Xn:Harmful;
75-09-2Relevant articles and documents
Reductive electrochemical decomposition of chloroform on metal electrodes
Sonoyama, Noriyuki,Hara, Kohjiro,Sakata, Tadayoshi
, p. 131 - 132 (1997)
The electrochemical reductive decomposition of chloroform was carried out using 15 kinds of metal electrodes. The efficiency of the decomposition and the main product of reaction largely depended on the metal electrodes. The hydrogenation of chloroform by Ag, Zn, Pd and Cu electrodes proceeded in about 100% efficiency. These electrodes produced methane mainly. Pb electrode produced dichloromethane selectively.
Kinetics and mechanism of the gas phase reaction of atomic chlorine with CH2ICl at 206-432 K
Bilde,Sehested,Nielsen,Wallington,Meagher,McIntosh,Piety,Nicovich,Wine
, p. 8035 - 8041 (1997)
The title reaction was studied using two different experimental techniques: laser flash photolysis with resonance fluorescence detection of Cl atoms and continuous photolysis with FTIR detection of end products. Over the temperature range 206-432 K the rate constant for reaction of Cl atoms with CH2ICl is given (to within ±15%) by the Arrhenius expression k1 = 4.4 × 10-11 exp(195/T) cm3 molecule-1 s-1, which gives k1 = 8.5 × 10-11 cm3 molecule-1 s-1 at 298 K. Variation of the total pressure of N2 diluent over the range 5-700 Torr at 295 K had no discernible (2 the reaction proceeds via iodine transfer to give CH2Cl radicals. As part of this work the rate constant k(CH2Cl+O2+M) was measured at 295 K in the presence of 1-800 Torr of N2 diluent. The results were well described by the Troe expression with a broadening factor Fc of 0.6 and limiting low- and high-pressure rate constants of k0 = (1.8 ± 0.1) × 10-30 cm6 molecule-2 s-1 and k∞ = (3.3 ± 0.3) × 10-12 cm3 molecule-1 s-1. The results are discussed with respect to the available literature for reactions of Cl atoms with halogenated organic compounds and the potential role of the title reaction in atmospheric chemistry.
Redox-active porous coordination polymers prepared by trinuclear heterometallic pivalate linking with the redox-active nickel(II) complex: Synthesis, structure, magnetic and redox properties, and electrocatalytic activity in organic compound dehalogenation in heterogeneous medium
Lytvynenko,Kolotilov,Kiskin,Cador,Golhen,Aleksandrov,Mishura,Titov,Ouahab,Eremenko,Novotortsev
, p. 4970 - 4979 (2014)
Linking of the trinuclear pivalate fragment Fe2CoO(Piv) 6 by the redox-active bridge Ni(L)2 (compound 1; LH is Schiff base from hydrazide of 4-pyridinecarboxylic acid and 2- pyridinecarbaldehyde, Piv- = pivalate) led to formation of a new porous coordination polymer (PCP) {Fe2CoO(Piv)6}{Ni(L) 2}1.5 (2). X-ray structures of 1 and 2 were determined. A crystal lattice of compound 2 is built from stacked 2D layers; the Ni(L) 2 units can be considered as bridges, which bind two Fe 2CoO(Piv)6 units. In desolvated form, 2 possesses a porous crystal lattice (SBET = 50 m2 g-1, V DR = 0.017 cm3 g-1 estimated from N2 sorption at 78 K). At 298 K, 2 absorbed a significant quantity of methanol (up to 0.3 cm3 g-1) and chloroform. Temperature dependence of molar magnetic susceptibility of 2 could be fitted as superposition of X MT of Fe2CoO(Piv)6 and Ni(L)2 units, possible interactions between them were taken into account using molecular field model. In turn, magnetic properties of the Fe2CoO(Piv) 6 unit were fitted using two models, one of which directly took into account a spin-orbit coupling of CoII, and in the second model the spin-orbit coupling of CoII was approximated as zero-field splitting. Electrochemical and electrocatalytic properties of 2 were studied by cyclic voltammetry in suspension and compared with electrochemical and electrocatalytic properties of a soluble analogue 1. A catalytic effect was determined by analysis of the catalytic current dependency on concentrations of the substrate. Compound 1 possessed electrocatalytic activity in organic halide dehalogenation, and such activity was preserved for the Ni(L)2 units, incorporated into the framework of 2. In addition, a new property occurred in the case of 2: the catalytic activity of PCP depended on its sorption capacity with respect to the substrate. In contrast to homogeneous catalysts, usage of solid PCPs may allow selectivity due to porous structure and simplify separation of product.
