H2S-promoted thermal isomerization of cis-2-pentene to 1-pentene and trans-2-pentene around 800 K

H₂S accelerates the thermal isomerization of cis-2-pentene (P2c) to 1-pentene (P1) and trans-2-pentene (P2t) to around 800 K. This effect is interpreted on the basis of a free radical mechanism in which 2-pentenyl and thiyl radicals are the main chain carriers. P1 formation is essentially explained by the competing processes: P2t formation is due to addition-elimination processes: the importance of which has been evaluated against process (?4μ): The following ratios of rate constants have been measured and are discussed: (RT in cal mol^?1).     

Thermal isomerization of cis- or trans-2-butene. The unimolecular elimination of hydrogen from cis-2-butene around 500°C

An analytical and kinetic study of the thermal reaction of cis- or trans-2-butene has been performed in a static system over the temperature range of 480–550°C and at a low extent of reaction and initial pressures of 10–100 torr. The rate constant of the unimolecular cis–trans isomerization of cis-2-butene, determined under the conditions (2.3 RT in cal/mole) is in good agreement with previous measurements made at lower pressures. A comparison between the formation rates of hydrogen from the thermal reactions of cis- and trans-2 butene around 500°C leads to the rate constant value (2.3 RT in cal/mole) for the unimolecular 1,4? hydrogen elimination from cis? 2? butene.     

The thermal reaction of 2-pentene around 500°C at low extent of reaction

The thermal reaction of 2-pentene (cis or trans) has been performed in a static system over the temperature range of 470°–535°C at low extent of reaction and for initial pressures of 20–100 torr. The main products of decomposition are methane and 1,3-butadiene. Other minor primary products have been monitored: trans-2-pentene, trans- and cis-2-butenes, ethane, 1,3-pentadienes, 3-methyl-1-butene, propylene, 1-butene, hydrogen, ethylene, and 1-pentene. The initial orders of formation, 0.8–1.1 for most of the products and 1.5–1.8 for 1-pentene, increase with temperature. The formation of the products and the influence of temperature on their orders can be essentially explained by a free radical chain mechanism. But cis–trans or trans–cis isomerization and hydrogen elimination from cis-2-pentene certainly involve both molecular and free radical processes. The formation of 1-pentene mainly occurs from the abstraction of the hydrogen atom of 2-pentene by resonance stabilized free radicals (C₅H₉.).     

Polymerization of butene-2 with isomerization to butene-1

An attempt has been made to prepare a high molecular weight isotactic polybutene-1 from cis- or trans-butene-2. Polymerization of butene-2 did not occur due to the steric effect of the substituents. In the presence of TiCl₃–Al(C₂H₅)₃ catalyst, however, both butene-2 monomers were found to polymerize at a slower rate than butene-1 and to give polymers consisting of the repeating unit of butene-1. From the gas chromatographic determination of the isomer distribution of the butenes recovered after the polymerization, it was found that the butenes isomerized, in the presence of the catalyst system containing TiCl₃, to approach the thermodynamic equilibrium mixture of butene-1, cis-butene-2, and trans-butene-2. It was also found that the rates of polymerization of butene-2 for the catalyst systems used were proportional to the isomerization rates. These results show that butene-2 isomerizes first to butene-1 which has less steric hindrance and then polymerizes as butene-1, through ordinary vinyl polymerization by a coordinated anionic mechanism. This type of polymerization was observed in some other linear β-olefins such as n-pentene-2 and n-hexene-2.     

Thermal reaction of hydrogen–butene-2-cis mixtures at 500°C: Hydrogenation,hydrogenolysis, and thermal reaction of the olefin

The thermal reaction of hydrogen–butene-2-cis mixtures has been studied in a static system at low extent of reaction around 500°C. Hydrogen does not affect the thermal reaction itself of the olefin, but gives rise to new stoichiometries of hydrogenolysis and hydrogenation, which are specified: The reaction is described in terms of a molecular and free-radical mechanism. It is shown that the key process for the hydrogenolysis–hydrogenation reaction is (1) and that the rate constant of this process can be determined from either propylene, or methane, or butene-1 formations: with θ = 4.57 × 10^?3 T kcal/mol. Other rate constants are estimated and agree with literature data.     

Carbon nanofibers grown on sodalime glass at 500°C using thermal chemical vapor deposition

Carbon nanofibers are grown homogeneously on a large area of nickel-deposited sodalime glass substrate by thermal chemical vapor deposition of acetylene at 500°C. The diameters of carbon nanofibers are uniformly distributed in the range between 50 and 60 nm. Most of the carbon nanofibers are curved or bent in shape, but some fractions are twisted. They consist of defective graphitic sheets with a herringbone morphology. The maximum emission current density from the carbon nanofibers is 0.075 mA/cm² at 16 V/μm, which is sufficient for commercializing the carbon-nanofibers-based field emission displays.     

