Méthode de calcul des colonnes de distillation et d'extraction application de l'équation NRTL

The NRTL equation (non random two liquids) associated with an equation of state of the vapour phase reprensents the vapor—liquid and liquid—liquid equilibria.     

The remarkable difference between surface and step atoms in the magnetic anisotropy of two-dimensional nanostructures

The original magnetic properties of nanometre-sized particles are due to the distinct contributions of volume, surface and step atoms. To disentangle these contributions is an ongoing challenge of materials science. Here we introduce a method enabling the identification of the remarkably different contributions of surface and perimeter atoms to the magnetic anisotropy energy of two-dimensional nanostructures. Our method uses the generally nonlinear relationship between perimeter length and surface area. Atomic-scale characterization of the morphology of ensembles of polydisperse nanostructures, combined with in situ measurements of their temperature-dependent magnetic susceptibility, gives access to the role played by the differently coordinated atoms. We show for Co nanostructures on a Pt(111) surface that their uniaxial out-of-plane magnetization is entirely caused by edge atoms having 20 times more anisotropy energy than their bulk and surface counterparts. Identification of the role of perimeter and surface atoms opens up unprecedented opportunities for materials engineering. As an example, we separately tune magnetic hardness and moment in bimetallic core-shell nanostructures.     

Are biomarkers of chronic alcohol misuse useful in the assessment of DWI recidivism status?

A first driving while impaired by alcohol (DWI) conviction is a key opportunity to identify offenders who are at high risk for recidivism. Detection of alcohol use disorder (AUD) is a major target of current DWI assessments. However, offenders frequently underreport their alcohol consumption, and use of biomarkers has been proposed as a more objective indicator. Among the best established are aspartate aminotranferase (AST), alanine aminotransferase (ALT), gamma-glutamyl transferase (GGT), mean corpuscular red blood cell volume (MCV), carbohydrate-deficient transferrin (CDT), and thiamine. To our knowledge, no research has directly verified whether AUD biomarkers predict DWI recidivism status. Using a cross-sectional design, this study tested three hypotheses related to the utility of biomarkers in DWI assessment.

Hypotheses

(1) DWI recidivists possess biomarkers indicative of greater prevalence of AUD compared to first-time offenders; (2) multiple biomarkers better differentiate first-time offenders from recidivists compared to individual biomarkers; and (3) biomarkers add significantly to the prediction of recidivism over and above psychosocial questionnaires.

Methods

First-time offenders (n = 49) and recidivists (n = 95) participated in the study. In addition to self-reported information on sociodemographic and driving characteristics, data from several AUD questionnaires were gathered: Michigan Alcoholism Screening Test, Alcohol Use Disorders Identification Test, Composite International Diagnostic Interview, and Timeline Follow-Back. Blood samples were collected to measure AST, ALT, GGT, MCV, CDT, and thiamine.

Results

AUD biomarkers, taken individually or in combination, did not indicate that recidivists had more frequent AUD compared to first-time offenders. Also, they failed to significantly differentiate first-time offenders from recidivists or predict recidivism status. Finally, the superiority of biomarkers over psychosocial AUD questionnaires was not supported in the laboratory setting.

Conclusion

The present findings suggest that biomarkers of chronic patterns of heavy drinking may not be adequate to capture the multiple processes that appear to promote recidivism (e.g., binge drinking, other risky behavioural and personality features). Despite their objectivity, caution is warranted in the interpretation of a positive score on these biomarkers in DWI assessment. Longitudinal research is needed to more comprehensively explore the relationship between positive biomarkers in first-time offenders and their risk of becoming recidivists.     

High-throughput approach to the catalytic combustion of diesel soot II: Screening of oxide-based catalysts

Following the development of a high-throughput (HT) methodology for the evaluation of diesel soot oxidation catalysts in a 16 parallel channels reactor, a library of over 60 catalysts was tested under optimized conditions. The catalyst compositions were chosen to include solids which specific properties like oxygen storage capacity, oxygen mobility and ionic conductivity. The key parameters for high activity appear related to the presence of active and mobile surface oxygen species, and to an appropriate catalyst particle size in order to favour the number of contacts with the soot. In contrast, high oxygen storage capacity and bulk oxygen ion mobility do not appear as relevant properties for high catalytic activity. Nine new formulations were found to perform better than the reference catalyst “high surface area (HSA) ceria” (Rhodia).     

