On the rate constants of OH + HO2 and HO2 + HO2: A comprehensive study of H2O2 thermal decomposition using multi-species laser absorption

Hydrogen peroxide (H₂O₂) and hydroperoxy (HO₂) reactions present in the H₂O₂ thermal decomposition system are important in combustion kinetics. H₂O₂ thermal decomposition has been studied behind reflected shock waves using H₂O and OH diagnostics in previous studies (Hong et al. (2009) [9] and Hong et al. (2010) [6,8]) to determine the rate constants of two major reactions: H₂O₂ + M → 2OH + M (k₁) and OH + H₂O₂ → H₂O + HO₂ (k₂). With the addition of a third diagnostic for HO₂ at 227 nm, the H₂O₂ thermal decomposition system can be comprehensively characterized for the first time. Specifically, the rate constants of two remaining major reactions in the system, OH + HO₂ → H₂O + O₂ (k₃) and HO₂ + HO₂ → H₂O₂ + O₂ (k₄) can be determined with high-fidelity.No strong temperature dependency was found between 1072 and 1283 K for the rate constant of OH + HO₂ → H₂O + O₂, which can be expressed by the combination of two Arrhenius forms: k₃ = 7.0 × 10¹² exp(550/T) + 4.5 × 10¹⁴ exp(?5500/T) [cm³ mol^?1 s^?1]. The rate constants of reaction HO₂ + HO₂ → H₂O₂ + O₂ determined agree very well with those reported by Kappel et al. (2002) [5]; the recommendation therefore remains unchanged: k₄ = 1.0 × 10¹⁴ exp(?5556/T) + 1.9 × 10¹¹⁺exp(709/T) [cm³ mol^?1 s^?1]. All the tests were performed near 1.7 atm.     

Temperature derivatives of the bulk modulus of ZrB2 calculated by using the pressure derivative of the bulk modulus

The temperature dependence of the bulk modulus of ZrB₂ above room temperature was calculated by using the equations by Garai and Laugier (J. Appl. Phys. 101 (2007) p.023514) and Lawson and Ledbetter (Philos Mag. 91 (2011) p.1425). The present calculations involve the accurate data for pressure derivative of the bulk modulus for the Anderson–Grüneisen parameter in addition to the other experimental parameters involved. It is interesting to note that the cited equations derived by different thermodynamic approaches give almost equivalent values for the temperature dependencies of the bulk modulus of ZrB₂. The present results for the temperature derivatives of the bulk modulus of ZrB₂ vary from ?0.016?GPa/K at 300–400?K to ?0.022?GPa/K at 1500–1600?K, being in good agreements with the corresponding experimental values.     

Phase Transitions of Ruthenium-Doped Iron Oxide Studied by 57Fe Mössbauer Spectroscopy at Elevated Temperatures

Hyperfine Interactions - The 57Fe Mössbauer spectra recorded in situ from 5% ruthenium-doped maghemite show parameters typical for maghemite up to 600 K and a hyperfine field distribution...     

High temperature stability of maghemite in partially oxidized basalt lava

Mössbauer spectroscopy of basalt lava samples, exhibiting reversible thermal magnetization (J_S-T) curves with Curie temperatures of about 580°C, has revealed considerable amounts of maghemite (γ-Fe₂O₃) in many samples. In view of the expected instability, of maghemite at temperatures above 350°C, this reversibility is rather surprising. Here we report Mössbauer studies on heated lava samples, showing high content of maghemite. The samples were kept at 600°C in oxidizing, reducing, and inactive atmospheres, respectively, for different lengths of time, and then analyzed with Mössbauer spectroscopy at room temperature. The Mössbauer spectra showed that maghemite is stable in the oxidizing atmosphere for at least several hours. In the inactive atmosphere a considerable amount of maghemite still exists after two hours heating. In the reducing atmosphere maghemite had transformed to magnetite after only 30 minutes.     