Pyrolysis of acetylene-vinylacetylene mixtures between 400 and 500°C

Acetylene and vinylacetylene mixtures were pyrolyzed at 400-500°C in the absence and presence of O₂ or NO. The major product of the interaction between C₂H₂ and C₄H₄ is polymer, but benzene is also produced. Both the C₂H₂ removal and C₆H₆ formation rates arefirst-order in C₂H₂ and C₄H₄. The rate coefficients are where R is the ideal gas constant in kJ/mol-K. Benzene formation occurs by two processes: a concerted molecular mechanism (?60%) and a singlet diradical mechanism (?40%).     

The thermal reactions of ethylene at 500°C in the presence and absence of small quantities of oxygen

Initial rates of formation of primary products have been measured in the pyrolysis of ethylene at 500°C, and a mechanism for the reaction is proposed based on the isomerization of the n?hexyl radical. Additions of oxygen in amounts less than 0.1% markedly increased the rate of formation of all products, but oxygen was not completely consumed in the reaction. It is shown that secondary initiation processes are important at very low conversions, and butene-1 is the most reactive product. Bimolecular reactions between olefins and with oxygen are important steps in the mechanism.     

Darstellung und Charakterisierung der Fulleren-Kokristallisate C60 · 12 C6H12, C70 · 12 C6H12, C60 · 12 CCl4, C60 · 2 CHBr3, C60 · 2 CHCl3, C60 · 2 H2CCl2

Synthesis and Characterization of the Fullerene Co-Crystals C₆₀ · 12 C₆H₁₂, C₇₀ · 12 C₆H₁₂, C₆₀ · 12 CCl₄, C₆₀ · 2CHBr₃, C₆₀ · 2CHCl₃, C₆₀ · 2H₂CCl₂ By crystallization of fullerenes from non-polar solvents (C₆H₁₂, CCl₄, CHBr₃, CHCl₃, H₂CCl₂) compounds of the following compositions were obtained: C₆₀ · 12C₆H₁₂, C₇₀ · 12C₆H₁₂, C₆₀ · 12CCl₄, C₆₀ · 2CHCl₃, C₆₀ · 2CHBr₃ and C₆₀ · 2H₂CCl₂. Lattice parameters have been determined by X-ray diffraction of powder samples; according to single-crystal examinations on C₆₀ · 12C₆H₁₂, C₆₀ · 12CCl₄ and C₆₀ · 2CHBr₃ the fullerene is orientationally disordered. C₆₀ · 12C₆H₁₂, cubic, a = 28.167(1) Å; C₇₀ · 12C₆H₁₂, cubic, a = 28.608(2) Å; C₆₀ · 12CCl₄, cubic, a = 27.42(1) Å; C₆₀ · 2CHBr₃, hexagonal, a = 10.212(1), c = 10.209(1) Å; C₆₀ · 2CHCl₃, hexagonal, a = 10.08(1), c = 10.11(2) Å; C₆₀ · 2H₂CCl₂, tetragonal, a = 16.400(1) Å, c = 11.645(7) Å.     

Über die Phasenbreite von V2O5 im Temperaturbereich von 450°C bis 620°C

About the Homogeneity Range of V₂O₅ in the Temperature Range of 450°C to 620°C The influence of the deposition temperature T₁ on the homogeneity range of V₂O₅-crystalls was investigated by using a solid electrolyte cell. The deviation x in V₂O_5–x from the stoichiometric composition was obtained with: x = 0.0066 at T₁ = 450°C up to x = 0.0326 at T₁ = 620°C.     

Crystallographic data for KNO2III at −35 °C and KNO2VII at −100°C

KNO₂ III below ?13°C is monoclinic, space group P2₁ or P2₁/m, with a₀, b₀, c₀ = 4.677, 9.650, 6.395 Å, β = 93.8° at ?35°C. There is a further phase transformation between ?35°C and ?100°C to a new phase KNO₂ VII, which is also monoclinic, space group P2₁ or P2₁/m: with a₀, b₀, c₀ = 8.397, 4.773, 7.644 Å, β = 112° at ?100°C. Both these phases appear to be ordered.     

Kinetics of thermal decomposition of CuSO4 · 5H2O to CuO

The effect of particle size, type of crucible, and heating rate on the thermal curves obtained simultaneously for CuSO₄ · 5H₂O were discussed. The dissociation steps were confirmed. Thermogravimetric techniques for determining the rate-controlling processes and kinetic parameters were applied for the dehydration steps and the calcination of CuSO₄ and CuSO₄ · CuO. For the dehydration of the monohydrate one mechanism operates but the activation energy and preexponential factor vary over wide ranges. Differentiating between various mechanisms using the same technique was sometimes difficult giving completely different values for the kinetic parameters. In view of such difficulties the various methods were assessed, the best techniques to treat similar results were recommended and the operating mechanisms and kinetic parameters for the various steps were thus established.     

