A New Model for Prediction of One Electron Reduction Potential of Nitroaryl Compounds

This paper introduces a simple model for prediction of one electron reduction potential [E(RNO₂/R ^? NO₂^–)] of various nitroaryl compounds. The new method uses energy difference between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) in gas phase at the B3LYP/6‐311++G** level (ΔE_HOMO‐LUMO) and some structural parameters. It was used for 35 nitroaryl compounds including nitrobenzenes, nitrofurans, 2‐nitroimidazoles, 4‐nitroimidazoles, 5‐ninuintidazoles, nitroazaindoles, nitroacridines, and miscellaneous nitroaryl compounds. The root mean square (rms) percent deviation and the average absolute error of predictions of E(RNO₂/R ^? NO₂^–) relative to experiment were decreased from 12.4 % and 0.42 V to 3.5 % and 0.11 V, respectively, upon consideration of several structural parameters. Increment of the value of ΔE_HOMO‐LUMO and inclusion of specific polar groups can increase thermodynamic stability of these compounds.     

Highly stable copper/carbon dot nanofluid

Copper/carbon dot nanohybrids (Cu/CD NHs) were prepared via a facile precipitation method through a disproportionation reaction. The surface characterization was performed by various techniques such as XRD, FTIR and TEM. Then, water-based nanofluids composed of Cu/CD NHs at 0.1 and 0.5 mass% were prepared, and their thermo-physical properties including thermal conductivity, viscosity, density and specific heat were evaluated at various temperatures. The water-based Cu/CD nanofluid demonstrated to be a potential heat transfer fluid with a high stability. It was found that the thermal conductivity can be enhanced by increasing the nanoparticle concentration and temperature. Almost 1.25-fold increase in thermal conductivity has been achieved by raising the temperature up to 50 °C and at the concentration of 0.5 mass%. The heat capacity was found to increase with increasing concentration. Moreover, by increasing temperature the density and viscosity of the as-prepared nanofluid decreased, whereas the heat capacity showed an increasing trend.     

Self-assembled diisocyanide monolayer films on gold and palladium

Self-assembled monolayers (SAMs) of the aromatic diisocyanides, 1,4-phenylenediisocyanide, 2,3,5,6-tetramethyl-1,4-phenylenediisocyanide, 4,4'-biphenyldiisocyanide, 3,3',5,5'-tetramethyl-4,4'-biphenyldiisocyanide, and 4,4' '-p-terphenyldiisocyanide, were prepared on gold and palladium surfaces. The SAMs were characterized by ellipsometry, polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS), and grazing-angle attenuated total reflectance infrared spectroscopy (GATR). Based on the position of the metal-coordinated isocyanide stretching band, the SAMs on gold were found to bind in the terminal (eta(1)) geometry, while the SAMs on palladium prefer a different geometry which is possibly a triply bridging (mu(3)-eta(1)) geometry. A side-reaction of the unbound isocyanide in the SAM was identified as oxidation to an isocyanate group.     

An organic‐inorganic heterogeneous catalyst based on Keplerate polyoxometalates for oxidation of dibenzothiophene derivatives with Hydrogen peroxide

An organic‐inorganic material (NH₄)₂(MimAM)₄₀[Mo₁₃₂O₃₇₂(CH₃COO)₃₀(H₂O)₇₂] have been synthesized by reacting [(NH₄)₄₂[Mo^VI₇₂ Mo^V₆₀O₃₇₂(CH₃COO)₃₀(H₂O)₇₂] with the ionic liquid 3‐Aminoethyl‐1‐methylimidazolium bromide. The catalyst showed remarkably a high catalytic performance in the oxidation of dibenzothiophene (DBT) derivatives with H₂O₂ 35% as a safe and green oxidant. The main parameters affecting the process including catalyst, acid additive, hydrogen peroxide amounts and temperature have been investigated in detail. Sulfur removal of DBT in n‐heptane reached to 98.3% yield at 40 °C using 2.5 mmol H₂O₂ and 100 mg of (NH₄)₂(MimAM)₄₀[Mo₁₃₂O₃₇₂(CH₃COO)₃₀(H₂O)₇₂] after 90 min. Under the optimal conditions, BT (benzothiophene), DBT (dibenzothiophene) and 4,6‐DMDBT (4,6‐dimethyl‐dibenzothiophene) achieved high desulfurization efficiency. Our results showed that the reactivity order of different model sulfur compounds are thiophene <4,6‐dimethyl dibenzothiophene< dibenzothiophene. The catalysts could be easily separated from the reaction solution by simple filtration and recycled for several times without loss of activity.     

