On the mechanism of thermal oxidation of methane

Using the method of freezing radicals in conjunction with ESR spectroscopic measurements, the kinetics of the thermal oxidation of methane has been studied under atmospheric pressure depending on the temperature, composition of the mixture, and nature of the surface of the reaction vessel. It has been shown that in a reactor treated with boric acid, the intermediates methylhydroperoxide and hydrogen peroxide are responsible for chain branching. It has been established that the leading active centers of the reaction are the HO₂ radicals, while chain branching occurs as a result of the decomposition of peroxy compounds—methylhydroperoxide and hydrogen peroxide. In reactors treated with potassium bromide, the concentrations of radicals and peroxy compounds were found to be lower than the sensitivity of the method of measurement. Computations were performed for the scheme of methane oxidation at 738 K for a reactor treated with boric acid. Satisfactory agreement was found between the experimental and computed kinetic curves of accumulation of main intermediates CH₂O, H₂O₂, CH₃OOH. The influence of their addition on the kinetics of the reaction has been considered. It has been shown that the addition of formaldehyde does not lead to chain branching, however; it contributes to the formation of those peroxy compounds that bring about chain branching. Mathematical modeling confirmed conclusions made on the basis of experimental data concerning the nature of the leading active centers and the products that are responsible for the degenerate chain branching.     

The mechanism and pathway of the ozonation of 4-chlorophenol in aqueous solution

Chlorophenols (CPs) have been widely used in dif- ferent formulations as preservatives, herbicides, insec- ticides, bactericides and solvents. Parts of chlorophe- nols were released to the natural environment during the usage. As a result, many water sources were con- taminated with CPs[1,2]. Furthermore, they also can be formed during the disinfection of phenol containing water by chlorination. Several CPs are recognized as the priority pollutants by the United States EPA (En- vironmenta…     

Effect of solvation on the reactivity of peroxide radicals in oxidation reactions

The reactivity of RO ₂ ^. peroxide radicals in oxidation reactions depends greatly on specific and nonspecific solvation by the solvent. With increasing dielectric constant () of the medium, the rate constant for the interaction of RO ₂ ^. radicals with methyl ethyl ketone (k₂) and the rate constant of the recombination of RO ₂ ^. radicals (k₆) increase. The specific solvation of RO ₂ ^. radicals due to hydrogen bonds of water diminishes their reactivity. Equilibrium constants for the solvation of peroxide radicals and all rate constants of chain propagation and termination reactions involving solvated and unsolvated RO ₂ ^. radicals were measured. The change in composition of the oxidation products when methyl ethyl ketone was diluted with benzene or water is caused by nonspecific and specific solvation by the solvent affecting the chain propagation reaction.     

Deactivation of Molybdenum-Containing Zeolites in the Course of Nonoxidative Methane Conversion

It was found that the nonoxidative dehydroaromatization of methane occurs over Mo-containing pentasil-type zeolites with various framework compositions at 750°C. This reaction is accompanied by catalyst deactivation because of coke formation. The effects of the space velocity of methane and the composition of the zeolite matrix on the amount and properties of the resulting condensation products were studied. It was found that the lowest amount of coke with a relatively low degree of polycondensation was formed on zeolite with SiO₂/Al₂O₃ = 40 containing Mo nanoparticles.     

Oxidation of azo dye Orange II with hydrogen peroxide catalyzed by 5,10,15,20-tetrakis[4-(diethylmethylammonio)phenyl]porphyrinato-cobalt(II)tetraiodide in aqueous solution

The catalytic oxidation of the azo dye Orange II by hydrogen peroxide in aqueous solution has been investigated using 5,10,15,20-tetrakis-[4-(diethylmethylammonio)phenyl]porphyrinato-cobalt(II) tetra iodide 1as catalyst. The oxidation reaction was followed by recording the UV–vis spectra of the reaction mixture with time at λ_max = 485 nm. The factors that may influence the oxidation of Orange II, such as the effect of reaction temperature, concentration of catalyst, hydrogen peroxide and orange II have been studied. The results of total organic carbon analysis showed 52% of dye mineralization under mild reaction conditions. Residual organic compounds in the reaction mixture were identified by using Gas chromatography-mass spectrometry. The decolorization rate and mineralization of the dye has been found to increase with increase of catalyst concentration and reaction temperature. The rate of dye oxidation decreased with increasing the concentration of dye, H₂O₂ and at higher pH than 9. Radical scavenging measurement indicated that decolorization of Orange II by H₂O₂/cobalt (II) porphyrin complex 1 involved the formation of hydroxyl radicals as the active species.     

