74-87-3Relevant articles and documents
Controlled methyl chloride synthesis at mild conditions using ultrasound irradiation
Iersel, Maikel M. van,Schilt, Marcus A. van,Benes, Nieck E.,Keurentjes, Jos T.F.
, p. 315 - 317 (2010)
A new route for the chlorination of methane is described using ultrasound irradiation, which allows for an intrinsically safe process at ambient pressure and temperature. By tuning the gas feed composition methyl chloride yields of up to 19% have been obtained.
Pressure Dependence of the Rate Constants for the Reactions CH3 + O2 and CH3 + NO from 3 to 10E4 Torr
Kaiser, E. W.
, p. 11681 - 11688 (1993)
A relative rate technique is used to measure the pressure dependence of the rate constants for reaction 1 (CH3 + O2 + M -> CH3O2 + M) and reaction 3 (CH3 + NO + M -> CH3NO + M) relative to reaction 2 (CH3 + Cl2 -> CH3Cl + Cl).The pressure dependence of the rate constant of reaction 3 at 297 K can be represented in the Troe equation by the parameters (k3)0 = (3.5 +/- 0.4)E-30 cm6 molecule-2 s-1, (k3)infinite = (1.68 +/- 0.1)E-11 cm3 molecule-1 s-1, and Fcent = 0.46.The values of k3 are identical to those observed in recent absolute rate measurements at 296 K and 27-600 Torr, verifying that the rate constant chosen for reaction 2, k2 = 3.95E-12 exp(-530/RT), is both pressure independent and correct at 296 K.This value of k2 was used to determine absolute values of k1 from the k1/k2 in N2 diluent for pressures between 3 and 11000 Torr at 297 K, between 20 and 1500 Torr at 370 K, and between 40 and 1500 Torr at 264 K.All data in N2 can be fitted using the following parameters in the Troe equation: (k1)0 = (7.56 +/- 1.1)E-31 (T/300)-3.64+/-1.0 cm6 molecule-2 s-1; (k1)infinite = (1.31 +/- 0.1)E-12 (T/300)1.2+/-0.8 cm3 molecule-1 s-1; Fcent = 0.48 (264 K), 0.46 (297 K), 0.42 (370 K).Error limits include statistical error and the uncertainty in k2.In He, N2, and SF6 diluents the relative third-body efficiencies are 0.56 : 1.0 : 1.52, respectively, assuming that Fcent is independent of diluent.The high-pressure limit in SF6 is identical to that in N2.Rate constant ratios were also measured at 297 K for CD3 + O2 + M -> CD3O2 + M (1D) between 5 and 6000 Torr.Assuming that k2D = k2, the limiting rate constants using Fcent = 0.46 are (k1D)0 = (11.8 +/- 1.6)E-31 cm6 molecule-2 s-1 and (k1D)infinite = (1.38 +/- 0.08)E-12 cm3 molecule-1 s-1.
Study of the reaction methyl 4-nitrobenzene-sulfonate + Cl- in mixed hexadecyltrimethyl-ammonium chloride-Triton X-100 micellar solutions
Fernandez, Gaspar,Rodriguez, Amalia,Del Mar Graciani, Maria,Munoz, Maria,Moya, Maria Luisa
, p. 45 - 51 (2003)
The reaction methyl 4-nitrobenzenesulfonate + Cl- was studied in hexadecyltrimethylammonium chloride (CTAC) in the absence and presence of 0.1 M NaCl, as well as in mixed CTAC/Triton X-100 (polyoxyethylene(9.5)octylphenyl ether) aqueous micella
Methane to Chloromethane by Mechanochemical Activation: A Selective Radical Pathway
Bilke, Marius,Losch, Pit,Vozniuk, Olena,Bodach, Alexander,Schüth, Ferdi
, p. 11212 - 11218 (2019)
State-of-The-Art processes to directly convert methane into CH3Cl are run under corrosive conditions and typically yield a mixture of chloromethanes requiring subsequent separation. We report a mechanochemical strategy to selectively convert methane to chloromethane under overall benign conditions, employing trichloroisocyanuric acid (TCCA) as a cheap and noncorrosive solid chlorinating agent. TCCA is shown to release active chlorine species upon milling with Lewis acids such as alumina and ceria to functionalize methane at moderate temperatures (4,conv) (g(catalyst) s)-1. Findings were compared to the thermal reaction of methane with TCCA and evidenced that mechanochemical activation permitted significantly lower reaction temperatures (90 vs 200 °C) at a drastically improved CH3Cl selectivity (95% vs 66% at 30% conversion). Considering the characterization of the interaction between TCCA and Lewis acids as well as the in-depth analysis of byproducts, we suggest a plausible reaction mechanism and a possible regeneration of the chlorinating agent.
Vibrational excitation in products of nucleophilic substitution: The dissociation of metastable X-(CH3Y) in the gas phase
Graul, Susan T.,Bowers, Michael T.
, p. 3875 - 3883 (1994)
The relative kinetic energy distributions for the Y- + CH3X nucleophilic substitution products from dissociation of metastable X-(CH3Y) (X = Cl, Br; Y = Br, I) have been analyzed by means of ion kinetic energy spectroscopy, and the results modeled using statistical phase space theory. Comparison of the experimental distributions with the theoretical distributions predicted for statistical partitioning of the available energy reveals that the substitution products are translationally cold. The theoretically calculated distributions can be made to agree with experiment if most of the energy released in the dissociation is assumed to be unavailable for randomization, such that it cannot partition to relative translation. This unavailable energy must correspond to internal energy, most likely vibrational excitation, in the CH3X products. These results are consistent with recent theoretical predictions of non-RRKM dynamics in gas-phase SN2 reactions.
