On the redox reactions between allyl radicals and NOx

NO_x mitigation is a central focus of combustion technologies with increasingly stringent emission regulations. NO_x can also enhance the autoignition of hydrocarbon fuels and can promote soot oxidation. The reaction between allyl radical (C₃H₅) and NO_x plays an important role in the oxidation kinetics of propene. In this work, we measured the absolute rate coefficients for the redox reaction between C₃H₅ and NO_x over the temperature range of 1000–1252 K and pressure range of 1.5–5.0 bar using a shock tube and UV laser absorption technique. We produced C₃H₅ by shock heating of C₃H₅I behind reflected shock waves. Using a Ti:Sapphire laser system with frequency quadrupling, we monitored the kinetics of C₃H₅ at 220 nm. Unlike low-temperature chemistry, the two target reactions, C₃H₅ + NO → products (R1) and C₃H₅ + NO₂ → products (R2), exhibited a strong positive temperature dependence for this radical-radical type reaction. However, these reactions did not show any pressure dependence over the pressure range of 1.5–5.0 bar, indicating that the measured rate coefficients are close to the high-pressure limit. The measured values of the rate coefficients resulted in the following Arrhenius expressions (in unit of cm³/molecule/s):$k_1\left({\mathrm{C}}_3{\mathrm{H}}_5+\text{NO}\right)=1.49\times {10}^{?10}\exp \left(?6083.6\frac{\mathrm{K}}{T}\right)\left(1017?1252K\right)$$k_2\left({\mathrm{C}}_3{\mathrm{H}}_5+\mathrm{N}{\mathrm{O}}_2\right)=1.71\times {10}^{?10}\exp \left(?3675.7\frac{\mathrm{K}}{T}\right)\left(1062?1250K\right)$To our knowledge, these are the first high-temperature measurements of allyl + NO_x reactions. The reported data will be highly useful in understanding the interaction of NO_x with resonantly stabilized radicals as well as the mutual sensitization effect of NO_x on hydrocarbon fuels.     

Raman spectra and structure of As40−xS60Ix glasses

The Raman spectra of bulk As_40?xS₆₀I_x glasses with 0?x?20 have been studied. The obtained spectra can be successfully explained assuming the structure of these glasses to be composed of As₂S_3.45 polymer network matrix with dissolved AsBr₃ and S₈ molecules.     

Optical absorption and fluorescence investigation of the precipitated phases of Eu2+ in KBr single crystals

Europium precipitation in monocrystalline KBR has been studied using optical absorption and photoluminescence techniques. The annealing of quenched samples at temperatures below 100°C produces the growth of an emission band peaking at 433 nm which appears to be related with the presence of Suzuki-type precipitates in the crystals. The aging at higher temperatures, however, produces the appearence in the emission spectrum of two other bands peaking at 427 and 459 nm. The data presented in this paper strongly suggest that the former band is associated with the stable dihalide phase EuBr₂ in the host KBr, while the latter is due to a metastable precipitate whose structure appears to be quite similar to that of europium bromide. Some of the characteristics of the second phase precipitates were obtained by measuring the crystal field splitting (10 Dq) of the 4f⁶5d configuration of the Eu²⁺ ions in each one of them.     

CNDO/S-CI calculation of Hubbard parameters for doubly charged TCNQ tetramer

Using the CNDO/S-CI method the energies of the low-lying singlets and triplets of a doubly charged tetramer of TCNQ in the eclipsed geometry were calculated. The exact solution of the nearest-neighbour-version of the EHH for the case of two electrons and four sites was found. Fitting the EHH energy levels on the CNDO/S-CI spectra, the Hubbard parameters were estimated:U ₀=2.50 eV,V ₁=0.71 eV, ¦t¦=0.32 eV. The effect of strong correlation of the unpaired electrons on the electronic distribution in the ground and optically excited states of the tetramer is discussed.Dedicated to Professor Miroslav Trlifaj on the occasion of his sixtieth birthday.     

Birefringence in YAlO3∶Ce between 2–5 eV

This contribution presents birefringence spectra for orthorhombic YAlO₃Ce single crystal in the region 2–5 eV. The spectra were measured by means of a reflection method of null ellipsometry and were compared with spectra of YAlO₃:Nd determined from values measured in the region of lower energies (1·1–2·2 eV). We have found that there are differences between the spectra of YAlO₃Nd and YAlO₃:Ce which are most pronounced in thea-axis direction.The author is most grateful to Ing. . Viovský CSc. for helpful discussions during the course of this work and to Monokrystaly Turnov for preparation of the samples.     

A comparison of the stochastic theory of the crystal growth and the Stefan problem

The stochastic theory of the crystal growth is compared with the solution of the Stefan problem in the case of Sn solidification. It is shown that the stochastic theory gives the same results as the solution of the Stefan problem if kinetic processes at the solidification front are very rapid.     

Energy independent number of clusters and multiplicity distribution at Collider and beyond

Multiplicity distributions up to the Collider energies could be described by various two-parameter compounded distributions having in common Poisson distributed number of clusters. Among them the logarithmic distribution for hadronization via decaying clusters leads to energyindependent number of clusters above the ISR energies, replacing the previous KNO-scaling.Dedicated to the 30th anniversary of the Joint Institute for Nuclear Research.     

Carbon monoxide and hydrogen chemisorption studies on small supported iron carbide particles

The influence of chemisorption of CO and H₂ has been studied on small iron carbide particles by Mössbauer spectroscopy. The line with is increased by 2–3 times upon evacuation and also the values of isomer shift and magnetic hyperfine field were increased in vacuum. The effect is attributed to the chemisorption induced uniformization of the magnetic exchange interaction among the particles.