Study of the mechanism of polysulfone decomposition by pyrolysis/gas chromatography and pyrolysis/gas chromatography/mass spectrometry

Both co- and terpolysulfones have been flash-pyrolyzed at high temperature followed by separation and identification of the products by gas chromatography and/or gas chromatography/mass spectrometry. As expected, most of the products were the corresponding olefin and SO₂. Additionally, higher molecular weight products, including aromatics, and olefin isomerization products, were produced. Mechanisms for initiation and formation of the higher molecular weight products are presented which include the back reaction of intermediate free radicals to abstract hydrogen or to form C? C bonds followed by expulsion of SO₂. The free-radical intermediates formed by the SO₂ expulsion undergo transformations to give the aromatic products. No breakdown products were found with either O or S present, nor was SO₂H found.     

Experimental and Theoretical Study on Pyrolysis of Isopsoralen

The pyrolysis of isopsoralen was studied by synchrotron vacuum ultraviolet photoionization mass spectrometry at low pressure. The pyrolysis products were detected at different photon energies, the ratios of products to precursor were measured at various pyrolysis temperatures. The experimental results demonstrate that the main pyrolysis products are primary CO and sequential CO elimination products (C₁₀H₆O₂ and C₉H₆O). The decomposition channels of isopsoralen were also studied by the density functional theory, then rate constants for competing pathways were calculated by the transition state theory. The dominant decom-position channels of isopsoralen and the molecular structures for corresponding products were identified by combined experimental and theoretical studies.     

Crossed Molecular Beam Study of H+CH4 and H+CD4 Reactions: Vibrationally Excited CH3/CD3 Product Channels

We study the H+CH₄/CD₄→H₂/HD+CH₃/CD₃ reactions using the time sliced velocity map ion imaging technique. Ion images of the CH₃/CD₃ products were measured by the (2+1) resonance enhanced multi-photon ionization (REMPI) detection method. Besides the CH₃/CD₃ products in the ground state, ion images of the vibrationally excited CH₃/CD₃ products were also observed at two collision energies of 0.72 and 1.06 eV. It is shown that the angular distribution of the products CH₃/CD₃ in vibrationally excited states gradually vary from backward scattering to sideways scattering as the collision energy increases. Compared to the CH₃/CD₃ products in the ground state, the CH₃/CD₃ products in vibrationally excited states tend to be more sideways scattered, indicating that larger impact parameters play a more important role in the vibrationally excited product channels.     

Conversion of hydrocarbon gases in dielectric barrier discharge in the presence of water

The conversion of C₁–C₄ hydrocarbons into gaseous and liquid products in a dielectric barrier discharge plasma in the presence of water has been studied. The formation of a deposit on the electrode surface is prevented by introducing water in the liquid state into a gaseous hydrocarbon stream, a finding that has been confirmed by IR spectroscopic study of the electrode surface. Hydrogen and C₂₊ hydrocarbons have been detected among the gaseous products of conversion, the liquid products being represented by C₆–C₁₀₊ alkanes. The total liquid products have amounted to 13.4, 26.0, or 36.6% for the methane, propane, or n-butane conversion, respectively. A 10% propane or butane admixture to methane increases the yield of the liquid products to make 22.0 and 31.7% for the methane–propane and the methane–butane mixture, respectively.     

The selective catalytic oxidation of toluene

It was found for the first time that the selectivity of toluene transformations into benzaldehyde and benzoic acid decreased and into maleic anhydride and deep oxidation products increased as the ability of vanadium-containing catalysts of toluene oxidation to generate the singlet form of molecular oxygen grew. A scheme of the formation of the products of toluene oxidation with oxygen was suggested. Quinones were shown to be final rather than intermediate oxidation products. The selectivity of the reaction with respect to mild oxidation products in the presence of V₂O₅, MoO₃, and V₂O₅ · MoO₃ could be increased by changing the temperature of catalyst preparation from 400 to 500°C.     