Reaction of zirconium alkoxides with tert-butyl hydroperoxide. Oxidative ability of the Zr(OBu-t)4-t-BuOOH system

Oxidation of the isopropoxy group in the Zr(i-PrO)₄·i-PrOH complex involves both direct reaction with tert-butyl hydroperoxide and intermediate formation of zirconium peroxy compound. Zirconium tetra-tert-butoxide reacts with tert-bytyl hydroperoxide to form metal-containing peroxide and trioxide. Decomposition of the latter leads to oxygen evolution and is accompanied by radical formation. The alkoxyl and peroxyl radicals formed were identified by ESR spectroscopy. The nature of the oxidant (oxygen, zirconium-containing peroxide and-trioxide) in the Zr(OBu-t)₄-t-BuOOH system is determined by the structure of the substrate molecule.     

Reactions of CH3O2 radicals on solid surface

The reaction probability of CH₃O₂ radicals with NO₂, CH₄, C₃H₆, and CH₃CHO on the solid surface of KCl in flow at low pressure and temperature range of 297–353 K has been studied. The chosen conditions allowed excluding homogeneous interaction of radicals. The heterogeneous radical decay of peracetic acid served as a source of CH₃O₂ radicals. On the basis of ESR measurements of CH₃O₂ radicals with the above‐mentioned compounds, a heterogeneous reaction mechanism has been identified. The reactivity of NO₂ was greatest for the compounds studied. The effective activation energy was evaluated to be 10.4 ± 0.8 kJ/mol for the reaction of RO₂ radicals with NO₂ and ?21.3 ± 2.8 kJ/mol for methane. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 591–595, 2004     

Reactions of methylaluminoxane and trimethylaluminum with zirconium and titanium tetracyclopentadienyl derivatives

Gas volumometry, gas chromatography, mass spectrometry, and ESR were used to study reactions of methylaluminoxane (MAO) and Me₃Al with Cp₄Zr, Cp₄Ti, and 2,2,6,6-tetra-methylpiperidine-1-oxyl (TEMPO). It was shown that the reaction is accompanied by evolution of methane, whose amount exceeds the initial concentration of the starting metallocene or free radical by a few hundred times, but in all the cases is no more than 15% of the starting amount of the Me??Al fragments in the organoaluminum compound. Metal-centered radicals were detected by ESR in the systems with Zr and Ti metallocene derivatives. Mechanism of the observed reactions is discussed.     

Mechanism of the reaction of radicals with peroxides and dimethyl sulfoxide in aqueous solution

The reactions of methyl and methylperoxyl radicals derived from dimethyl sulfoxide (DMSO) with hydrogen peroxide, peroxymonocarbonate (HCO4 (-)), and persulfate were studied. The major reaction observed for the hydroperoxides was the abstraction of the hydrogen atom by the radicals. The radicals interact with a lone pair of electrons on the peroxide to produce methanol and formaldehyde. Furthermore, the results indicate that in RO2H and RO2R', electron-withdrawing groups cause a considerable increase in the reactivity of the peroxides towards the radicals and not only towards nucleophiles. The HO2 (.)/O2 (.-) and CO3 (.-) radicals react with DMSO to produce methyl radicals. Thus, the formation of the (.)CH3 radicals in the presence of DMSO is not proof of the formation of the (.)OH radicals in the system. These reactions must be considered when radical processes, such as in biological and catalytic systems, are studied. Especially, the plausible role of HCO4 (-) ions in biological systems as a source of oxidative stress cannot be overlooked.     

Kinetics and mechanism of hydrogen peroxide decomposition in the presence of the tetraaquapalladium(<Emphasis Type="SmallCaps">II</Emphasis>) complex

Kinetics of hydrogen peroxide decomposition in the presence of the tetraaquapalladium(II) complex in an aqueous solution at 40–70 °C was studied. The reaction rate is the first order with respect to the concentration of both Pd^II and H₂O₂ and the negative first order with respect to perchloric acid. Using free radicals traps, the reaction mechanism was found to differ from the traditional free-radical mechanism known for d-metal aqua ions and proceeds without generation of hydroxyl radicals. The kinetic data obtained suggest a mechanism involving the formation of an intermediate palladium complex with oxygen. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1077–1082, May, 2005.     

