactor in the laboratory under different conditions and also in the outdoor EUPHORE simulation chamber in Valencia, Spain. Using the relative kinetic technique, a rate coefficient of k = (1.24 ± 0.04) × 10-11 cm3 molecule-1 s-1 was determined for the reaction at 298 K in 1000 mbar of synthetic air, which is in good agreement with other published values. The major reaction product both in the presence and absence of NO was ethylene glycol diformate (EDF). This compound has been synthesized, and authentic samples have been used for calibration. Integrated band intensities have been calculated for the three strongest bands of EDF: (4.99 ± 0.06) × 10-17 cm molecule-1 for 1100-1225 cm-1, (3.90 ± 0.05) × 10-17 cm molecule-1 for 1670-1820 cm-1, (9.34 ± 0.11) × 10-18 cm molecule-1 for 2775-3075 cm-1. In the laboratory reactor, yields for EDF of 87 ± 9 and 95 ± 10 mol % were obtained using the photolysis of MeONO/NO/air and H2O2/NO/air as the OH radical sources, respectively. Using only the photolysis of H2O2/ air as the OH source resulted in a molar yield of 55 ± 6 mol % for EDF. In the outdoor EUPHORE simulation chamber a yield of 95 ± 10 mol % was obtained from irradiation of a DOX/NOx/air mixture. The OH-radical- and Cl-atom-initiated oxidation of EDF has also been investigated. Rate coefficients of kOH = (4.72 ± 0.31) × 10-13 cm3 molecule-1 s-1 and kcl = (3.52 ± 0.09) × 1012 cm3 molecule-1 s-1 have been determined for the reaction of EDF with OH radicals and Cl atoms, respectively, at 298 K and 1000 mbar total pressure. The products determined in the Cl-initiated oxidation in the presence of NOx were formic acid anhydride (FAA), formic acid (FA), and carbon monoxide (CO) with yields of 173 ± 34 mol %, 45 ± 9 mol %, and 41 ± 8 mol %, respectively. Formation of a peroxy formyl nitrate was also observed. In the absence of NOx the yields of FAA, FA and CO were 144 ± 29 mol %, 39 ± 8 mol %, and 22 ± 4 mol %, respectively.
Atmospheric degradation of glycidaldehyde: Photolysis and reaction with OH radicals
Ma,Barnes,Becker
, p. 3515 - 3521 (1998)
Epoxide aldehydes have recently been detected among the oxidation products of aromatic hydrocarbons. Many epoxides are toxic and very little is known about their atmospheric fate. The products and kinetics of the atmospheric oxidation, OH radical reaction, and photolysis of glycidaldehyde have been investigated in a large volume reactor at 298 K using in situ long- path FT-IR spectroscopy for the analysis. A rate coefficient of k = (1.69 ± 0.04) x 10-11 cm3 molecule-1 s-1 has been determined for the reaction of glycidaldehyde with the OH radical using the relative kinetic technique. The UV absorption spectrum of glycidaldehyde was measured in the range 220380 nm from which upper limits of its photolysis frequencies in the troposphere have been deduced, e.g., J (hv) ~ 1.0 x 10-4 s-1 (for July 1, noon, and 50°N). The OH radical initiated photooxidation of glycidaldehyde yields CO, CO2, formic acid, formic acid anhydride, formaldehyde, and hydroperoxymethyl formate as major products. A reaction mechanism is postulated to account for the product formation. Epoxide aldehydes have recently been detected among the oxidation products of aromatic hydrocarbons. Many epoxides are toxic and very little is known about their atmospheric fate. The products and kinetics of the atmospheric oxidation, OH radical reaction, and photolysis of glycidaldehyde have been investigated in a large volume reactor at 298 K using in situ long-path FT-IR spectroscopy for the analysis. A rate coefficient of k = (1.69 ± 0.04) × 10-11 cm3 molecule-1 s-1 has been determined for the reaction of glycidaldehyde with the OH radical using the relative kinetic technique. The UV absorption spectrum of glycidaldehyde was measured in the range 220-380 nm from which upper limits of its photolysis frequencies in the troposphere have been deduced, e.g., J(hv) approx. 1.0 × 10-4 s-1 (for July 1, noon, and 50° N). The OH radical initiated photooxidation of glycidaldehyde yields CO, CO2, formic acid, formic acid anhydride, formaldehyde, and hydroperoxymethyl formate as major products. A reaction mechanism is postulated to account for the product formation.
Practical and efficient synthesis of N-formylbenzotriazole
Matheson, Mhairi,Pasqua, Adele E.,Sewell, Alan L.,Marquez, Rodolfo
, p. 358 - 366 (2014/04/03)
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An Experimental and Computational Study of the Kinetics and Mechanism of the Reaction of Methyl Formate with Cl Atoms
Good, David A.,Hansen, Jaron,Kamoboures, Mike,Santiono, Randy,Francisco, Joseph S.
, p. 1505 - 1511 (2007/10/03)
Ab initio molecular orbital theory has been used to examine the kinetics and mechanism for the reaction of chlorine atoms with methyl formate. From the ab initio parameters, the room-temperature rate constant is calculated and found to be in reasonable agreement with the experimental determination. It is found that 90% of the reaction proceeds via abstraction of the carbonyl hydrogen from methyl formate by chlorine atoms, resulting in the formation of CH3OCO radical.