Research of thermal decomposition of hydrated methanesulfonates

Hydrated methanesulfonates Ln(CH₃SO₃)₃·nH₂O (Ln=La, Ce, Pr, Nd and Yb) and Zn(CH₃SO₃)₂·nH₂O were synthesized. The effect of atmosphere on thermal decomposition products of these methanesulfonates was investigated. Thermal decomposition products in air atmosphere of these compounds were characterized by infrared spectrometry, the content of metallic ion in thermal decomposition products were determined by complexometric titration. The results show that the thermal decomposition atmosphere has evident effect on decomposition products of hydrated La(III), Pr(III) and Nd(III) methanesulfonates, and no effect on that of hydrated Ce(III), Yb(III) and Zn(II) methanesulfonates. This revised version was published online in August 2006 with corrections to the Cover Date.     

Fast-neutron radiolysis of acid water at elevated temperatures

Determination of G-values of water decomposition products in acid formed by irradiation of fast neutrons from a reactor YAYOI at elevated temperatures up to 275°C was carried out with a combination of an aerated and a deaerated Fricke dosimeters and a cerium dosimeter. As a first step, the dosimetry of the radiation field revealed that the average energy of the fast neutrons is 0.8 MeV, and over 90% of the total dose absorbed by the aqueous solutions comes from fast neutrons. At room temperature, G-values evaluated for water decomposition products, G_H + Ge^-_aq = 1.25, G_OH = 0.68, G_H2 = 0.99, G_H2O2 = 1.27 and G_-H2O = 3.21, coincide with those at initial LET of about 4 eV/Å. With increasing temperature, radical products increase and molecular products decrease, and above 150°C, relative G-values of the products seem to be similar to those obtained in γ-radiolysis at room temperature; however, G_-H2O decreases slightly. On the basis of the above results, the temperature effect of water decomposition with fast neutron at elevated temperatures is concluded to be very different from that by γ-rays, where no drastic change in the decomposition pattern with temperature was found.     

Investigation of lead thiosulfate photolysis in aqueous solutions

A model of photolysis of PbS₂O₃ aqueous solutions has been proposed on the basis of identified photolysis products and semiempirical quantum-chemical calculations. The degradation of PbS₂O₃ starts with the dissociation of the sulfur-sulfur bond in the thiosulfate group via photochemical excitation and transition of the system a whole to the activated state, which is decomposed by the solvent. The interaction of the primary photolysis products with PbS₂O₃ results in the formation of final products.     

Photolysis of 1,1,1-trifluoromethylazomethane as a source of methyl and trifluoromethyl radicals

The photochemistry of 1,1,1-trifluoromethylazomethane has been partially characterized. The quantum yield for N₂ formation from photolysis at 366 nm and room temperature was unity at low pressure and decreased to 0.5 at 630 torr. At room temperature the principal products were C₂H₆, C₂F₆, CH₃CF₃ (or CH₂CF₂ + HF at reduced pressures), plus substituted hydrazines, which mainly arise from addition of CF₃ to the parent followed by combination of these radicals with CH₃ or CF_3. These fluorinated methyl hydrazine products detract from the general utility of CF₃-N₂-R compounds as sources for simultaneous study of the chemistry of CF₃ and R radicals. At room temperature the hydrazine products accounted for more than 50% of the total yield; however, these products can be reduced by lowering the temperature and at 195°K their yields are negligible. The quantum yield for intramolecular (direct) formation of CH₃CF₃ + N₂ was shown to be ≤0.002.     

The radiolysis of mixtures of carbon dioxide and hydrogen

The self-radiolysis of CO₂ in excess tritium (³H₂) has been studied at pressures of 0.1 to 1.0 atm, temperatures of ?80° to +100°C, and in the presence of added H₂O, He, or Ar. The primary products of decomposition are CO and ³H₂O. Secondary products are C³H₄, C₂³H₄, and a white polymer. The rates of disappearance of CO₂ and formation of products and G-;values were measured. The disappearance of CO₂ initially obeys first-order kinetics, then slows down with time at a rate depending upon the initial pressure of ³H₂. The initial rates are proportional to pressures of CO₂ and ³H₂. They are independent of temperature, decreased by addition of H₂O vapor, and increased by addition of He or Ar. The proposed mechanism of decomposition of CO₂ and formation of products involves ionization of CO₂ followed by dissociative recombination forming CO and O. Then the O reacts with a hydrogen-containing species forming OH and H₂O, and a back reaction forms CO₂ from CO and OH.     

