624-91-9Relevant articles and documents
Atmospheric chemistry of hexafluorocyclobutene, octafluorocyclopentene, and hexafluoro-1,3-butadiene
Wallington,Hurley
, p. 19 - 23 (2011)
The relative rate method was used to measure k(Cl + hexafluorocyclobutene) = (8.88 ± 0.69) × 10-13, k(Cl + octafluorocyclopentene) = (1.02 ± 0.11) × 10-12, k(Cl + hexafluoro-1,3- butadiene) = (7.28 ± 0.99) × 10-11, k(OH + hexafluorocyclobutene) = (8.6 ± 1.6) × 10-14, k(OH + octafluorocyclopentene) = (1.01 ± 0.16) × 10-13, and k(OH + hexafluoro-1,3-butadiene) = (9.64 ± 1.76) × 10-12 cm3 molecule-1 s-1 in 700 Torr N2, or air, diluent at 295 K. The atmospheric lifetimes of hexafluorocyclobutene, octafluorocyclopentene, and hexafluoro-1,3-butadiene were estimated to be 135, 104, and 1.1 days, respectively. The 100 year time horizon global warming potentials for hexafluorocyclobutene and octafluorocyclopentene are 42 and 28.
Photodissociation of Methyl Nitrate in a Molecular Beam
Yang, Xuefeng,Felder, Peter,Huber, J. Robert
, p. 10903 - 10910 (1993)
The photodissociation of methyl nitrate, CH3ONO2, has been investigated by photofragment translational spectroscopy.At the photolysis wavelength of 193 nm the predominant primary decay (ca. 70percent) involves the fission of the weak CH3O-NO2 bond (D10 ca. 41 kcal/mol) to yield CH3O + NO2 fragment pairs which show a bimodal translational energy distribution.The component consisting of the fast fragment pairs has an average translational energy (ET) = 41 kcal/mol and a recoil anistropy β = 0.9, while the slow component is characterized by (ET) = 19 kcal/mol and β = 0.A significant portion of the NO2 fragments of the slow component is subject to a unimolecular decay to NO + O(3P).An additional primary decay route leads to the formational of methyl nitrite, CH3ONO, and atomic oxygen O(1D) with (ET) = 6 kcal/mol and β = 1.2.This competing reaction requires fission of the strong N-O bond (D110 ca. 118 kcal/mol) and its occurrence indicates an initial localization of the photoexcitation on the NO2 moiety in the parent molecule.At higher laser fluence secondary photodissociation of the primary fragments CH3ONO was observed.Photolysis at 248 nm is shown to produce CH3O + NO2 fragment pairs exclusively, with (ET) = 17 kcal/mol.
Kinetics of the reactions of OH radicals with selected acetates and other esters under simulated atmospheric conditions
Williams,O'RJI,Stone
, p. 539 - 548 (1993)
The relative hydroxyl reaction rate constants from the simulated atmospheric oxidation of selected acetates and other acetates and other esters have been measured. Reactions were carried out at 297 ± 2K in 100-liter FEP teflon-film bags. the OH radicals were generated from the photolysis of methyl nitrite in pure air. Using a rate constant of 2.63 × 10-11 cm3 molecule-1 s-1 for the reaction of OH radicals with propene, principal reference organic compound, the rate constants (×1012 cm3 molecule-1 s-1) obtained for the acetates and esters used in this study. A linear correlation was observed for a plot of the measured relative rate constants vs. the number of CH2 groups per molecule of the following acetates: methyl acetate, ethyl acetate, n-propyl acetate, butyl acetate and pentyl acetate.
Wendschuh et al.
, p. 2931 (1973)
Collisional Quenching of CH3O(A2A1)
Wantuck, Paul J.,Oldenborg, Richard C.,Baughcum, Steven L.,Winn, Kenneth R.
, p. 3253 - 3259 (1987)
Room temperature rate constants for collisional quenching of CH3O(A2A1) have been measured for 20 collision partners.Methoxy radicals are produced by 248-nm photolysis of CH3ONO and the CH3O(A2A1) is produced by exciting the A-X transition using a pulsed dye laser.Rate constants are determined by monitoring the time-resolved fluorescence signal as a function of quenching gas pressure.The experimental quenching cross sections are best correlated in terms of the CH3O-collision partner interaction well depth.Reasonable correlation is observed for 15 quenching gases, but several exceptions are apparent.A similar trend in collision partner quenching efficiency for OH(A2Σ+) and CH3O(A2A1) is noted and discussed.
