Validation of a thermal decomposition mechanism of formaldehyde by detection of CH2O and HCO behind shock waves

The thermal decomposition of formaldehyde was investigated behind shock waves at temperatures between 1675 and 2080 K. Quantitative concentration time profiles of formaldehyde and formyl radicals were measured by means of sensitive 174 nm VUV absorption (CH₂O) and 614 nm FM spectroscopy (HCO), respectively. The rate constant of the radical forming channel (1a), CH₂O + M → HCO + H + M, of the unimolecular decomposition of formaldehyde in argon was measured at temperatures from 1675 to 2080 K at an average total pressure of 1.2 bar, k_1a = 5.0 × 10¹⁵ exp(‐308 kJ mol^?1/RT) cm³ mol^?1 s^?1. The pressure dependence, the rate of the competing molecular channel (1b), CH₂O + M → H₂ + CO + M, and the branching fraction β = k_1a/(kA_1a + k_1b) was characterized by a two‐channel RRKM/master equation analysis. With channel (1b) being the main channel at low pressures, the branching fraction was found to switch from channel (1b) to channel (1a) at moderate pressures of 1–50 bar. Taking advantage of the results of two preceding publications, a decomposition mechanism with six reactions is recommended, which was validated by measured formyl radical profiles and numerous literature experimental observations. The mechanism is capable of a reliable prediction of almost all formaldehyde pyrolysis literature data, including CH₂O, CO, and H atom measurements at temperatures of 1200–3200 K, with mixtures of 7 ppm to 5% formaldehyde, and pressures up to 15 bar. Some evidence was found for a self‐reaction of two CH₂O molecules. At high initial CH₂O mole fractions the reverse of reaction (6), CH₂OH + HCO ? CH₂O + CH₂O becomes noticeable. The rate of the forward reaction was roughly measured to be k₆ = 1.5 × 10¹³ cm³ mol^?1 s^?1. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 157–169 2004     

Indirect boundary element method for unsteady linearized flow over prolate and oblate spheroids and hemispheroidal protuberances

The indirect boundary element method was used to study the hydrodynamics of oscillatory viscous flow over prolate and oblate spheroids, and over hemispheroidal bodies hinged to a plate. Analytic techniques, such as spheroidal coordinates, method of images, and series representations, were used to make the numerical methods more efficient. A novel method for computing the hydrodynamic torque was used, since for oscillatory flow the torque cannot be computed directly from the weightings. Instead, a Green's function for torque was derived to compute the torque indirectly from the weightings. For full spheroids, the method was checked by comparing the results to exact solutions at low and high frequencies, and to results computed using the singularity method. For hemispheroids hinged to a plate, the method for low frequencies was checked by comparing the results to previous results, and to exact solutions at high frequencies. Copyright © 2004 John Wiley & Sons, Ltd.     

Electron Metal-Dielectric Phase Transitions in Semiconductors under Pressure

The effect of uniform pressure on the character of metal-dielectric transitions in compensated weakly- and highly doped semiconductors (WHDCS) is considered. The influence of hybridization of resonance quasilocalized impurity states with band continuum states on the transition is shown. Minimum metallic conductivities in p-CdSnAs₂ are determined for Mott and Anderson transitions. Special features of the metal-dielectric transformation in weakly-doped narrow- and high energy-gap semiconductors are discussed for the case of hydrogen-like impurities. Anderson localization in WHDCS is also considered. Phase diagrams are presented.     

Alternating copolymerization of carbon dioxide and epoxide by manganese porphyrin: The first example of polycarbonate synthesis from 1-atm carbon dioxide

The first successful example of the formation of polycarbonate from 1-atm carbon dioxide and epoxide was demonstrated by the alternating copolymerization of carbon dioxide and epoxide with manganese porphyrin as a catalyst. The copolymerization of carbon dioxide and cyclohexene oxide with (porphinato)manganese acetate proceeded under the 1-atm pressure of carbon dioxide to give a copolymer with an alternating sequence. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3549–3555, 2003     

Search for the emission of π<Superscript>0</Superscript> mesons from the neutron-induced fission of <Superscript>235</Superscript>U nuclei

A nuclear-reactor experiment on the search for the emission of neutral pions from the neutron-induced fission of ²³⁵U nuclei has been carried out. To this end, an experimental setup for searching for the emission of π⁰ mesons with high sensitivity to this process has been designed and produced. This setup consisted of two Cherenkov total-absorption spectrometers for the detection and measurements of the energy of two gamma-ray photons from π ⁰-meson decay. The spectrometers were placed at the exits of two coaxial horizontal experimental channels. To protect the detectors from low-energy β and γ rays and neutron fluxes, 3.5-m-long water filters were situated in the channels. To reject the cosmic background, large-area scintillation counters operating in the anticoincidence mode were placed over each spectrometer. The energy and time resolution of the spectrometers, as well as the efficiency of detecting charged particles by scintillation counters, were tested on the secondary electron beam of the Tomsk electron synchrotron Sirius. Runs of measurements of the effect on the operating reactor (duration of 805 h) were alternated with runs of measurements of background on the stopped reactor (duration of 403 h). Statistical processing of the experimental results yields an upper limit of ≤5.3×10 ^?12 with a 90% confidence level for the probability of the emission of neutral pions from the neutron-induced fission of ²³⁵U nuclei. This result and results of other works carried out with sources of spontaneously fissioning ²⁵²Cf nuclei show that the probabilities of the emission of π⁰ mesons from spontaneous fission and fission induced by fission-spectrum neutrons are equal to each other.     

Uncertainty of the two-loop RG upper bound on the Higgs mass

A modified criterion of the SM perturbative consistency is proposed. It is based on the analytic properties of the two-loop SM running couplings. Under the criterion adopted, the Higgs mass up to 380 GeV might not give rise to strong coupling prior to the Planck scale. This means that the light Higgs boson is possibly preferred for reasons other than the SM perturbative consistency, i.e., for reasons beyond the SM.     

The calculation of neutron self-shielding factors of a group of isolated resonances

The resonance neutron self-shielding factor, G _res, is required in neutron metrology and activation data analysis. In a previous paper, the authors have shown that a dimensionless variable can be introduced which converts the dependence of G _res on the physical and nuclear properties of the material samples into an universal curve, valid for the isolated resonances of any nuclide. This work presents a methodology based on the universal curve, which enables to calculate G _res for a group of isolated resonances by weighting its individual contributions. A good agreement was reached with results calculated by the MCNP code and with experimental values for Mo foils and wires. This revised version was published online in July 2006 with corrections to the Cover Date.     

Role of water vapor and CO2 in the paleoclimatic fluctuations along northwestern and southern Syria, and the adjacent Mediterranean Sea

Microscopic petrified grains were collected from a mafic–ultramafic pipe, NE of Dreikeesh, NW Syria. The grains were identified as anthers/gynoecia in herb/grass flowers. Three of the grains showed evidence of magnetism, two slowly dissolved in concentrated HCl, and three microprobed grains showed a montmorillonitic composition. Iron originating from pyroxene was oxidized to magnetite. Released silica formed the mineral suite agate–chalcedony–opal. Warm/cold paleoclimatic fluctuations, occurring during late Pliocene–Holocene, depended on water vapor, CO₂ production, and cinders in the atmosphere. Most of these were associated with changing volcanic/tectonic events. Fluctuations were controlled by heat reflected from the Earth's surface being absorbed by water vapor and CO₂, which both re-reflected the heat back to the surface, thus, raising the temperature. This cycle was repeated several times during late Pliocene–Holocene.