A solid state metathesis (SSM) reaction was investigated with respect to the formation of rare‐earth carbodiimides, the role of the co‐produced salt (LiCl), and the eutectic flux medium (LiCl/KCl). A SSM reaction is characterized by an exothermic reaction in which a salt (often LiCl) is coproduced. When the salt melts, it can serve as a useful medium for the crystallization of a desired product. An improved crystal growth can be observed by using an eutectic flux. However, the composition of an eutectic LiCl/KCl flux is altered when LiCl is produced during the reaction. The thermal effects concerning the endothermic melting of the flux and the exothermic ingnition of the SSM reaction may compensate each other, which is not necessarily a drawback for the reaction to proceed. 相似文献
YbSi2 and the derivatives YbTxSi2–x (T = Cr, Fe, Co) crystallizing in the α‐ThSi2 structure type were obtained as single crystals from reactions run in liquid indium. All silicides were investigated by single‐crystal X‐ray diffraction, I41/amd space group and the lattice constants are: a = 3.9868(6) Å and c = 13.541(3) Å for YbSi2, a = 4.0123(6) Å and c = 13.542(3) Å for YbCr0.27Si1.73, a = 4.0142(6) Å and c = 13.830(3) Å for YbCr0.71Si1.29, a = 4.0080(6) Å and c = 13.751(3) Å for YbFe0.34Si1.66, and a = 4.0036(6) Å, c = 13.707(3) Å for YbCo0.21Si1.79. YbSi2 and YbTxSi2–x compounds are polar intermetallics with three‐dimensional Si and M (T+Si) polyanion sub‐networks, respectively, filled with ytterbium atoms. The degree of substitution of transition metal at the silicon site is signficant and leads to changes in the average bond lengths and bond angles substantially. 相似文献
A permanent magnet assembly in which the flux density can be altered by a mechanical operation is often significantly smaller than comparable electromagnets and also requires no electrical power to operate. In this paper five permanent magnet designs in which the magnetic flux density can be altered are analyzed using numerical simulations, and compared based on the generated magnetic flux density in a sample volume and the amount of magnet material used. The designs are the concentric Halbach cylinder, the two half Halbach cylinders, the two linear Halbach arrays and the four and six rod mangle. The concentric Halbach cylinder design is found to be the best performing design, i.e. the design that provides the most magnetic flux density using the least amount of magnet material. A concentric Halbach cylinder has been constructed and the magnetic flux density, the homogeneity and the direction of the magnetic field are measured and compared with numerical simulation and a good agrement is found. 相似文献
The mechanism of isomerization of hydroxyacetone to 2-hydroxypropanal is studied within the framework of reaction force analysis at the M06-2X/6-311++G(d,p) level of theory. Three unique pathways are considered: (a) a step-wise mechanism that proceeds through the formation of the Z-isomer of their shared enediol intermediate, (b) a step-wise mechanism that forms the E-isomer of the enediol, and (c) a concerted pathway that bypasses the enediol intermediate. Energy calculations show that the concerted pathway has the lowest activation energy barrier at 45.7 kcal mol−1. The reaction force, chemical potential, and reaction electronic flux are calculated for each reaction to characterize electronic changes throughout the mechanism. The reaction force constant is calculated in order to investigate the synchronous/asynchronous nature of the concerted intramolecular proton transfers involved. Additional characterization of synchronicity is provided by calculating the bond fragility spectrum for each mechanism. 相似文献
Single crystals of three new strontium nitridogermanates(IV) were grown in sealed niobium ampules from sodium flux. Dark red Sr4[GeN4] crystallizes in space group P21/c with a = 9.7923(2) Å, b = 6.3990(1) Å, c = 11.6924(3) Å and β = 115.966(1)°. Black Sr8Ge2[GeN4] contains Ge4– anions coexisting with [GeIVN4]8– tetrahedra and adopts space group Cc with a = 10.1117(4) Å, b = 17.1073(7) Å, c = 10.0473(4) Å and β = 115.966(1)°. Black Sr17Ge6N14 features the same anions alongside trigonal planar [GeIVN3]5– units. It crystallizes in P1 with a = 7.5392(1) Å, b = 9.7502(2) Å, c = 11.6761(2) Å, α = 103.308(1)°, β = 94.651(1)° and γ = 110.248(1)°. 相似文献
Quantum chemical calculations were used to study the mechanism of Diels-Alder reactions involving chiral anthracenes as dienes and a series of dienophiles. The reaction force analysis was employed to obtain a detailed scrutiny of the reaction mechanisms, it has been found that thermodynamics and kinetics of the reactions are quite consistent: the lower the activation energy, the lower the reaction energy, thus following the Bell-Evans-Polanyi principle. It has been found that activation energies are mostly due to structural rearrangements that in most cases represented more than 70% of the activation energy. Electronic activity mostly due to changes in σ and π bonding were revealed by the reaction electronic flux (REF), this property helps identify whether changes on σ or π bonding drive the reaction. Additionally, new global indexes describing the behavior of the electronic activity were introduced and then used to classify the reactions in terms of the spontaneity of their electronic activity. Local natural bond order electronic population analysis was used to check consistency with global REF through the characterization of specific changes in the electronic density that might be responsible for the activity already detected by the REF. Results show that reactions involving acetoxy lactones are driven by spontaneous electronic activity coming from bond forming/strengthening processes; in the case of maleic anhydrides and maleimides it appears that both spontaneous and non-spontaneous electronic activity are quite active in driving the reactions. 相似文献
The purpose of this investigation is to theoretically shed some light on the effect of the unsteady electroosmotic flow (EOF) of an incompressible fractional second-grade fluid with low-dense mixtures of two spherical nanoparticles, copper, and titanium. The flow of the hybrid nanofluid takes place through a vertical micro-channel. A fractional Cattaneo model with heat conduction is considered. For the DC-operated micropump, the Lorentz force is responsible for the pressure difference through the microchannel. The Debye-Hükel approximation is utilized to linearize the charge density. The semi-analytical solutions for the velocity and heat equations are obtained with the Laplace and finite Fourier sine transforms and their numerical inverses. In addition to the analytical procedures, a numerical algorithm based on the finite difference method is introduced for the given domain. A comparison between the two solutions is presented. The variations of the velocity heat transfer against the enhancements in the pertinent parameters are thoroughly investigated graphically. It is noticed that the fractional-order parameter provides a crucial memory effect on the fluid and temperature fields. The present work has theoretical implications for biofluid-based microfluidic transport systems.
A square-shaped heat flux cloak and a square-shaped heat flux concentrator have been designed theoretically according to the invariance symmetry of steady state thermal conductive equation. The direction of heat flux in these devices can be modulated as desired. Using the method of coordinate transformation, the inhomogeneous and anisotropic thermal conductivity in the transformation region have been acquired. Two-dimensional finite element simulations were performed to confirm the theoretical results. 相似文献