An improved detailed chemical kinetic model for C3-C4 linear and iso-alcohols and their blends with gasoline at engine-relevant conditions

Propanol and butanol isomers have received significant research attention as promising fuel additives or neat biofuels. Robust chemical kinetic models are needed that can provide accurate and efficient predictions of combustion performance across a wide range of engine relevant conditions. This study seeks to improve the understanding of ignition and combustion behavior of pure C3-C4 linear and iso-alcohols, and their blends with gasoline at engine-relevant conditions. In this work, a kinetic model with improved thermochemistry and reaction kinetics was developed based on recent theoretical calculations of H-atom abstraction and peroxy radical reaction rates. Kinetic model validations are reported, and the current model reproduces the ignition delay times of the C3 and C4 alcohols well. Variations in reactivity over a wide range of temperatures and other operating conditions are also well predicted by the current model. Recent ignition delay time measurements from a rapid compression machine of neat iso-propanol and iso-butanol [Cheng et al., Proc. Combust Inst. (2020)] and blends with a research grade gasoline [Goldsborough et al., Proc. Combust Inst. (2020)] at elevated pressure (20–40 bar) and intermediate temperatures (780–950 K) were used to demonstrate the accuracy of the current kinetic model at conditions relevant to boosted spark-ignition engines. The effects of alcohol blending with gasoline on the autoignition behavior are discussed. The current model captures the suppression of reactivity in the low-temperature and negative-temperature-coefficient (NTC) region when either isopropanol and isobutanol are added to a research grade gasoline. Sensitivity and reaction flux analysis were performed to provide insights into the relevant fuel chemistry of the C3-C4 alcohols.     

Biradicaloid Character of Thiophene‐Based Heterophenoquinones: The Role of Electron–Phonon Coupling

The quinoidal versus biradicaloid character of the ground state of a series of thiophene‐based heterophenoquinones is investigated with quantum‐chemical calculations. The role of the ground‐state electronic character on molecular structure and vibrational properties is emphasized. The vibrational activities are experimentally determined and their analysis is performed by taking advantage of the definition of a collective vibrational coordinate (the

     

Particle-packed column versus silica-based monolithic column for liquid chromatography-electrospray-linear ion trap-tandem mass spectrometry multiallergen trace analysis in foods

A bicarbonate buffer-based extraction method for the simultaneous analysis of five nut allergens (Ana o 2, cashew-nut; Cor a 9, hazelnut; Pru 1, almond; Ara h3/4, peanut; Jug r 4, walnut) in cereals and biscuits using liquid chromatography-electrospray-linear ion trap-tandem mass spectrometry (LC-ESI-LIT-MS(2)) was developed and validated. The method was based on our earlier published LC-MS(2)-based method in a research frame aimed at the identification and determination of hidden allergens in foods by using selective biomarker peptides. A C18 particle-packed column and a silica-based C18 monolithic column were compared in terms of chromatographic performances, such as peak shape, resolution, analysis time and selectivity. The C18 particle-packed column exhibited better performances and was further used for method development and validation. By operating under MS(2) selected reaction monitoring (SRM) acquisition mode, linearity, limits of detection (LOD) and quantitation, trueness and precision were evaluated on breakfast samples enriched with a mix of the five nuts. Good linearity of the matrix matched-calibration curves was obtained and detection limit values generally varied from 14 to 55 mg nut/kg matrix. Recoveries were in the 76±4% to 94±3% range with RSD <15%. The capabilities of LIT to perform MS(n) fragmentation was exploited to improve selectivity of the analysis, and the LC-(SRM) MS(2) method was compared in terms of LOD, linearity, precision and accuracy with a LC-(SRM) MS(3) method. Finally, both the LC-MS(2) and LC-MS(3) methods were successfully applied to the analysis of nut traces in commercially available breakfast cereals and biscuits.     

Magnesium nanoparticles with transition metal decoration for hydrogen storage

We report on the hydrogen storage behaviour of Mg nanoparticles (NPs) (size range 100 nm–1 μm) with metal-oxide core–shell morphology synthesized by inert gas condensation and decorated by transition metal (TM) (Pd or Ti) clusters via in situ vacuum deposition. The structure and morphology of the as-prepared and hydrogenated NPs is studied by electron microscopy, X-ray diffraction including in situ experiments and X-ray absorption spectroscopy, in order to investigate the relationships with the hydrogen storage kinetics measured by the volumetric Sieverts method. With both Pd and Ti, the decoration deeply improves the hydrogen sorption properties: previously inert NPs exhibit complete hydrogenation with fast transformation kinetics, good stability and reversible gravimetric capacity that can attain 6 wt%. In the case of Pd-decoration, the occurrence of Mg–Pd alloying is observed at high temperatures and in dependence of the hydrogen pressure conditions. These structural transformations modify both the kinetics and thermodynamics of hydride formation, while Ti-decoration has an effect only on the kinetics. The experimental results are discussed in relation with key issues such as the amount of decoration, the heat of mixing between TM and Mg and the binding energy between TM and hydrogen.     

A new synthetic entry to 3-carboxamido-4-carboxylic acid derivatives of isoxazole and pyrazole

Ethyl 2-amino-3-methoxycarbonyl-4-oxo-2-pentenoate (3) reacts with hydroxylamine or hydrazines to give isoxazole and pyrazole ortho-dicarboxylic acid esters 4 and 5, respectively. Partial hydrolysis of diesters 4 and 5 afforded the corresponding dicarboxylic acid monoesters 6 and 7. Amidation of the intermediate acid chlorides 8,9 followed by hydrolysis of 4-methylesters 10, 11 gave the title compounds 1 and 2, respectively.     

A Model for Information Processing Capacity: Formalizing the Impact of Structural and Information System Choices on Organizational Performance

This paper proposes a formal model of information processing inorganizations. The model takes a process view of organizations and includesboth structural and IS features of processes. Two structural properties areconsidered, networking and parallelism. Information systems are representedin terms of quantity of information used and level of informationcustomization allowed. Process performance is measured in terms of totalinformation processing capacity and flexibility afforded by a process. Therelationship between structural and information system choices and processperformance is studied by simulating the model for a range of values. Thepaper derives a set of propositions describing the independent and combinedimpact of structural and information system choices on performance. The results suggest the predominance of networking over parallelism and ofinformation customization over information quantity in determininginformation processing capacity. They also show a negative effect ofnetworking on process flexibility and an amplifying effect of networking onthe benefits of information customization. Overall, the findings validatethe interdependence between structural and information system variables indetermining process performance.     

Partial and unsharp quantum logics

The total and the sharp character of orthodox quantum logic has been put in question in different contexts. This paper presents the basic ideas for a unified approach to partial and unsharp forms of quantum logic. We prove a completeness theorem for some partial logics based on orthoalgebras and orthomodular posets. We introduce the notion of unsharp orthoalgebra and of generalized MV algebra. The class of all effects of any Hilbert space gives rise to particular examples of these structures. Finally, we investigate the relationship between unsharp orthoalgebras, generalized MV algebras, and orthomodular lattices.