Chlorodefluorination of Fluoromethanes and Fluoroolefins at a Lewis Acidic Aluminum Fluoride
Braun, Thomas,Pan, Xinzi,Scholz, Gudrun,Talavera, Maria
, (2022/03/27)
Chlorodefluorination reactions of fluoromethanes and fluoroolefins catalysed by the highly Lewis acidic nanoscopic aluminum chlorofluoride (ACF, AlClxF3?x, x≈0.05–0.3) in the presence of ClSiEt3 were studied. Both fluoromethanes and fluoroolefins convert under mild reaction conditions by fluorine-chlorine exchange steps into chlorinated fluoro derivatives. MAS NMR studies provided information on the interaction of silanes and hexafluoropropene with the ACF surface.
CROSSLINKED ARTIFICIAL NUCLEIC ACID ALNA
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, (2022/01/12)
The present invention provides a novel bridged artificial nucleic acid and an oligomer containing the same as a monomer. The present invention provides specifically a compound represented by general formula (I) (wherein each symbol is the same as defined in the specification) or salts thereof; as well as an oligonucleotide compound represented by general formula (I′) (wherein each symbol is the same as defined in the specification) or salts thereof.
Method of Converting a Brominated Hydrocarbon to a Chlorinated Hydrocarbon
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Paragraph 0183-0186, (2021/02/19)
The present invention provides a method of converting a brominated hydrocarbon to a chlorinated hydrocarbon that involves contacting together the brominated hydrocarbon and a chlorinated ion exchange resin that has a water content of less than or equal to 30 percent by weight, based on the total weight of the chlorinated ion exchange resin and the water. The brominated hydrocarbon includes at least one replaceable bromo group, where each replaceable bromo group is independently covalently bonded to an sp3 hybridized carbon. Contact between the brominated hydrocarbon and the chlorinated ion exchange resin results in replacement of at least one replaceable bromo group of the brominated hydrocarbon with a chloro group, and correspondingly conversion of at least a portion of the brominated hydrocarbon to the chlorinated hydrocarbon.
A new strategy to improve catalytic activity for chlorinated volatile organic compounds oxidation over cobalt oxide: Introduction of strontium carbonate
Liu, Hao,Shen, Kai,Zhao, Hailin,Jiang, Yongjun,Guo, Yanglong,Guo, Yun,Wang, Li,Zhan, Wangcheng
, (2021/07/31)
Co3O4–SrCO3 catalysts with various Sr/Co ratios were synthesized by the coprecipitation method, and their properties were tuned by adjusting the Sr/Co molar ratio. Furthermore, the catalytic combustion of vinyl chloride (VC) was used to evaluate the catalytic activity of the Co3O4–SrCO3 catalysts. The physicochemical properties of the catalysts were studied by X-ray diffraction (XRD), infrared spectroscopy (IR), N2 sorption, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), H2 temperature-programmed reduction (H2-TPR) and VC temperature-programmed desorption (VC-TPD). The results showed that the Co3O4–SrCO3 catalysts exhibited composite phases of Co3O4 and SrCO3 and the presence of interactions between them. As a result, the crystallization of the Co3O4 phase for the Co3O4–SrCO3 catalysts was restrained, and the state of Co on the catalyst surface was adjusted. Furthermore, the reducibility and VC adsorption capacity of the Co3O4–SrCO3 catalysts with Sr/Co molar ratios of 0.2 and 0.4 were enhanced compared with those of the Co3O4 catalyst. Otherwise, catalyst SrCo-0.4 exhibited excellent catalytic performance, accompanied by the highest reaction rate and the lowest apparent activation energy. More importantly, the optimized SrCO3–Co3O4 catalyst showed superior catalytic performance compared with other transition metal oxides in previous literature. These results brought a new idea for promoting the activity of transition metal catalysts for the deep oxidation of chlorinated volatile organic compounds (CVOCs) by introducing alkaline-earth metal salts.
