Kinetics of benzonitrile nitration with mixed acid under homogeneous conditions

Chemical kinetics of benzonitrile nitration with mixed acid is investigated in the temperature range 283–299 K. Pseudo-first-order rate constants are evaluated by means of rate experiments on homogeneous reacting mixtures having large stoichiometric excesses of nitric acid. The second-order kinetic constants for nitronium ion attack to the aromatic substrate are derived on the basis of the assessed nitration mechanism. An activation energy of 604 ± 37 kJ mol^?1 is calculated for this reaction step. © 1993 John Wiley & Sons, Inc.     

Enhancement of the backscattered intensity from fractal aggregates

Comparative measurements were conducted for the backscattered intensities of light from uniform random and fractal aggregated media. Different features are found for the backscattered intensity peak shapes. A crossover between the θ^1-D and θ^-2 dependences of the backscattered intensity occurs in the case of fractal aggregated medium, where D indicates the fractal dimension.     

Magnetic resonance imaging: a new window into industrial processing.

Although the most important use of nuclear magnetic resonance imaging (MRI) continues to be for diagnostic medicine, recognition is being gained for many nonmedical applications. Examples include the following areas: petrogeology, food, agriculture, polymers and polymer-composites, and pharmaceuticals. These areas all involve studies of species that have short spin-spin relaxation times, and consequently need far fast gradient switching. These technical details are discussed and typical applications given.     

The epitaxial growth of gaas using alkylarsine: Part 2. molecular orbital calculation

Semi-empirical molecular orbital calculations were carried out for the compounds (C₂H₅)₃As, (C₂H₅)₃Ga and RAsH₂ (R = C₂H₅, i-C₃H₇, i-C₄H₉, and t-C₄H₉) by using the CNDO/2-U program, and their capability of β-elimination reaction is compared on the basis of the torsion energy to the transition state, electrostatic interactions and orbital overlapping between the central atom and the β-hydrogen, and bond order of the metal-carbon, and carbon-hydrogen bond. In the comparison of (C₂H₅)₃As with (C₂H₅)₃Ga, we found that the β-elimination of (C₂H₅)₃As could hardly be expected to take place in the thermal decomposition. The capability of β-elimination would be smaller in C₂H₅AsH₂ than that in (C₂H₅)₃As. Moreover when the ethyl group is replaced by a t-butyl group in RAsH₂, the β-elimination reaction appears to become more difficult and a large possibility for a radical process is suggested.     

THE USE OF THERMOELASTICITY TO EVALUATE STRESS REDISTRIBUTION AND NOTCH SENSITIVITY IN CERAMIC MATRIX COMPOSITES

Thermoelastic stress analysis was used to document the effect of composite damage on the stress distribution in three ceramic matrix composites. Composite damage was found to significantly alter the thermoelastic response of each material, with the greatest effect noted in SiC/CAS. Thermoelastic imaging of these materials affords a more complete picture of how the various damage mechanisms affect the stress distribution. In particular, a stress concentration factor computed from thermoelastic images, serves as an indicator of stress redistribution. The stress concentration factors were computed by comparing notch root to far field temperatures, and monitored after the introduction of various amounts of damage. In each material, the stress concentration factor diminished as the damaging load approached the ultimate stress. Reduction in the stress concentration is associated with local changes in modulus, mechanistically arising from combinations of fiber, matrix and interface fracture. Stress redistribution occurs as a consequence of modulus changes, leading to lower notch sensitivity in each of the tested composites.     

Shape transition from InAs quantum dash to quantum dot on InP(3 1 1)A

We report on the shape transition from InAs quantum dashes to quantum dots (QDs) on lattice-matched GaInAsP on InP(3 1 1)A substrates. InAs quantum dashes develop during chemical-beam epitaxy of 3.2 monolayers InAs, which transform into round InAs QDs by introducing a growth interruption without arsenic flux after InAs deposition. The shape transition is solely attributed to surface properties, i.e., increase of the surface energy and symmetry under arsenic deficient conditions. The round QD shape is maintained during subsequent GaInAsP overgrowth because the reversed shape transition from dot to dash is kinetically hindered by the decreased ad-atom diffusion under arsenic flux.     

Sympathetic cooling rate of gas-phase ions in a radio-frequency-quadrupole ion trap

We theoretically investigated the mass dependence of the sympathetic cooling rate of gas-phase ions trapped in a linear radio-frequency-quadrupole ion trap. Using an a priori molecular dynamical calculation, tracing numerically with Newtonian equations of motion, we found that ions with a mass greater than 0.54±0.04 times that of the laser-cooled ions are sympathetically cooled; otherwise, they are heated. To understand the mass dependence obtained using the molecular-dynamical calculation, we made a heat-exchange model of sympathetic cooling, which shows that the factor of 0.54±0.04 is a consequence of absence of micro-motion along the axis of the linear ion trap. Received: 10 December 2001 / Revised version: 28 January 2002 / Published online: 14 March 2002     

The application of the construction of Kolmogorov complexity and of a theorem by Maslov to semiotic systems

The results obtained in V. P. Maslov’s article [1] can automatically be carried over to arbitrary semiotic systems if the string of signs is sufficiently long. We shall show in this article, by using arguments based on the ideas of Kolmogorov complexity and by applying the theorem of V. P. Maslov from [2], that one can obtain similar formulas for the distribution of various semiotic objects. In order to do this, we must introduce notions generalizing the occurrence frequency of words in corpora of texts. We also interpret a formula due to Maslov (appearing in [3]) from the point of view of the general semiotic notions introduced here.     

A critical review of the chemical kinetics of SF4, SF5, and S2F10 in the gas phase

The gas phase chemical kinetics of SF₄, SF₅, and S₂F₁₀ are reviewed with particular emphasis on relevance to the general problem of the dielectric breakdown of SF₆. Specific reaction systems treated are SF₄ + F₂, SF₅ + SF₅, and the pyrolysis of S₂F₁₀. Computer modeling calculations were carried out to arrive at the best estimates of rate parameters. Based on the results of these calculations, sets of recommended rate parameters are provided. The major discrepancies and problems in establishing the kinetic data base are described. Thermochemical consequences of different model calculations are given.     

Fundamental aspects of initiated oxidation of tridecane and polyethylene in solutions

Specific features of the initiated oxidation of polyethylene and its low-molecular-weight analogue tridecane, associated with the occurrence of the process in the short-chain mode, were studied.