Methyl formate oxidation: Speciation data,laminar burning velocities,ignition delay times,and a validated chemical kinetic model

The oxidation of methyl formate (CH₃OCHO) has been studied in three experimental environments over a range of applied combustion relevant conditions:

• 1. A variable‐pressure flow reactor has been used to quantify reactant, major intermediate and product species as a function of residence time at 3 atm and 0.5% fuel concentration for oxygen/fuel stoichiometries of 0.5, 1.0, and 1.5 at 900 K, and for pyrolysis at 975 K.
• 2. Shock tube ignition delays have been determined for CH₃OCHO/O₂/Ar mixtures at pressures of ≈ 2.7, 5.4, and 9.2 atm and temperatures of 1275–1935 K for mixture compositions of 0.5% fuel (at equivalence ratios of 1.0, 2.0, and 0.5) and 2.5% fuel (at an equivalence ratio of 1.0).
• 3. Laminar burning velocities of outwardly propagating spherical CH₃OCHO/air flames have been determined for stoichiometries ranging from 0.8–1.6, at atmospheric pressure using a pressure‐release‐type high‐pressure chamber.

A detailed chemical kinetic model has been constructed, validated against, and used to interpret these experimental data. The kinetic model shows that methyl formate oxidation proceeds through concerted elimination reactions, principally forming methanol and carbon monoxide as well as through bimolecular hydrogen abstraction reactions. The relative importance of elimination versus abstraction was found to depend on the particular environment. In general, methyl formate is consumed exclusively through molecular decomposition in shock tube environments, while at flow reactor and freely propagating premixed flame conditions, there is significant competition between hydrogen abstraction and concerted elimination channels. It is suspected that in diffusion flame configurations the elimination channels contribute more significantly than in premixed environments. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 527–549, 2010     

An unexpected ring contraction of two nitroaryl pro-drugs: conversion of N-(nitroaryl)-3-chloropiperidine derivatives into N-(nitroaryl)-2-chloromethylpyrrolidines

Treatment of the N-nitroaryl-3-hydroxypiperidine derivatives 12 and 13 with thionyl chloride afforded the corresponding N-aryl-2-chloromethylpyrrolidines 5 and 15 via a ring-contraction process involving an intermediate aziridinium ion.     

Effective learning hyper-heuristics for the course timetabling problem

Course timetabling is an important and recurring administrative activity in most educational institutions. This article combines a general modeling methodology with effective learning hyper-heuristics to solve this problem. The proposed hyper-heuristics are based on an iterated local search procedure that autonomously combines a set of move operators. Two types of learning for operator selection are contrasted: a static (offline) approach, with a clear distinction between training and execution phases; and a dynamic approach that learns on the fly. The resulting algorithms are tested over the set of real-world instances collected by the first and second International Timetabling competitions. The dynamic scheme statistically outperforms the static counterpart, and produces competitive results when compared to the state-of-the-art, even producing a new best-known solution. Importantly, our study illustrates that algorithms with increased autonomy and generality can outperform human designed problem-specific algorithms.     

Unified encoding for hyper-heuristics with application to bioinformatics

This paper introduces a new approach to applying hyper-heuristic algorithms to solve combinatorial problems with less effort, taking into account the modelling and algorithm construction process. We propose a unified encoding of a solution and a set of low level heuristics which are domain-independent and which change the solution itself. This approach enables us to address NP-hard problems and generate good approximate solutions in a reasonable time without a large amount of additional work required to tailor search methodologies for the problem in hand. In particular, we focused on solving DNA sequencing by hybrydization with errors, which is known to be strongly NP-hard. The approach was extensively tested by solving multiple instances of well-known combinatorial problems and compared with results generated by meta heuristics that have been tailored for specific problem domains.     

Where Forward-Looking and Backward-Looking Models Meet

The present paper begins by deriving an instantaneous formulation for the backward-looking (reinforcement based learning) satisfaction balance model of Gray and Tallman (1984). This model is then used to generate interactional data from four simulated agents in a network interaction experiment. Because this initial model does not generate stable interaction structures in the network experiment, it is altered step by step in the direction of a forward-looking (agent with goals) model that has been shown to generate such stable interaction structures. The purpose of the modifications are to learn what aspects of the forward-looking model are needed to evolve a stable interaction structure, and to learn how these aspects may be incorporated into a model that remains essentially reinforcement based.     

Redox behaviour of thermally activated platinum electrodes with particular reference to operation at elevated temperature

The present work is a continuation of an earlier investigation of the effect of severe thermal pretreatment on the redox properties of platinum electrodes in aqueous media. The most interesting observation was that raising the solution temperature to ca. 75 °C resulted in a dramatic anodic response in the positive sweep at ca. 0.25 V (RHE). Such behaviour was noted earlier at room temperature but only when the thermally pretreated sample was further activated by cathodic polarization. This transition at 0.25 V was partially reversed on the negative sweep, but the cathodic process involved was subject to severe inhibition. There is independent evidence for similar behaviour for gold in aqueous acid solution. The relevance of the present results to the operation of fuel cell anodes is outlined. Received: 2 December 1999 / Accepted: 24 February 2000     

Spectral conditioning and pseudospectral growth

Using the language of pseudospectra, we study the behavior of matrix eigenvalues under two scales of matrix perturbation. First, we relate Lidskii’s analysis of small perturbations to a recent result of Karow on the growth rate of pseudospectra. Then, considering larger perturbations, we follow recent work of Alam and Bora in characterizing the distance from a given matrix to the set of matrices with multiple eigenvalues in terms of the number of connected components of pseudospectra. J. V. Burke’s research was supported in part by National Science Foundation Grant DMS-0505712. A. S. Lewis’s research was supported in part by National Science Foundation Grant DMS-0504032. M. L. Overton’s research was supported in part by National Science Foundation Grant DMS-0412049.     

Determination of the ratior v =d v u v of the valence quark distributions in the proton from neutrino and antineutrino reactions on hydrogen and deuterium

Zeitschrift für Physik C Particles and Fields - A set of proton longitudinal polarized distributions, worked out under the assumption of small gluon polarization, is used to evaluate several...     

Self-injection length in La0.7Ca0.3MnO3-YBa2Cu3O7-δ ferromagnet-superconductor multilayer thin films

We have carried out extensive studies on the self-injection problem in barrierless heterojunctions between La_0.7Ca_0.3MnO₃ (LCMO) and YBa₂Cu₃O_7-δ (YBCO) thin films. The heterojunctions were formed in situ by sequentially growing LCMO and YBCO films on 〈100〉 LaAlO₃ (LAO) substrate using a pulsed laser deposition (PLD) system. YBCO micro-bridges with 64 μm width were patterned both on the LAO (control) and LCMO side of the substrate. Critical current, I _c, was measured at 77 K on both the control side as well as the LCMO side for different YBCO film thickness. It was observed that while the control side showed a J _c of ∼ 2 × 10⁶ A/cm², the LCMO side showed about half the value for the same thickness (1800 ?). The difference in J _c indicates that a certain thickness of YBCO has become ‘effectively’ normal due to self-injection. From the measurement of J _c at two different thicknesses (1800 ? and 1500 ?) of YBCO films both on the LAO as well as the LCMO side, the value of self-injection length (at 77 K) was estimated to be ∼ 900 ?. To the authors’ best knowledge, this is the first time that self-injection length has been quantified. A control experiment carried out with LaNiO₃ deposited by PLD on YBCO did not show any evidence of self-injection.