Rate constants for the gas phase reaction of chloride ion with methyl bromide over the pressure range 300 to 1100 torr
Sahlstrom,Knighton,Grimsrud
, p. 5543 - 5546 (1997)
Rate constants for the reaction of chloride ion with methyl bromide have been determined over a range of buffer gas pressures from 300 to 1100 Torr at 125 °C by ion mobility spectrometry (IMS). The rate constants were found to increase slightly with increased pressure over this range and also increased slightly with a change from nitrogen to methane buffer gas. Parallel measurements for the reaction of chloride ion with n-butyl bromide indicated no dependence of the observed rate constants on changes in the pressure or identity of the buffer gas, as expected. The present measurements indicate that the high-pressure limit (HPL) of kinetic behavior is not achieved for the Cl-/CH3Br reaction system by use of buffer gases in the near-atmospheric pressure range and are consistent with a recent suggestion by Seeley et al. that this reaction should occur with near-collision frequency in its high-pressure limit.
Low-temperature combustion of chlorinated hydrocarbons over CeO 2/H-ZSM5 catalysts
De Rivas, Beatriz,Sampedro, Carmen,López-Fonseca, Rubén,Gutiérrez-Ortiz, Miguel ángel,Gutiérrez-Ortiz, Jose Ignacio
, p. 93 - 101 (2012)
The performance of various CeO2/H-ZSM5 catalysts was evaluated for the oxidation of one of the most common chlorinated pollutants found in waste streams, namely 1,2-dichloroethane. The supported samples with varying CeO2 loading (6-50 wt.%) were prepared by impregnation and subsequently calcined at 550 °C. Structural, morphological and physico-chemical changes caused by the CeO2 addition were analysed by X-ray diffraction, transmission electronic microscopy, N2- physisorption, temperature-programmed desorption of ammonia and temperature-programmed reduction with hydrogen. The enhancement of the catalytic behaviour of the resulting samples with respect to plain H-ZSM5 could be accounted for on the basis of the synergetic role played by oxygen mobility and acid sites. Hence, an optimum cerium loading of 11 wt.% was found with a T 50 value around 210 °C. At 350 °C, where conversion of the chlorinated feed is about 99%, the major oxidation products were carbon oxides and hydrogen chloride with a reduced presence of chlorinated by-products and molecular chlorine. A relatively good catalytic stability was noticed during 80 h time on line.
Kinetics of the liquid-phase hydrochlorination of methanol
Makhin,Zanaveskin,Dmitriev
, p. 163 - 166 (2014)
The kinetics of the liquid-phase hydrochlorination of methanol with hydrogen chloride in the absence of a catalyslt is reported. A kinetic equation is suggested for the reaction. The values of the preexponential factor, activation energy, and empiric coefficients characterizing the influence of the hydration of the chlorine anion on the rate of hydrochlorination have been.
Boron halide chelate compounds and their activity towards the demethylation of trimethylphosphate
Keizer, Timothy S.,De Pue, Lauren J.,Parkin, Sean,Atwood, David A.
, p. 1463 - 1468 (2002)
Salen(t-Bu)H2 (N,N′-ethylenebis(3,5-di-tert-butyl(2-hydroxy)benzylidenimine) and its derivatives were used to prepare boron compounds having the formula L(BCl2)2 (L = salen(t-Bu) (1), salpen(t-Bu) (2), salben(t-Bu) (3), salpten(t-Bu) (4), salhen(t-Bu) (5)). These are formed from the reaction of the corresponding (L[B(OMe)2]2 with BCl3. In addition to being a new type of boron compound, they are also potential two-point Lewis acids. Indeed, they demonstrate Lewis acidic behavior in the dealkylation of trimethylphosphate. All of the compounds were characterized by mp, elemental analysis, 1H and 11B NMR, IR, MS, and in the case of 2 by X-ray crystallography.
On the mechanism of catalytic oxidation of CH2Cl2 on γ-Al2O3 and its oscillatory behaviour
Haber, Jerzy,Machej, Tadeusz,Derewiński, Miros?aw,Janik, Robert,Kry?ciak, Joanna,Sadowska, Halina
, p. 97 - 112 (1996)
Adsorption of CH2Cl2 and its oxidation with dioxygen have been investigated on pure γ-Al2O3 by means of infrared spectroscopy and gas chromatographic analysis. Infrared spectroscopy showed that CH2Cl2 may be adsorbed on the alumina surface through chlorine ions either on two adjacent exposed Al ions at the (111) plane of Al2O3, or on the isoloated Lewis acid sites. The oxidation of CH2Cl2 at temperatures below 450°C yields an intermediate product CH3Cl with 50% of selectivity whereas the other half of the CH2Cl2 amount is totally oxidized to CO2 and HCl. At temperatures higher than 450°C practically total conversion of CH2Cl2 to CO2 and HCl takes place. Selfsustained oscillations of the CH2Cl2 conversion in a broad range are observed when water vapour is added to the feed. The mechanism explaining the nature of the activity of alumina in the CH2Cl2 oxidation and selectivity to CH3Cl as well as a possible reason of oscillations of the conversion are proposed. by R. Oldenbourg Verlag, 1996.