Atmospheric chemistry of C2F5CH2OCH 3 (HFE-365mcf)
Thomsen,Andersen,Nielsen,Wallington
, p. 2758 - 2764 (2011)
FTIR smog chamber techniques were used to measure k(Cl + C 2F5CH2OCH3) = (2.52 ± 0.37) × 10-11 and k(OH + C2F5CH 2OCH3) = (5.78 ± 1.02) × 10-13 cm3 molecule-1 s-1 in 700 Torr of air diluent at 296 ± 1 K. The atmospheric lifetime of C2F 5CH2OCH3 is estimated to be 20 days. Reaction of chlorine atoms with C2F5CH2OCH3 proceeds 18 ± 2% at the -CH2- group and 82 ± 2% at the -CH3 group. Reaction of OH radicals with C2F 5CH2OCH3 proceeds 44 ± 5% at the -CH2- group and 56 ± 5% at the -CH3 group. The atmospheric fate of C2F5CH2OCH2O radicals is reaction with O2 to give C2F 5CH2OCHO. The atmospheric fate of C2F 5CH(O)OCH3 radicals is C-C bond-cleavage to give C 2F5 radicals and CH3OCHO (methyl formate). The infrared spectrum was recorded and used to estimate a global warming potential of 6 (100 year time horizon) for C2F5CH 2OCH3.
Arrhenius parameters for the OH-initiated degradation of methyl crotonate, methyl-3,3-dimethyl acrylate, (: E)-ethyl tiglate and methyl-3-butenoate over the temperature range of 288-314 K
Colomer, Juan P.,Blanco, María B.,Pe?é?ory, Alicia B.,Barnes, Ian,Wiesen, Peter,Teruel, Mariano A.
, p. 53723 - 53729 (2016)
The relative-rate technique has been employed to obtain rate coefficients for the reactions between the OH radical and four unsaturated esters (methyl crotonate (k1), methyl-3,3-dimethyl acrylate (k2), (E)-ethyl tiglate (k3) and methyl-3-butenoate (k4)) between 288 and 314 K in 760 Torr of synthetic air. The experiments were performed in a multiple-pass environmental chamber with in situ FTIR detection of the esters and reference compounds. The rate coefficients for the reactions displayed a negative dependence with temperature and low pre-exponential factors. The following Arrhenius expressions (in units of cm3 per molecule per s) were obtained: k1 = (3.39 ± 0.78) × 10-12exp[(750 ± 159)/T], k2 = (2.95 ± 0.63) × 10-12exp[(838 ± 182)/T], k3 = (1.49 ± 0.56) × 10-12exp[(522 ± 114)/T] and k4 = (1.90 ± 1.25) × 10-12exp[(834 ± 185)/T]. The kinetic results are in agreement with a mechanism involving mainly OH radical addition to the double with the reversible formation of an OH-adduct. Atmospheric implications are discussed with particular reference to the rate coefficients obtained as a function of the temperature.
Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: Kinetics, product yields and mechanism at 298 K and atmospheric pressure
Blanco, María B.,Cardona, Alejandro L.,Gibilisco, Rodrigo G.,Teruel, Mariano,Wiesen, Peter
, p. 22618 - 22626 (2019)
Relative rate coefficients and product distribution of the reaction of 2-butanethiol (2butSH) with OH radicals and Cl atoms were obtained at atmospheric pressure and 298 K. The experiments were performed in a 480 L borosilicate glass photoreactor in synthetic air coupled to a long path "in situ" FTIR spectrometer. The rate coefficients obtained by averaging the values from different experiments were: kOH = (2.58 ± 0.21) × 10-11 cm3 per molecule per s and kCl = (2.49 ± 0.19) × 10-10 cm3 per molecule per s. The kinetic values were compared with related alkyl thiols and homologous alkyl alcohols, where it was found that thiols react faster with both oxidants, OH radicals and Cl atoms. SO2 and 2-butanone were the major products identified for the reactions of 2-butanethiol with OH radicals and Cl atoms. The product yield of the reaction of 2-butanethiol and OH radicals were (81 ± 2)percent, and (42 ± 1)percent for SO2 and 2-butanone, respectively. For the reactions of 2-butanethiol with Cl atom, yields of SO2 and 2-butanone were (59 ± 2)percent and (39 ± 2)percent, respectively. A degradation mechanism was proposed for the pathways that leads to formation of identified products. The product distribution observed indicated that the H-atom of the S-H group abstraction channel is the main pathway for the reaction of OH radicals and Cl atoms with 2-butanethiol.
Investigation into the Kinetics and Mechanism of the Reaction of NO3 with CH3 and CH3O at 298 K between 0.6 and 8.5 Torr: Is there a Chain Decomposition Mechanism in Operation?
Biggs, Peter,Canosa-Mas, Carlos E.,Fracheboud, Jean-Marc,Shallcross, Dudley E.,Wayne, Richard P.
