Homogeneous and unimolecular gas‐phase thermal decomposition kinetics of methyl benzoylformate: experimental and theoretical study

The kinetics of the gas‐phase thermal decomposition of the α‐ketoester methyl benzoylformate was carried out in a static system with reaction vessel deactivated with allyl bromide, and in the presence of the free radical inhibitor propene. The rate coefficients were determined over the temperature range of 440–481 °C and pressures from 32 to 80 Torr. The reaction was found to be homogenous, unimolecular and obey a first‐order rate law. The products are methyl benzoate and CO. The temperature dependence of the rate coefficient gives the following Arrhenius parameters: log₁₀ k (s^?1) = 13.56 ± 0.31 and E_a (kJ mol^?1) = 232.6 ± 4.4. Theoretical calculations of the kinetic and thermodynamic parameters are in good agreement with the experimental values using PBE1PBE/6‐311++g(d,p). A theoretical Arrhenius plot was constructed at this level of theory, and the good agreement with the experimental Arrhenius plot suggests that this model of transition state may describe reasonably the elimination process. These results suggest a concerted non‐synchronous semi‐polar three‐membered cyclic transition state type of mechanism. The most advanced coordinate is the bond breaking C^δ+‐‐‐^δ‐OCH₃ with an evolution of 66.7%, implying this as the limiting factor of the elimination process. Copyright © 2014 John Wiley & Sons, Ltd.     

Experimental and theoretical study of the mechanism for the kinetic of elimination of methyl carbazate in the gas phase

The elimination kinetic of methyl carbazate in the gas phase was determined in a static system over the temperature range of 340–390 °C and pressure range of 47–118 Torr. The reaction is homogeneous, unimolecular, and obeys a first order rate law. The decomposition products are methyl amine, nitrous acid, and CO gas. The variation of the rate coefficients with temperatures is given by the Arrhenius expression: log k₁ (s^?1) = (11.56 ± 0.34) ? (180.7 ± 4.1) kJ mol^?1(2.303 RT)^?1. The estimated kinetics and thermodynamics parameters are in good agreement to the experimental values using B3LYP/6‐31G (d,p), and MP2/6‐31G (d,p) levels of theory. These calculations imply a molecular mechanism involving a concerted non‐synchronous quasi three‐membered ring cyclic transition state to give an unstable intermediate, 1,2‐oxaziridin‐3‐one. Bond order analysis and natural charges implies that polarization of O (alkyl)? C (alkyl) bond of the ester is rate determining in this reaction. Copyright © 2008 John Wiley & Sons, Ltd.     

Application of low intensity ultrasonics to cheese manufacturing processes

Ultrasound has been used to non-destructively assess the quality of many foods such as meat, fish, vegetables and dairy products. This paper addresses the applications of low intensity ultrasonics in the cheese manufacturing processes and highlights the areas where ultrasonics could be successfully implemented in the future. The decrease of ultrasonic attenuation during the renneting process can be used to determine the optimum cut time for cheese making. The ultrasonic velocity increases during maturation for those types of cheese that become harder during this manufacturing stage, thus being an indicator of the maturity degree. Moreover, ultrasonic measurements could be linked to sensory parameters. From the ultrasonic velocity measurements at two different temperatures, it is possible to assess cheese composition, thus allowing an improvement in the quality and uniformity of cheese commercialization. In addition, in pulse-echo mode it is possible to detect cracked pieces due to abnormal fermentations and also to assess the distance of the crack from the surface.     