High-Resolution Experimental Study on Photodissocaition of N2O

We study the photodissociation dynamics of nitrous oxide using the time-sliced ion velocity imaging technique at three photolysis wavelengths of 134.20, 135.30, and 136.43 nm. The O(¹S_J=0)+N₂(X¹∑_g⁺) product channels were investigated by measuring images of the O(¹S_J=0) products. Vibrational states of N₂(X¹∑_g⁺) products were fully resolved in the images. Product total kinetic energy releases (TKER) and the branching ratios of vibrational states of N₂ products were determined. It is found that the most populated vibrational states of N₂ products are v=2 and v=3. The angular anisotropy parameters (β values) were also derived. The β values are very close to 2 at low vibrational states of the correlated N₂(X¹∑_g⁺) products at all three photolysis wavelengths, and gradually decrease to about 1.4 at v=7. This indicates the dissociation is mainly through a parallel transition state to form products at lower vibrational states, and the highly vibrational exited products are from a more bent configuration. This is consistent with the observed shift of the most intense rotational structure in the TKER as the vibrational quantum number increases.     

“Spontaneous” growth of fibrous products on the surface of silicic acid gels

We have observed occurrence of fibrous products on gel surface in four-component system of KK (silicic acid sol)–H₂O–HCl–NH₃, KK–H₂O–HCl–NaOH and KK–H₂O–HCl–TEA (triethanolamine). Bundles of fibres occur in the system with NH₃, sticks and needles in system with NaOH, and finally in the system with TEA we can mostly observe the occurrence of crystalline products. Dependency of product morphology on initial sol composition is occurring in observed systems. In the case of system with NH₃, mostly the length of nascent fibres is influenced by the composition, and in the systems with NaOH and TEA it is also final shape of nascent products. Morphology of nascent products in systems with NH₃ and NaOH is controlled by quantity of added HCl, but in the system with TEA it is quantity of added TEA. It is characteristic for all observed systems that “spontaneously” occurring products consist of crystalline phase, that is chloride of respective alkali, and amorphous phase, that is SiO₂. Beginning of respective chloride crystallization in observed systems probably initializes occurrence of products on gel surface. Further growth of crystals is influenced by present colloid of SiO₂ that interacts with surface of growing crystal leading to anisotropy of its growth and therefore to “spontaneous” occurrence of fibrous products.     

Thermal decomposition and creation of reactive solid surfaces

Three chromia precursors, namely CrO₃, (NH₄)₂Cr₂O₇ and chromia gel, were subjected to thorough thermal analysis by means of TG and DTA. The thermal decomposition products obtained by calcination of these precursors at various temperatures (150–500°) for 5 h were investigated by infrared and X-ray techniques. The results obtained allowed a thorough physicochemical characterization of the intermediate steps and products throughout the thermal decomposition.     

Preparation and thermal stability of trioxalatocobaltates of bivalent metals KM2+ [Co(C2O4)3]·xH2O

Trioxalatocobaltates of bivalent metals KM²⁺[Co(C₂O₄)₃]·x H₂O, with M²⁺ = Ba, Sr, Ca and Pb, have been prepared, characterized and their thermal behaviour studied. The compounds decompose to yield potassium carbonate, bivalent metal carbonate or oxide and cobalt oxide as final products. The formation of the final products of decomposition is influenced by the surrounding atmosphere. Bivalent metal cobaltites of the types KM²⁺CoO₃ and M²⁺CoO_3—x are not identified among the final products of decomposition. The study brings out the importance of the decomposition mode of the precursor in producing the desired end products.     