Über die Alkaliselenoarsenate(III) KAsSe3 · H2O,RbAsSe3 · 1/2 H2O und CsAsSe3 · 1/2 H2O

On the Alkali Selenoarsenates(III) KAsSe₃ · H₂O, RbAsSe₃ · 1/2 H₂O, and CsAsSe₃ · 1/2 H₂O The alkali selenoarsenates(III) KAsSe₃ · H₂O, RbAsSe₃ · 1/2 H₂O, and CsAsSe₃ · 1/2 H₂O have been prepared by hydrothermal reaction of the respective alkali carbonate with As₂Se₃ at a temperature of 135°C. Their X-ray structural analyses demonstrated that the compounds contain polyselenoarsenate(III) anions (AsSe₃^?)_n, in wich the basic units are ψ-AsSe₃ tetrahedra, which are linked together through Se? Se bonds into infinite zweier single chains. The Rb and Cs salts are isotypic.     

Zur Struktur von zwei Hydraten des Natriumphenolats: C6H5ONa · H2O und C6H5ONa · 3 H2O

The Structures of two Hydrates of Sodium Phenoxide: C₆H₅ONa · H₂O and C₆H₅ONa · 3 H₂O In the monohydrate of sodium phenoxide sodium is coordinated by 4 oxygen atoms having an average distance Na? O of about 2.631 Å being arranged in form of a distorted tetrahedron. The oxygen atoms of water and phenoxid serve as bridging ligands. Hence, the structure can be considered as a network with a general formula [Na^[4]O]. Moreover, the oxygen atoms are linked via hydrogen bonding. In the trihydrate of sodium phenoxide sodium is surrounded with 5 oxygen atoms with an average distance of 2.39 Å forming a tetragonal pyramide. The oxygen of the phenoxide, however, does not participate in the coordination of the sodium ion. The coordination polyhedrons are connected by sharing edges and verteces. The resulting layer can be described by the general formula [Na^[5]O₂^[2]O^[2]O^[1]]. Via hydrogen bonding the phenoxide ions are attached to this layer.     

Wall effects in the pyrolysis of diethylether. A case of hetero-homogeneous pyrolysis at 500°C

The pyrolysis of diethylether has been studied at 500°C and 50 Torr initial pressure in packed vessels (surface-to-volume ratio 11 cm^?1). In untreated vessels the reaction appears to be essentially homogeneous as reported before. On the contrary, it is very sensitive to the walls of PbO-coated or NaOH-treated vessels. Thus most of the initial rates of product formation are increased in the PbO-coated vessel and decreased in the NaOH-treated vessel. The efficiency of the walls has been monitored for several weeks and was shown to decrease slowly with the vessel aging time. These phenomena are interpreted in terms of a free-radical chain mechanism in which a part of the initiation or termination steps occurs at the walls, the propagating steps being homogeneous. The present work clearly proves the existence of hetero-homogeneous chain reactions at 500°C. This new class of reaction could be of practical interest in the design of industrial reactors.     

Structures of decomposing and non-decomposing gas-phase [C4H6O]+· radical cations,and their [C2H2O]+· and [C3H6]+· product ions

The structures of gas-phase [C₄H₆O]^+· radical cations and their daughter ions of composition [C₂H₂O]^+· and [C₃H₆]^+· were investigated by using collisionally activated dissociation, metastable ion measurement, kinetic energy release and collisional ionization tandem mass spectrometric techniques. Electron ionization (70 eV) of ethoxyacetylene, methyl vinyl ketone, crotonaldehyde and 1-methoxyallene yields stable [C₄H₆O]^+· ions, whereas the cyclic C₄H₆O compounds undergo ring opening to stable distonic ions. The structures of [C₂H₃O]^+· ions produced by 70-eV ionization of several C₄H₆O compounds are identical with that of the ketene radical cation. The [C₃H₆]^+· ions generated from crotonaldehyde, methacrylaldehyde, and cyclopropanecarboxaldehyde have structures similar to that of the propene radical cations, whereas those ions generated from the remainder of the [C₄H₆O]^+· ions studied here produced a mixed population of cyclopropane and propene radical cations.     

Fluorenyl Zinc Phosphonate Zn(H2O)PO3–C13H9·H2O: Hybrid Columnar Structure with Strong C–H···π Interactions

A new zinc phosphonate Zn(H₂O)PO₃–C₁₃H₉ · H₂O with a columnar structure was synthesized in hydrothermal conditions. This compound crystallizes in space group P2₁/c [a = 15.832(4) Å, b = 5.1915(10) Å, c = 17.519(4) Å and β = 114.479(6)°]. Its inorganic framework consists of isolated chains of corner‐sharing ZnO₃(H₂O) and PO₃C tetrahedra. These chains are linked to fluorene cycles, forming hybrid columns, interconnected through C–H ··· π bonds. The photoluminescence properties of this hybrid material show that its emission bands are red shifted with respect to those of the mother phosphonic acid. This effect is explained on the basis of the structural constraints imposed by the inorganic Zn‐phosphonate chains.