Long-wave light absorption and photochemical decomposition of peroxide radicals

Photochemical decomposition of alkylperoxide radicals in glassy matrices at 77 K was experimentally studied. Irradiation with light up to 405 nm leads to the photodecomposition of peroxide radicals. The quantum yield of the reaction was estimated to be 10^–2. A light-induced angular dependence of the ESR spectra of peroxide radicals resulting from photoselection was detected. The photoselection found proves that the photodecomposition is induced by the absorption of light in the inherent absorption band of RO₂.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1074–1077, June, 1995.The work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 95-03-08505) and the International Science Foundation (Grants NBU 000 and NBU 300).     

The oxidation and thermal transformations of macrooradicals in gamma irradiated cellulose

The secondary reactions of the oxidation and thermal transformations of gamma irradiated (at 77 K) and plasticized (with water) cellulose radicals were studied by 3 cm-and 2 mm-band EPR spectroscopy. The radiolysis of cotton cellulose was found to produce the H-C*=O formyl radical, and heating the irradiated samples to 190–200 K resulted in the formation of the ROO* peroxide radical. The EPR spectra of microcrystalline cellulose recorded at room temperature contained an individual triplet (α _β ^H = 2.5–2.7 mT) with an additional quadruplet structure (splitting 0.5–0.7 mT) from three γ-hydrogens. This triplet was interpreted as a signal of the primary radical at C4. The main direction of thermal transformations of primary radicals was synchronous reactions of the dehydration of the polycarbohydrate complex accompanied by the dissociation of the C-H, C-OH, and C-C bonds and elimination of H₂O, H₂, CO, and CO₂ with successive formation of allyl and then polyene radicals, which were a source of the growth of polyconjugated systems in macromolecules.     

The kinetics and mechanism of gas-phase N-oxidation of pyridine with hydrogen peroxide

The kinetics of N-monooxidation of 4-vinylpyridine as a π-deficient heteroaromatic compound under the conditions of gas-phase free-radical chain oxidation was studied. The experimental interference kinetic curves of synchronous hydrogen peroxide decomposition and 4-vinylpyridine N-oxidation reactions were obtained. The region of selective N-oxidation was determined and optimum conditions of N-oxide preparation found. The most probable mechanism was suggested. According to this mechanism, a key role in the free-radical N-oxidation of the substrate and its synchronization with the H₂O₂ decomposition reaction was played by HO₂ radicals.     

The influence of hydrogen on the kinetics of plasmapyrolytic methane conversion

The plasma pyrolysis of methane in the presence of excess hydrogen was kinetically modeled by means of a single pulse shock tube (SPST) technique. Pyrolytic decomposition of methane and the product formation including quenching was investigated as a function of temperature and dwell time in order to elucidate the kinetic role of hydrogen. Methane pyrolysis with an excess of hydrogen leads to lower conversion degrees and lower product yields as compared to pure methane. The decay curves may be described kinetically by first- and second-order ate equations, depending on reaction conditions. An excess of hydrogen causes a decrease in the overall rate constants for the methane decomposition and a straightening of the Arrhenius plots. According to the reaction mechanisms the recombination of primary radicals, especially CH₃, with H₂ molecules and H atoms is significant.     

有序介孔锰氧化物催化过氧化氢降解水中诺氟沙星

采用硬模板法制备了有序介孔氧化锰,并用过氧化氢氧化诺氟沙星的降解率及其抗菌活性变化评价了其催化活性.研究发现,有序介孔锰氧化物表现出较高的催化活性;低pH有利于提高其催化活性.与单独过氧化氢氧化过程相比,有序介孔锰氧化物的存在明显减弱了诺氟沙星的抗菌活性.叔丁醇对催化体系的抑制作用表明有序介孔锰氧化物促进了过氧化氢分解生成羟基自由基.通过对诺氟沙星在催化过程中的分解产物鉴定,提出了可能的分解途径.     

The photopolymerization of isoprene with the use of hydrogen peroxide as photoinitiator

The photochemical polymerization reactions of isoprene with the use of H₂O₂ as the photoinitiator have been studied in benzene, acetone, and tetrahydrofuran solutions. Hydrogen peroxide is photodecomposed to form hydroxyl radicals which may initiate the polymerization of isoprene with hydroxyl terminated polyisoprene as the product. Average molecular weight, microstructure, and the functionality of the hydroxyl terminated polyisoprene are determined. A suitable reaction mechanism and the polymerization rate equations are proposed. The overall activations energy is evaluated to be about 3.8 kcal/mol.     