A process of preparing methyl chloride using multistage reaction
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Paragraph 0092-0100; 0112; 0120, (2020/06/10)
The present invention relates to a method of producing methyl chloride by multistage reactions. The method of the present invention comprises: a) a chlorination step for sufficiently increasing the conversion rate of methane, which is an initial reactant; and b) a subsequent reaction step for actively utilizing hydrogen chloride (HCl), which is a hazardous byproduct of chlorination, efficiently treating harmful hydrogen chloride, and at the same time, improving the overall production of methyl chloride.COPYRIGHT KIPO 2020
Control of methane chlorination with molecular chlorine gas using zeolite catalysts: Effects of Si/Al ratio and framework type
Kwon, Seungdon,Chae, Ho-Jeong,Na, Kyungsu
, p. 111 - 117 (2020/01/31)
CH4 chlorination with Cl2 gas is used for the production of chlorinated products via C–H bond activation in CH4. Due to the high reactivity of Cl2, this reaction can occur spontaneously under UV irradiation or with mild thermal energy even in the absence of a catalyst via a free radical-mediated chain reaction mechanism that undesirably causes excessive chlorination of the CH4 and is thus non-selective. In this work, CH4 chlorination is investigated using HY and MFI zeolites with various Si/Al ratios, by which the reaction is catalytically controlled for selective production of the mono-chlorinated product (CH3Cl). Depending on the framework type, Si/Al ratio of the zeolites, and reaction conditions, different degrees of CH4 conversion, CH3Cl selectivity, and hence CH3Cl yield were achieved, by which systematic relationships between the catalyst properties and performance were discovered. A high aluminum content facilitated the production of CH3Cl with up to ～20 % yield at a high gas hourly space velocity of 2400 cm3gcat?1 h?1 with a CH4/Cl2 ratio of 1 at 350 °C. HY zeolites generally furnished a slightly higher CH3Cl yield than MFI zeolites, which can be attributed to the larger micropores of the HY zeolites that support facile molecular diffusion. With various flow rates and ratios of CH4 and Cl2, the CH4 conversion and CH3Cl selectivity changed simultaneously, with a trade-off relationship. Unfortunately, all zeolite catalysts suffered from framework dealumination due to the HCl produced during the reaction, but it was less pronounced for the zeolites having a low aluminum content. The results shed light on the detailed roles of zeolites as solid-acid catalysts in enhancing CH3Cl production during electrophilic CH4 chlorination.
METHOD OF CONVERTING ALKANES TO ALCOHOLS, OLEFINS AND AROMATICS
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Paragraph 0054-0055, (2019/08/08)
A cost-effective and energy-efficient process is disclosed for converting a methane-containing gas to a methane sulfonyl halide comprising reacting the methane-containing gas, under illumination by a light emitting diode (LED) source, with a sulfuryl halide or a halogen in the presence of sulfur dioxide, whereby the methane sulfonyl halide is obtained for isolation or further reactions. The further reactions may sequentially include, in order, contacting the methane sulfonyl halide with a catalyst complex to form a methane monohalide; catalytically converting the methane monohalide to a value-added chemical such as an alcohol, an olefin, an aromatic, derivatives thereof, or mixtures thereof; releasing any hydrogen halide formed in the process; and converting the hydrogen halide to a halogen and recycling it for re-use.
