Kinetics of Hydrogen Peroxide Decomposition in Guaiacol Solution, Catalyzed by Hexacyanoferrate(II)

The kinetics of hydrogen peroxide decomposition in a guaiacol solution, catalyzed by potassium hexacyanoferrate(II), were studied. The reaction mainly follows the pathway of guaiacol hydroxylation. The reaction order is 1 with respect to H₂O₂, 0.5 with respect to hexacyanoferrate, and from 0.4 to 0 with respect to guaiacol (the latter parameter decreases with increasing guaiacol concentration). The apparent activation energy is 105 kJ mol^{- 1}. A kinetic scheme of the process was proposed. An expression consistent with the experiment was obtained for the rate of hydrogen peroxide decomposition in the presence of guaiacol, catalyzed by hexacyanoferrate(II).     

Interference inspection of the aspherical components of an objective for nanolithography

Methods and schemes to inspect the EUV mirror shape are developed on the basis of a point diffraction interferometer with computer processing of interferograms. A measurement accuracy to within 0.001 of a wavelength in the visual range is achieved.     

Kinetics and mechanism of the formation of poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene] and poly(methyldecylsiloxane) by hydrosilylation

The kinetics of the formation of poly(carbosiloxane), as well as of alkyl-substituted poly(siloxane), by Karstedt's catalyst catalyzed hydrosilylation were investigated. Linear poly(carbosiloxane), poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene], (PTMDSE), was obtained by hydrosilylation of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while alkyl-substituted poly(siloxane), poly(methyldecylsiloxane), (PMDS), was synthesized by hydrosilylation of poly(methylhydrosiloxane) (PMHS) and 1-decene. To investigate the kinetics of PTMDSE formation, two series of experiments were performed at reaction temperatures ranging from 25 to 56 °C and with catalyst concentrations ranging from 7.0 × 10⁻⁶ to 3.1 × 10⁻⁵ mol Pt/mol CHCH₂. A series of experiments was performed at reaction temperatures ranging from 28 to 48 °C, with catalyst concentrations of 7.0 ×10⁻⁶ mol of Pt per mol of CHCH₂, when kinetics of PMDS formation was investigated. All reactions were carried out in bulk, with equimolar amounts of the reacting Si H and CHCH₂ groups. The course of the reactions was monitored by following the disappearance of the Si H bands using quantitative infrared spectroscopy. The results obtained showed typical first order kinetics for the PTMDSE formation, consistent with the proposed reaction mechanism. In the case of PMDS an induction period occurred at lower reaction temperatures, but disappeared at 44 °C and the rate of Si H conversion also started to follow the first-order kinetics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2246–2258, 2007     

Calculation of the Radiating Characteristics of a Thermodynamically Nonuniform Gas Medium

Passive methods of remote analysis of waste gases of industrial enterprises and aircrafts engines and gases ejected in eruptions of volcanos, in fires, and in other processes disturbing the atmosphere are now of limited utility because of the lack of well-developed mathematical techniques for solving the inverse problems of gas analysis. However, the advantage of these methods is obvious, since the equipment is limited to a receiving device and the gas medium serves as a radiator. At the same time, in modern techniques, the interpretation of measurements of emissivities of gases is performed using a phenomenological approach such that experimental data on radiation characteristics of various objects are approximated by simple polynomial relations whose coefficients are determined by minimization methods. This approach does not allow one to investigate the mechanism of the processes occurring in a radiating medium and gives no way of solving the inverse problem of monitoring the composition and thermodynamic parameters of a medium which disturbs the atmosphere by thermal effects. In elaborating theoretical methods of gas analysis, the elaboration of the direct problem of calculation of radiating characteristics of gases is of importance, since it is not clear how the emissivity of a gas medium depends on its thermodynamic parameters. This paper is devoted to the above problem. Here, the error is estimated that arises in modeling a nonuniform gas medium with an actual temperature distribution, which linearly depends on coordinate, by a uniform gas layer. It is shown that the difference between the radiation intensities calculated for uniform and nonuniform media can be significant in the practically important case where the recording device is in a zone of normal temperatures. This implies that the error of reconstruction of the spectroscopic and molecular parameters of gaseous compounds from high-temperature measurements of the radiating and absorbing characteristics should take into account the thermodynamic nonuniformity of the medium.     