The pyrolysis of ethane in the presence of nitric oxide

The kinetics of the ethane pyrolysis have been studied at temperatures from 550 to 596°C and with 0 to 62% of added nitric oxide. The rates of production of various products were studied by gas chromatography; ethylene, hydrogen, methane, nitrogen, water, nitrous oxide and acetonitrile were found as primary products, with hydrogen cyanide, carbon monoxide, acetaldehyde, n-butane, 1-butene, cis- and trans-2-butene and 1,3-butadiene as secondary products. For all the primary products the orders with respect to C₂H₆and NO were determined, as were the activation energies at two different percentages of NO (15.7 and 45.5%). Nitric oxide was found to be rapidly consumed with a finite initial rate, and the rate of production of H₂O was close to that of C₂H₄ at higher nitric oxide pressures. A mechanism is proposed which gives good agreement with all of the observed results. Its main features are: (1) Initiation takes place mainly by the unimolecular dissociation of ethane; there is no evidence for or against the process NO + C₂H₆ → HNO + C₂H₅; (2) NO scavenges ethyl radicals to form acetaldoxime which decomposes, and in this way the breakdown of C₂H₅ is hastened; (3) termination takes place mainly by the unimolecular decomposition of acetaldoxime to give inactive products. Some of the relevant rate parameters are evaluated. Reactions are proposed to account for the formation of the secondary products observed.     

Direct identification of reactive routes and measurement of rate constants in the reactions of oxygen atoms with methanethiol,ethanethiol, and methylsulfide

The room temperature reactions between oxygen atoms and methanethiol, ethanethiol, and methylsulfide have been studied in crossed jets to directly detect and identify the free-radical and stable products they produce. Knowledge of the products was used to assign reactive routes. The overall rate constants for all three O-atom reactions were also measured at 300 ± 2°K using a fast-flow reactor. They are 1.9 (CH₃SH), 2.8 (C₂H₅SH), and 63 (CH₃SCH₃) × 10^?12cm³/mol · sec. The identity of the detected products and the trend in rate constants in these reactions support an electrophilic addition mechanism followed by decomposition of the excited adduct by S-R bond cleavage (R = H, CH₃, or C₂H₅).     

A Facile Asymmetric Approach to the Multicyclic Core Structure of Mangicol A

Chiral propargylic ether‐based triene–ynes are synthesized with high enantiomeric purity by employing an asymmetric enyne addition to aldehydes catalyzed by 1,1′‐bi‐2‐naphthol in combination with ZnEt₂, Ti(OiPr)₄ and dicyclohexylamine at room temperature. These substrates are found to undergo a one‐pot domino Pauson–Khand and Diels–Alder cycloaddition catalyzed by [RhCl(CO)₂]₂ under CO to generate a series of multicyclic products with high chemoselectivity and stereoselectivity. These products contain the multicyclic core structure of mangicol A which could facilitate the synthesis and study of this class of natural products.     

Products of Reaction of NH with NO

The products of reaction of NO with breakdown products of NH₃ in an H₂/N₂/O₂ flame at 1500 K were investigated by mass spectrometric analysis of the hot gases. It is concluded that the major process involving NO and NH is NO + NH → N₂ + O + H and that not more than 10% of reactive collisions between these species lead to N₂O + H.     

Oxidative nucleophilic substitution of hydrogen in nitroarenes with phenylacetic acid derivatives

Oxidative nucleophilic substitution of hydrogen (ONSH) in nitroarenes with carbanion of isopropyl phenyl acetate gives various products depending on the conditions and oxidant. The reaction carried out in liquid ammonia and KMnO₄ oxidant gives iso-propyl α-hydroxy-α-nitroarylphenylacetates formed via hydroxylation of the initial ONSH products. In some cases additionally dimeric, trimeric and tetrameric products are formed. In THF and Bu₄N⁺MnO₄⁻ or DDQ oxidants simple ONSH products are formed whereas oxidation by dimethyl dioxirane (DMD) gave iso-propyl hydroxyaryl phenyl acetates. The dimeric and trimeric products are apparently formed via coupling of nitrobenzylic radicals generated in course of oxidation with nitrobenzylic carbanions of the ONSH products.     

A thermoanalytical study of the interaction of vanadiumoxide(V) with calcium oxide and calcium carbonate

The interaction of V₂O₅ with calcium oxide and calcium carbonate was studied by thermal analysis. The results indicated that the macrosuccession of the phase transformations in the systems CaO-V₂O₅ and CaCO₃-V₂O₅ corresponds to an increasing calcium content in each successively formed calcium vanadate. Thermodynamical calculations carried out by methods available in the literature for determining the primary products and the succession of the subsequently formed products demonstrate that chemical reactions proceeding in the above systems are controlled by kinetic and not by thermodynamic factors.