, p. 1197 - 1204 (1994)
The reactions CH3 + NO3 -> products (1), and CH3O + NO3 -> products (2), have been studied using a flow system at T = 298 K and at pressures between 0.6 and 8.5 Torr.The laser-induced fluorescence (LIF) technique was used to detect CH3O and multi-pass optical absorption to detect NO3.The chemical systems were studied as a pair of consecutive reactions; however, a simple analytical treatment was not sufficient to describe them because CH3O2 was formed as one of the products in the major channel of reaction (2).This species also reacts with NO3 regenerating CH3O.Use of a numerical model to correct for this regeneration process allowed rate parameters of k1 = (3.5 +/- 1.0)E-11 cm3 molecule-1 s-1 and k2 = (2.3 +/- 0.7)E-12 cm3 molecule-1 s-1 to be determined at 2.4 Torr.There is no pressure dependence observed for reaction (1) between 1 and 2.4 Torr, but the possibility of a slight pressure dependence for reaction (2) exists.These pressure effects are examined using the semi-empirical quantum RRK method.
Hanst,Calvert
, p. 71,104 (1959)
Preparation, Vapor Pressure, and Infrared Spectrum of Methyl Nitrite
Rook, Frederick L.
, p. 72 - 73 (1982)
A convenient preparation of ordinary and deuterated methyl nitrite has been described, their high-resolution infrared spectra have been recorded, and the vapor-pressure curve of CH3ONO has been measured in the region 154 /= T(K) /=225: log P(torr) = -1365/T + 8.102.
PROCESS AND SYSTEM FOR PRODUCING ALKYL NITRITES
-
Page/Page column 9; 10; 11; 12, (2020/06/10)
A process for producing an alkyl nitrite is provided, comprising: mixing oxygen and a circulating gas in a pre-reactor, mixing the oxidized circulating gas and an alkyl alcohol liquid in a first esterification tower to generate alkyl nitrite, heating a portion of a first esterification tower bottom liquid in a circulating heating device external to the first esterification tower and transferring the heated collected first esterification tower bottom liquid into the first esterification tower, mixing a second portion of the collected first esterification tower bottom liquid and the circulating gas in a second esterification tower to generate alkyl nitrate, transferring a second esterification tower bottom liquid into an alkyl alcohol recycling tower. A related production system is also provided with a pre-reactor, a first esterification tower, a circulating heating device, a second esterification tower and an alkyl alcohol recycling tower.
Search for the shortest intermetallic Tl—Tl contacts: Synthesis and characterization of Thallium(I) coordination polymers with several mono- and bis-cyanoximes
Curtis, Scott,Lottes, Brett,Robertson, Daniel,Lindeman, Sergey V.,Gerasimchuk, Nikolay
supporting information, (2020/04/08)
Five new Tl(I) coordination compounds based on aryl monocyanoximes, such as phenylcyanoxime – HPhCO, 1, 2-fluorophenylcyanoxime – H(2F-PhCO, 2, 3-fluorophenylcyanoxime – H(3F-PhCO), 3, of TlL composition, and aryl biscyanoximes, such as 1,3-cyanoxime (benzene) – H2(1,3-BCO, 4 and 1,4-cyanoxime (benzene) – H2(1,4-BCO), 5 of Tl2L stoichiometry were synthesized and characterized using spectroscopic methods, thermal stability studies, and X-ray analysis. All obtained complexes represent coordination polymers of different complexity, ranging in dimensionality from 1D in Tl(2F-PhCO) to 3D in Tl2(1,3-BCO). The most interesting feature of all synthesized complexes is the formation of Tl2O2 rhombs: non planar and non-centrosymmetric in Tl(PhCO), and planar and centrosymmetric in the other three compounds. These rhombi are interconnected, forming zigzag and ladder-type polymers in which very short thallophilic Tl—Tl distances were observed. Thus, in the structure of Tl2(1,3-BCO) the closest distance between metal centers was found to be 3.670 ?. This is the second shortest on-record intermetallic contact in non-organometallic and non-cluster, but Werner type complexes, and is close to that in metallic thallium: 3.456 ?. In all five new coordination polymers the central atom has a stereo-active 6 s2 lone pair that significantly distorts the shape of the coordination polyhedron of Tl(I). The first time, Tl–O vibrations in Tl2O2 rhombs were observed in Raman spectra of the obtained complexes. Thermal analysis studies evidenced stability of all complexes, but Tl(PhCO), to ～200 °C. The Tl2(1,3-BCO) compound demonstrates properties of the high energy compound, and violently exothermically decomposes at ～255 °C with the release of a significant amount of kinetic energy. The final product of anaerobic decomposition of all studied Tl-cyanoximates is metallic thallium sponge.