Microstructural assessment of InN-on-GaN films grown by plasma-assisted MBE

The structural properties of InN thin films, grown by rf plasma-assisted molecular beam epitaxy on Ga-face GaN/Al₂O₃(0001) substrates, were investigated by means of conventional and high resolution electron microscopy. Our observations showed that a uniform InN film of total thickness up to 1 μm could be readily grown on GaN without any indication of columnar growth. A clear epitaxial orientation relationship of , was determined. The quality of the InN film was rather good, having threading dislocations as the dominant structural defect with a density in the range of 10⁹–10¹⁰ cm⁻². The crystal lattice parameters of wurtzite InN were estimated by electron diffraction analysis to be a=0.354 nm and c=0.569 nm, using Al₂O₃ as the reference crystal. Heteroepitaxial growth of InN on GaN was accomplished by the introduction of a network of three regularly spaced misfit dislocation arrays at the atomically flat interface plane. The experimentally measured distance of misfit dislocations was 2.72 nm. This is in good agreement with the theoretical value derived from the in-plane lattice mismatch of InN and GaN, which indicated that nearly full relaxation of the interfacial strain between the two crystal lattices was achieved.     

Molecular Complexes of Crown Ethers in Crystals and Solutions

A review of the experimental and theoretical studies of the crown ether complexes with polar molecules in their crystals, solutions, and in a gas phase is given. The type of the molecular bonds in the complexes, their stoichiometry, and the change in the macrocycle conformation during complex formation are considered, as well as the effect of the macrocycle structure and the nature of the medium on the efficiency of the molecular bonding. New data are given on the enthalpies of transfer of the crown ethers from tetrachloromethane into solvents capable of forming hydrogen bonds. The enthalpies of specific interactions of macrocycles with the molecules of the solvents in the medium of the same solvents are characterized. The conformations of the crown ethers in the media under study are discussed.     

A rapid and sensitive extractive spectrophotometric determination of copper(II) in pharmaceutical and environmental samples using benzildithiosemicarbazone.

Benzildithiosemicarbazone (BDTSC) is proposed as a sensitive and selective analytical reagent for the extractive spectrophotometric determination of copper(II). BDTSC reacts with copper(II) in the pH range 1.0-7.0 to form a yellowish complex. Beer's law is obeyed in the concentration range 0.5-0.4 microg cm(-3). The yellowish Cu(II)-BDTSC complex in chloroform shows a maximum absorbance at 380 nm, with molar absorptivity and Sandell's sensitivity values of 1.63 x 10(4) dm3 mol(-1) cm(-1) and 0.00389 microg cm(-2), respectively. A repetition of the method is checked by finding the relative standard deviation (RSD) (n = 10), which is 0.6%. The composition of the Cu(II)-BDTSC complex is established as 1:1 by slope analysis, molar ratio and Asmus' methods. An excellent linearity with a correlation coefficient value of 0.98 is obtained for the Cu(II)-BDTSC complex. The instability constant of the complex calculated from Edmond and Birnbaum's method is 7.70 x 10(-4) and that of Asmus' method is 7.66 x 10(-4), at room temperature. The method is successfully employed for the determination copper(II) in pharmaceutical and environmental samples. The reliability of the method is assured by analyzing the standard alloys (BCS 5g, 10g, 19e, 78, 32a, 207 and 179) and by inter-comparison of experimental values, using an atomic absorption spectrometer.     

Growth and study of single crystals of (Na,K)NbO<Subscript>3</Subscript> solid solutions

(Na, K)NbO₃ crystals with a perovskite structure and a KNbO₃ content up to 40 mol % were grown from flux with the use of the solvent NaBO₂. The dielectric measurements of the crystals grown revealed phase transitions that had never been observed before in ceramic samples.