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321.
Linear, steady, axisymmetric flow of a homogeneous fluid in a rigid, bounded, rotating, saturated porous medium is analyzed.
The fluid motions are driven by differential rotation of horizontal boundaries. The dynamics of the interior region and vertical
boundary layers are investigated as functions of the Ekman number E(=v/ΩL
2) and rotational Darcy 3 numberN(=kΩ/v) which measures the ratio between the Coriolis force and the Darcy frictional term. IfN≫E
−1/2, the permeability is sufficiently high and the flow dynamics are the same as those of the conventional free flow problem
with Stewartson'sE
1/3 andE
1/4 double layer structure. For values ofN≤E
−1/2 the effect of porous medium is felt by the flow; the Taylor-Proudman constraint is no longer valid. ForN≪E
−1/3 the porous medium strongly affects the flow; viscous side wall layer is absent to the lowest order and the fluid pumped by
the Ekman layer, returns through a region of thicknessO(N
−1). The intermediate rangeE
−1/3≪N≪E
−1/2 is characterized by double side wall layer structure: (1)E
1/3 layer to return the mass flux and (ii) (NE)1/2 layer to adjust the interior azimuthal velocity to that of the side wall. Spin-up problem is also discussed and it is shown
that the steady state is reached quickly in a time scaleO(N). 相似文献
322.
323.
Mixed chelate formation of indium with severalβ-diketones has been studied from benzene media. The extraction of indium by BFA and FFA has been carried out as a function of pH and concentration of the ligand to ascertain the nature of the complexes. The extraction of indium by a mixture ofβ-diketones,viz., BFA-BA, BFA-DBM, FFA-BA, FFA-DBM, FFA-BFA and DBM-BA has also been studied as a function of the solution parameters. The nature of the mixed complexes formed as well as their equilibrium constants, statistical and stabilisation constants have been evaluated. 相似文献
324.
A detailed kinetic study of the Mn(II)-catalyzed and -uncatalyzed oxidation of pinacol by bromate has been carried out in aqueous acetic acid media containing Hg(II) ions. The uncatalyzed reaction exhibits 1.5 order that is, 0.5 order in [pinacol] and 1.0 in [bromate]. A decrease in k1 by increasing [bromate] has been accounted for due to the formation of Br2O5, which is inactive toward reduction. Mn(II)-catalyzed oxidation follows first order in [oxidant], 0.5 order in [manganous ion], and variable order with respect to [pinacol]. At lower [pinacol] (0.005–0.025M) the order is 0.5, but at higher concentration (0.03–0.15M) it becomes negative (?1.0). These observations can be accounted for qualitatively by the formation of 1:1 and 1:2 Mn(II)–pinacol complexes of which only 1:1 is active toward bromate oxidation. At higher [pinacol] the ratio of 1:2 and 1:1 complexes reached 98.2. All reactions were accelerated with acidity, and the rate constant follows the h0 function. Participation of H2O in the rate-limiting step and a free-radical mechanism were proposed for the manganous-ion-catalyzed reaction, whereas for the uncatalyzed reaction this was not true. The effects of NaClO4, Na4P2O7, and the dielectric constant of the media are also in accordance with the proposed mechanism. 相似文献
325.
The Monte Carlo method has been applied to the study of surface segregation in a multi-layer, regular solution model of alloy surfaces. Three different alloy configurations have been investigated: semi-infinite slabs, thin films and small particles. The results show that the alloy component with the lowest surface energy tends to segregate to the first three or four surface atom layers and that segregation is greater in clustering alloys than in ordering alloys. Furthermore, segregation is more pronounced in low coordination surfaces, as evidenced by a comparison of {110} and {100}-oriented surfaces of fcc alloys. The degree of surface segregation in thin films and small particles (in the particle size range studied) tends to be smaller than in semi-infinite slabs, because of mass conservation constraints, and decreases with decreasing film thickness and particle size. The results obtained are contrasted with previous calculations and possible avenues for improving surface segregation models are discussed. 相似文献
326.
Color detection of bile acids in thin-layer chromatography 总被引:1,自引:0,他引:1
327.
Yumiko Suzuki Naoto Iwata Kohei Dobashi Ryo Takashima Sundaram Arulmozhiraja Erika Ishitsubo Naoya Matsuo Hiroaki Tokiwa 《Tetrahedron》2018,74(3):392-400
A combined experimental and computational study on the key intermediates of NHC-catalyzed acylation reaction, Breslow intermediates (BIs), has been conducted in order to achieve a direct nucleophilic alkanoylation of N-heterocycles. Various BI precursors are alternatively prepared and used in the reaction with 4-chloroquinazoline. The present study reveals that the intermediates having benzimidazole moiety serve as acylating agents for the introduction of straight-chain alkanoyl groups. Natural bond orbital analysis indicates that the reactivity of intermediates partly correlates to the occupancy of the πC-C bonds of the hydroxyl enamine moieties. The putative rate-determining step of the acylation reaction has been theoretically investigated. Several new 4-alkanoylquinazolines are synthesized using the BI precursors. 相似文献
328.
New photo-induced electron transfer (PET) probes OMOX and OBOX, carrying an additional binding site in the form of ‘oxadiazole nitrogen’ have been designed to evaluate binding interactions with biologically significant Li+, Na+, K+, Ca2+, Mg2+, and Zn2+ including environmentally toxic Ba2+ and Cd2+ using optical spectral techniques. While Li+, Na+, and K+ did not appreciably perturb either the absorption or emission spectra, Ba2+, Ca2+, Mg2+, Zn2+, and Cd2+ induced slight red shifts (2-8 nm) in the UV-visible spectra as well as pronounced chelation induced enhanced fluorescence (CHEF). Both OMOX and OBOX exhibited the highest CHEF in contact with the zinc ion, whereas Ba2+, Ca2+, Mg2+, and Cd2+ induced relatively less emission enhancements. OBOX, which is a poorer emitter (Φf=0.0062) than OMOX (Φf=0.015), showed highly promising 160-fold emission enhancement in the presence of Zn2+. Potential, therefore is available in OBOX to function as a selective luminescent ‘off-on’ sensor for Zn2+ in the presence of coordinatively competing Ba2+, Ca2+, Mg2+, and Cd2+ ions. 相似文献
329.
330.
Arulmozhiraja S Coote ML Kitahara Y Juhász M Fujii T 《The journal of physical chemistry. A》2011,115(19):4874-4881
An unknown species has been detected in the analysis of the products in a pyrolysis of polycarbonate using Li(+) ion-attachment mass spectrometry (IAMS). The mass spectra exhibited a Li(+) adduct peak at m/z 233 that was tentatively assigned to bisphenol A (BPA) biradical. Experimentally, this assignment was supported by the observation that the production rate increased under an inert nitrogen atmosphere. To further confirm the assignment, the stability of the BPA biradical to intramolecular rearrangement reactions as well as unimolecular decomposition has been analyzed via density functional theory calculations [B3LYP/6-311+G(3df,2p)]. The results show that the bisphenol A biradical is an open-shell biradical singlet that is stable to unimolecular decomposition. Although some of the proposed intramolecular rearrangement products have lower energies than those of the BPA diradical, these pathways have large reaction barriers and the kinetic lifetime of the radical is expected to be of the order of hours under the conditions of the experiment. The calculations also reveal that the bisphenol A diradical has large Li(+) affinities supporting the fact that these Li(+) complexes could be detected in the Li(+) ion attachment mass spectrometry. On the basis of these results the Li(+) adduct peak at m/z 233 detected in the pyrolysis of polycarbonate is assigned to the bisphenol A biradical. 相似文献