Plasma property effects on spectral line broadening in double-pulse laser-induced breakdown spectroscopy

Double-pulse Laser-Induced Breakdown Spectroscopy (LIBS) in an orthogonal configuration was used to investigate plasma temperature and electron density effects on Mg II emission spectral line broadening. The experiments were carried out with two Nd:YAG lasers, one operating at 355 nm for ablation and the other one at 1064 nm for plasma reheating in air at atmospheric pressure. Temporally resolved plasma temperature and electron density were measured at various delay times. Data in this study show prolonged emission of Mg II (280.27 nm) as well as enhancement of the signal intensity when using double-pulse excitation compared to the single-pulse case. An enhancement of ～8× was attained with a delay between the laser pulses equal to 1 μs. The enhancement was accompanied by higher plasma temperature and increased electron density. The double-pulse LIBS configuration provides energy to sustain the plasma emission at a period in time when the linewidth is minimum, thereby improving the analytical capabilities of low spectral resolution instrumentation typically used in LIBS system.     

Minimal boundaries enclosing a given volume

We prove some facts concerning surfaces of minimal area bounding regions of prescribed volume in ⁿ. The main result we prove is that the mean curvature of such a surface is constant, if possibly a discontinuous function of the enclosed volume. The boundary behaviour of the solutions is also discussed.     

Self-Interactions of Strands and Sheets

Physical strands or sheets that can be modelled as curves or surfaces embedded in three dimensions are ubiquitous in nature, and are of fundamental importance in mathematics, physics, biology, and engineering. Often the physical interpretation dictates that self-avoidance should be enforced in the continuum model, i.e., finite energy configurations should not self-intersect. Current continuum models with self-avoidance frequently employ pairwise repulsive potentials, which are of necessity singular. Moreover the potentials do not have an intrinsic length scale appropriate for modelling the finite thickness of the physical systems. Here we develop a framework for modelling self-avoiding strands and sheets which avoids singularities, and which provides a way to introduce a thickness length scale. In our approach pairwise interaction potentials are replaced by many-body potentials involving three or more points, and the radii of certain associated circles or spheres. Self-interaction energies based on these many-body potentials can be used to describe the statistical mechanics of self-interacting strands and sheets of finite thickness.     

Acoustic Analysis of Pathological Voices Compressedwith MPEG System

The MPEG-1 Layer 3 compression schema of audio signal, commonly known as mp3, has caused a great impact in recent years as it has reached high compression rates while conserving a high sound quality. Music and speech samples compressed at high bitrates are perceptually indistinguishable from the original samples, but very little was known about how compression acoustically affects the voice signal. A previous work with normal voices showed a high fidelity at high-bitrate compressions both in voice parameters and the amplitude-frequency spectrum. In the present work, dysphonic voices were tested through two studies. In the first study, spectrograms, long-term average spectra (LTAS), and fast Fourier transform (FFT) spectra of compressed and original samples of running speech were compared. In the second study, intensities, formant frequencies, formant bandwidths, and a multidimensional set of voice parameters were tested in a set of sustained phonations. Results showed that compression at high bitrates (96 and 128 kbps) preserved the relevant acoustic properties of the pathological voices. With compressions at lower bitrates, fidelity decreases, introducing some important alterations. Results from both works, Gonzalez and Cervera and this paper, open up the possibility of using MPEG-compression at high bitrates to store or transmit high-quality speech recordings, without altering their acoustic properties.     

Leakage current study of Si1−xCx embedded source/drain junctions

This work investigates the impact of various processing parameters on the leakage current of in situ P-doped Si_1−xC_x embedded source/drain (S/D) junctions, i.e., the carbon content x (%) and the thermal budget used either before or after the selective epitaxial deposition. It is shown that while the area leakage current density, generated by defects in the depletion region is not affected by the epitaxial process or the strain in the substrate, the perimeter leakage current density (J_P) increases with x. From the stronger reverse bias dependence of J_P, it is derived that a higher electric field exists along the junction periphery. This is confirmed by capacitance-voltage (C-V) measurements, demonstrating a higher p-well B doping density for increasing x. It is believed that this originates from the strain dependence of the B diffusivity in the p-well region. No evidence of electrically active extended defect formation was found, so it is expected that the off-state current of embedded Si_1−xC_x S/D nMOSFETs will not be adversely affected by the selective epitaxial deposition.