Concomitant use of liquid–liquid batch and continuous plug flow reactors for kinetic model discrimination. Application to the Rh/TPPTS catalysed reduction of the C–C double bond in dimethylitaconate

The biphasic catalytic reduction of the C–C double bond of dimethylitaconate with a water soluble rhodium/triphenylphosphinetrisulphonated sodium salt (TPPTS) complex is investigated. Kinetic studies in a well-mixed batch reactor provide kinetics parameters and an activation energy of 71 kJ mol⁻¹ but cannot discriminate between a first order or a complex kinetic model within the range of substrate concentration where the approximation of linear liquid/liquid partition is respected. Catalytic tests in the centrifugal partition chromatograph (CPC) reactor under steady-state operations in chemical regime and plug flow mode allow discriminating the kinetic models, the complex kinetic rate law being preferred.     

Modeling of the Low-Frequency Noise in Thermal Lens Spectrometry

The low-frequency noise observed in thermal lens spectrometry (TLS) can be modeled by assuming that the heated region, constituted by the thermal lens gradient and associated convective stream, behaves as a weakly damped harmonic oscillator with a natural frequency, v_o, which is forced to move at an externally imposed pump frequency, v_p. Out-of-phase lower-frequency oscillations of the TLS signal can be produced both by transient events, such as the beginning of the TLS experiment and small changes in the pump beam stability, and by drift of boundary conditions, such as the temperature of the surroundings. A model is developed and checked using 1-(2-pyridylazo)-2-napthol (PAN) solutions in silicone oil. Consequences of analytical interest are drawn; e.g., the signal-to-noise ratio of the TLS experiments is improved by pumping at the resonance frequency, where v_p = v_o.     

Immiscible Blends of PC and PET,Current Knowledge and New Results: Rheological Properties

This paper deals with immiscible blends of poly(ethylene terephthalate) obtained by melt blending with polycarbonate. A large survey of the current knowledge in the field of these blends is presented. Resolved and unresolved issues concerning the effect of exchange reactions on the miscibility of the components are addressed. The experimental part of the paper focuses on the rheological behavior of PET/PC blends. Blends containing various polymer ratios were obtained by melt blending with and without transesterification catalysts. Oscillatory shear flow in the melt was used to characterize the rheology of the various samples. A plot of the oscillatory data, similar to the Van Gurp Palmen plot, is used to point out the broadening of the co‐continuity window when in situ compatibilization takes place.

     

Infrared study of nitrogen monoxide adsorption on palladium ion-exchanged ZSM-5 catalysts

The adsorption of NO at room temperature on a H-ZSM-5 catalyst exchanged with Pd(NH₃) ₄ ²⁺ complex and activated in oxygen at 773 K has been examined by FTIR spectroscopy. After the oxidizing treatment, the Pd tetrammine complex decomposed into Pd(II) ions and/or Pd(II) hydroxyl complexes dispersed in the zeolite channels. The subsequent adsorption of NO at room temperature led to the reduction of Pd(II) to Pd(I) entities, resulting in the formation and adsorption of NO₂ on H-ZSM-5. The Pd(I) entities were shown to adsorb NO and form mononitrosyl complexes dispersed in the zeolite porosity and characterized by a single infrared absorption band at 1881 cm^–1. The Pd(I) mononitrosyl complex was shown to reversibly coordinate water and NO₂ molecules. The resulting nitrosyl complex was characterized by a single NO vibration band at 1836 cm^–1.     

Effect of Water on α‐Methylstyrene Hydrogenation on Pd/Al2O3

α‐methylstyrene catalytic hydrogenation on Pd/Al₂O₃ is frequently used to characterize new reactors. However, whereas many authors report some problems of reproducibility or possible poisoning of the catalyst, no consistent advice is available in the literature to carry out the reaction without these problems. This work points out the inhibition of the reaction by trace amounts of water. An experimental procedure is explained to guarantee the reproducibility of the measures.