Mechanism and Linear Free Energy Relationships in Michael‐Type Addition of 4‐Substituted Anilines to Activated Olefin in Acetonitrile

Kinetic studies for the Michael‐type reactions of ethyl‐3‐(4′‐N,N‐dimethylaminophenyl)‐2‐(nonafluorobutane)sulfonylpro‐penoate 1 with 4‐X‐substituted anilines 2a–e (X = OCH₃, CH₃, H, F, and Cl) have been investigated in acetonitrile at 20°C. A quadratic dependence of the pseudo–first‐order rate constants (k_obsd) versus [ 2a–e ] has been observed and has been interpreted in terms of a dimer nucleophile mechanism. The finding of a relatively large negative ρ value (?3.09) for the Hammett plot suggests that the intermediate ( I^± ) is highly zwitterionic in nature. A linear correlation (r² = 0.9989) between the Hammett's substituent constants σ and nucleophilicity parameters N of 4‐X‐substituted anilines in acetonitrile has been observed. The electrophilicity parameters E of the olefin 1 is evaluated, using the correlations σ versus N and log k versus σ and compared with the electrophilicities of analogously Michael acceptors.     

The effect of the B-site size on the structural,magnetic and electrical properties of La0.7Ca0.3MnO3−δ compounds

The perovskite-type ceramic La_0.7Ca_0.3MnO_3−δ was prepared by the solid-state reaction with 0.00?δ?0.15. X-ray diffraction, electrical and magnetic measurements were performed to examine the effect of the B-site size on the properties of these materials. We have found that the structure is orthorhombic for 0.00?δ?0.075 and becomes rhombohedral for 0.10?δ?0.15. The measurements of the magnetization as a function of the temperature, M(T), shows a ferromagnetic-paramagnetic transition at the Curie temperature T_C for δ=0.00. When increasing δ, these curves report the presence of two types of transitions. The first one is from the ferromagnetic to the antiferromagnetic state, indicating the existence of a charge-ordering state (T_CO). The second antiferromagnetic-paramagnetic transition occurs at the Neel temperature T_N. The temperature dependence of the resistivity ρ(T), indicates a metallic behaviour at low temperature (T<T_p) and a semiconductor behaviour at high temperature (T>T_p) for δ=0.00. For 0.05?δ?0.10, the ρ(T) curves shows a semiconductor behaviour revealing the disappearance of the metallic state which reappear at low temperature for δ=0.125 and 0.150.     

Structural and electrical characteristics of rare earth simple perovskite oxide La0.57Nd0.1Pb0.33Mn0.8Ti0.2O3

Polycrystalline La_0.57Nd_0.1Pb_0.33Mn_0.8Ti_0.2O₃ (LNPMT) is prepared by the solid-state reaction technique. The formation of single phase material was confirmed by X-ray diffraction studies, and it was found to be a rhombohedral phase at room temperature. The impedance plane plot shows semicircle arcs at different temperatures and an electrical equivalent circuit has been proposed to explain the impedance results. The frequency dependent conductivity spectra follow the universal power law. The activation energy deduced from analysis of the imaginary part of electric modulus and imaginary impedance is found to be ∼75 meV. Such a value of activation energy indicates that the conduction mechanism for the sample is due to electron hopping. The imaginary part of the electric modulus suggests that the relaxation describes the same mechanism at various temperatures.     

Structure and magnetic properties of potassium doped bismuth ferrite

The influence of the potassium (K⁺) doping on the structure of multiferroic BiFeO₃ and its relation with ferroelectric and magnetic properties was investigated for perovskites with composition Bi_1−xK_xFeO₃ in the range 0?x?0.07. All the studied samples are described in R3c space group (No. 161). Typical cell parameters (BiFeO₃) in hexagonal setting are a_hex=5.5769(2) Å and c_hex=13.8531(2) Å with Z=6 formula units. The structure determination shows that as the K⁺ content increases, the average cations displacements decrease reducing the polar character of doped samples with respect to pure BiFeO₃ and leading to a change from rhombohedral to a pseudo-cubic symmetry. A structural disorder is related to the substitution of K⁺, which results in strong diffuse scattering (DS) located at the bottom of the Bragg peaks. Magnetic measurements reveal that all the compounds remain antiferromagnetic at room temperature (RT) with almost no change in the transition temperature (Néel temperature T_N).     

Structural properties and electrical behaviour in the polycrystalline lanthanum-deficiency La1−x□xMnO3 manganites

Electrical conductance and X-ray diffraction (XRD) measurements of lanthanum-deficiency La_1−x□_xMnO₃ (x=0.05, 0.10 and 0.20) polycrystalline samples were performed to examine the effect of the internal pressure at B-site on the conduction mechanism. The structural study reveals that all samples crystallize in the rhombohedral system. The electronic conduction appears to be thermally activated at high temperature, which indicates the presence of semiconductor behaviour. The increase of the x content converts 3x Mn³⁺ to 3x Mn⁴⁺ ions with smaller ionic radius, which reduces the internal pressure and leads to the increase of the one-electron bandwidth W. This increase causes the appearance of metallic behaviour at low temperature for x=0.10 and 0.20 content.     

Effects of Anisotropy and Drying Air Parameters on Drying of Deformable Porous Media Hydro-Dynamically and Thermally Anisotropic

The purpose of this work was to investigate numerically the drying of saturated deformable porous media. The considered sample is a rectangular porous plate which assumed to be both hydro-dynamically and thermally anisotropic, while the mechanical behavior of the sample is supposed to be isotropic. All walls of the plate are subjected to a convective heat flux. Moreover, the top and bottom walls are allowed the mass transfer. The Darcy–Brinkman extended model was used as the momentum balance equation for the liquid and solid phases. The energy balance equation is based on the local thermodynamic equilibrium assumption between the both phases. The lattice Boltzmann method is used to solve the governing differential equation system. A comprehensive analysis of the effect of anisotropy and the drying air parameters on macroscopic fields is investigated throughout this work.     

Structural,magnetic and magnetocaloric properties of AMn1−xGaxO3 compounds with 0≤x≤0.2

Structural, magnetic and magnetocaloric properties of manganites series with the AMn_1−xGa_xO₃ (A=La_0.75Ca_0.08Sr_0.17 and x=0, 0.05, 0.1 and 0.2) composition have been investigated to shed light on Ga-doping influence. Solid-state reaction method was used for preparation. From XRD study, all samples are found single phase and crystallize in the orthorhombic structure with the Pnma space group. The variation of the magnetization M vs. temperature T, under an applied magnetic field of 0.05 T, reveals a ferromagnetic–paramagnetic transition for all samples. The experimental results indicate that T_C decreases from 336 to 135 K with increasing Ga substitution. Magnetocaloric effect (MCE) was estimated, in terms of isothermal magnetic entropy change (−ΔS_M), using the M(T, μ₀H) data and employing the thermodynamic Maxwell equation. The maximum entropy change and Relative Cooling Power (RCP) show non-monotonic behaviors with increasing the concentration of Gallium. In fact, the maximum value of ΔS_Mmaxof AMn_1−xGa_xO₃ for x=0.00 and 0.2 samples is found to be, respectively, 2.87 and 1.17 J/kg/K under an applied magnetic field change of 2 T. For the same applied magnetic field (μ₀H=2 T), the RCP values are found to vary between 97.58 and 89 J/kg.