Identification of volatile products produced during the peroxide vulcanization of poly(vinyl alkyl ethers)

Volatile products are produced during vulcanization of the polymers of vinyl methyl, ethyl, isopropyl and n-butyl ethers with dicumyl peroxide, both in the presence and, absence of added sulfur. They were identified and estimated by gas-liquid chroma tography and mass spectrometry. The principal products formed during the vulcanization of poly(viny1 ethyl ether) with dicumyl peroxide were ethane and acetaldehyde and to a lesser extent methane. The addition of sulfur in the curing recipe resulted in a sharp increase in the proportion of ethyl alcohol, a large increase in methane, and a large decrease in ethane. The formation of these volatile products and the observed changes due to the presence of sulfur in the curing recipe can be accounted for on the basis of side-chain scission of the polymer radicals produced during vulcanization. The length and/or shape of the alkyl group in poly(viny1 alkyl ether) determine the composition of the volatile products. The data are in harmony with the postulated chemistry of vulcanization of these polymers.     

The oxidation of hydrocarbons by water vapor behind high-temperature shock-waves

The oxidation of acetylene by water vapor was studied behind the reflected shock in a single-pulse shock tube. Computer simulation experiments reproduced the experimental results in the temperature range of 1500 to 2000°K. The kinetic scheme suggested here involves three major processes, (1) production of hydrogen atoms by the sequence of reactions which lead from acetylene to carbon; (2) production of OH radicals, mainly by the reaction H + H₂O → H₂ + OH, and (3) fast oxidation of the acetylene and other C/H species by the available oxidants in the system. The experimental results of methane oxidation suggest that methane is converted to acetylene prior to its oxidation. The implication of the experimental results to processes occurring in planetary atmospheres as a result of thunder shock waves is briefly discussed.     

ESR studies of vinyl polymerization. II. Initial reactions of vinyl esters with redox systems in aqueous media

ESR measurements of transient radicals during redox polymerization of various vinyl esters in aqueous solutions have been made by using the rapid-mixing flow method. The initiation was by means of hydroxyl and amino radicals from the systems titanous chloride-hydrogen peroxide and titanous chloride-hydroxylamine, respectively. The well resolved hyperfine structures obtained at monomer concentrations of about 0.05 mole/1. are unambiguously assigned to the monomer radicals formed by addition of initiator radicals to monomers. At higher monomer concentrations, additional weak signals attributed to the growing polymer radicals were observed. The effect of reaction conditions on the signal intensity has been studied in particular for vinyl acetate. The coupling constants of monomer radicals from various vinyl esters (acetate, propionate, butyrate, crotonate, and isopropenyl acetate) were obtained and the spin densities calculated. From the ESR spectra, the monomer radicals have a conformation with the substituent R (R = HO or NH₂) of R? CH₂? CH(OCOR′) locked in a position above or below the radical plane. This is tentatively interpreted as due to formation of intramolecular hydrogen bonds to ring structures or complexes with titanium ions. In addition, hydrogen abstraction reactions of some model compounds for poly(vinyl acetate) have been briefly studied in relation to chain transfer and grafting reactions.     

Etching of GaAs (100) with gaseous H/CH3 mixtures

GaAs (100) wafers were etched in mixtures of hydrogen atoms and methyl radicals. The atoms were formed in a remote hydrogen plasma, and a fraction of these were converted into methyl radicals by introducing methane into the flow system upstream from the semiconductor surface. The flux of hydrogen atoms into the reaction chamber was determined by isothermal calorimetry. The methyl radical flux passing over the substrate was then calculated using previously determined rate parameters for the reaction between atomic hydrogen and methane, and a simple modeling program. The GaAs etch rates were about an order of magnitude faster when methyl radicals were present in the hydrogen atom stream, and were found to follow a first-order dependence on the partial pressure of methyl radicals. Absolute rate constants were determined and an Arrhenius activation energy of 1.2 kcal mol^?1 was calculated. The values of k and E_a are consistent with a diffusion-controlled process. SEM photographs of the surface revealed small crystallographic features that made the surface appear very rough. XPS analysis indicated that these surfaces were arsenic deficient. A mechanism is proposed for the etching of GaAs by a combination of methyl radicals and hydrogen atoms. © 1994 John Wiley & Sons, Inc.