Swirl effects on variable-density jet mixing in confined flows

An experimental investigation on swirl effects on inhomogeneous confined jet mixing in a combustor configuration is reported. The confined swirling flow was simulated by a swirler with a central jet mounted in a cyclindrical tube. Helium and air jets set at different velocities were injected into the confined swirling air flow. The resulting flow fields due to two vane swirlers with constant vane angles of 35° and 66° were compared. Results show that the 35° vane swirler produces a solid-body rotation core with a slope about twice that created by the 66° vane swirler. It is the behavior of this solid-body rotation core that determines jet mixing rather than the swirler vane angle. Consequently, the coaxial jet decays much faster, the mixing is more intense, and the turbulence intensities are higher for the 35° vane swirler. In view of these results, combustor designers should be more concerned with behavior of the solid-body rotation core produced by the swirler, instead of the swirler vane angle.     

Rates of redox reactions in basaltic melts determined by Mössbauer spectroscopy

Mössbauer spectroscopy has been widely used for determining the ferric/ferrous ratio in amorphous rock samples to reveal the oxygen pressure in the melt. In the present investigation, Mössbauer spectroscopy in conjunction with melting experiments at controlled oxygen pressures was used to determine the rates of redox reactions in basaltic melts at 1300°C. The samples were kept at a fixed oxygen pressure long enough to reach equilibrium at a well established ferric/ferrous ratio. Then, the oxygen fugacity in the furnace was changed abruptly and the samples were kept for different lengths of time, from 15 min, to 4 hrs, at the new condition. At the end of each run the samples were quenched and the ferric/ferrous ratio analyzed by Mössbauer spectroscopy. A geological corollary of our results is that natural volcanic glasses, representing quenched melts, retain and reflect the oxidation state in the melt immediately prior to eruption, and hence the oxygen fugacity in the magma.     

Experimental and molecular modeling investigation of (E)-N-{2-[(2-hydroxybenzylidene)amino]phenyl}benzenesulfonamide

The Schiff base compound (E)-N-{2-[(2-hydroxybenzylidene)amino]phenyl}benzenesulfonamide has been synthesized and characterized by IR, NMR and Uv-vis spectroscopies, and single-crystal X-ray diffraction technique. In addition, quantum chemical calculations employing density functional theory (DFT) method with the 6–311++G(d,p) basis set were performed to study the molecular, spectroscopic and some electronic structure properties of the title compound, and the results were compared with the experimental findings. There exists a good correlation between experimental and theoretical data. Enol-imine/keto-amine tautomerization mechanism was investigated in the gas phase and in solution phase using the polarizable continuum model (PCM) approximation. The energetic and thermodynamic parameters of the enol-imine?→?keto-amine transfer process show that the single proton exchange is thermodynamically unfavored both in the gas phase and in solution phase. However, the reverse reaction seems to be feasible with a low barrier height and is supported by negative values in enthalpy and free energy changes both in the gas phase and in solution phase. The solvent effect is found to be sizable with increasing polarity of the solvents for the reverse reaction. The predicted nonlinear optical properties of the compound are found to be much greater than those of urea.     

A time-dependent Hartree-Fock study of the neon isoelectronic sequence

For a wide range of frequencies the time-dependent Hartree-Fock equations are solved numerically for atoms of the Ne isoelectronic sequence. From the solutions properties of each system are calculated, notably excitation energies and bound-bound oscillator strengths. Excellent agreement is observed between the TDHF oscillator strengths and the most accurate experimental and theoretical data which are currently available.     

Nuclear quantum effects in calculated NMR shieldings of benzene; a Feynman path integral study

The Feynman path integral Monte Carlo approach has been coupled to the gauge including atomic orbital formalism in order to analyse the absolute magnetic shieldings of the benzene nuclei under the conditions of thermal equilibrium. The Hamiltonian employed in the derivation of ensemble averaged NMR quantities is of the Hartree-Fock type. The basis set used is of 6–31G quality. The spatial delocalization of the atoms leads to a deshielding of both types of benzene nuclei relative to the shieldings experienced at the minimum of the potential energy surface. This deshielding has to be traced back to bond length elongations in thermal equilibrium. The influence of the nuclear fluctuations on the NMR parameters of benzene is quantum driven up to temperatures of 400 K; classical fluctuations are of minor importance in this low-temperature window.