Investigating wettability alteration due to asphaltene precipitation: Imprints in surface multifractal characteristics

In the present study, multifractality and its formalism were employed to investigate the surface characteristics of an asphaltene deposited heterogeneous solid surface. Wettability alteration of the solid surface was found to affect the multifractal characteristics of an asphaltene deposited heterogeneous surface. Multifractal spectra f(α) show that the more oil wet the surface, the wider the spectrum, and the higher the f_max. The notable distinction between the multifractal spectra associated with different surface wettabilities can be used as a new aspect of wettability alteration.     

ON AVOIDANCE ACTIVITIES IN FISHERY ENFORCEMENT MODELS

Compliance and enforcement in fisheries are important issues from an economic point of view since management measures are useless without a certain level of enforcement. These conclusions come from the well‐established theoretical literature on compliance and enforcement problems within fisheries and a common result is that, it is efficient to set fines as high as possible and monitoring as low as possible, when fines are costless and offenders are risk neutral. However, this result is sensitive to the assumption that fishermen cannot engage in avoidance activities, e.g., activities to reduce the likelihood of being detected when noncomplying. The paper presents a model of fisheries that allows the fishermen to engage in avoidance activities. The conclusions from the model are that, under certain circumstances, fines are costly transfers to society since they not only have a direct positive effect on the level of deterrence, but also an indirect negative effect in the form of increased avoidance activities to reduce the probability of detection. The paper contributes to the literature on avoidance activities by introducing the externality from the illegal behavior as an endogenous effect on other offenders. For an externality, that has an exogenous effect on other actors, Malik shows that fines are only costly transfers for conditional deterrence (when one actor is deterred while another actor is not). For fisheries, we show that fines are also costly transfers under no deterrence (when no agents are deterred).     

Mechanism and equilibrium modeling of Re and Mo adsorption on a gel type strong base anion resin

A static-batch technique was used to demonstrate the adsorption behavior of Re (VII) and Mo ions onto Dowex 21K at equilibrium in single and binary component systems. The single equilibrium adsorption data were modeled through a linear form of four widely used equilibrium isotherm equations. The results indicated that Freundlich and D-R models for Re, and Temkin and D–R isotherms for Mo fitted the obtained data satisfactorily. Binary adsorptions of Re and Mo ions onto Dowex 21K were also analyzed using Extended Langmuir, Modified Langmuir, Extended Freundlich and Langmuir–Freundlich models. The competitive Extended Freundlich model fitted the binary adsorption equilibrium data adequately. Studies on mutual interference effects of Mo ions on Re adsorption capacity indicated that the adsorption of perrhenate ions is always suppressed. In this perspective, the results from EDX studies confirmed the rhenium atom decrease in the simulated Re–Mo adsorption. However, under the studied conditions the affinity of the Dowex 21K for rhenium ions is marginally greater than that of molybdenum ions.     

Experimental examination of the cooling performance of a cylindrical microchannel heat sink with straight and sinusoidal fins and alumina nanofluid coolant

Journal of Thermal Analysis and Calorimetry - Miniaturization of the electronic devices and dissipation of the heat generated during the operations within such equipment are of the most important...     

Model development for deactivation of bisphenol-A adduct particles during crystallization under the influence of impurity

A deactivation mechanism was developed to present the influence of 4-tert-butylphenol as a sample impurity on the bisphenol-A (BPA) adduct particles during the crystallization process. 4-tert-butylphenol is an organic sample impurity generally present in the reaction mixture of the industrial production of BPA. Kinetic parameters of growth, nucleation, agglomeration, and deactivation were estimated using the technique of model fitting to experimental data. The population and mass balances were used to model the adductive crystallization of BPA.