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1.
İ. B. Özdemir 《Experiments in fluids》1997,22(4):271-280
This paper is concerned with an experimental investigation of the mixing inside the vortex ring formed by the gravity slumping
motion of a dense cloud in a less dense atmosphere. The dynamics of the spreading and instantaneous structures of the turbulent
flow were examined by visualization, single and multi-point measurements of velocity and concentration for two heavy gases,
carbondioxide (CO2) and dichlorodifluoromethane (CCl2F2), in a configuration in that heavy gas, initially trapped in a reservoir, was released with the rise of a shutter into calm
air of a sector-shaped dispersion channel.
Visualization of the cloud as a whole showed a spreading motion in which an advancing frontal structure was followed by a
stratified flow with a layer of dense fluid of higher velocities near the wall and, on top of it, a layer of dilute fluid
whose concentration is controlled by the mixing mechanisms within the head. During the course of spreading, there was always
a phase in which the head attained to a constant speed of advance, which occurred as 0.13 m/s for CO2 and 0.48 m/s for CCl2F2. It was interesting to observe for CO2 that the phase of constant speed took place in between two acceleration phases; the former was due to the initial slumping
of the cloud at the exit of the reservoir, and the latter was attributed to the collapse of the head on the transition to
the passive dispersion phase.
Instantaneous two-dimensional velocity field, measured with particle image velocimeter (PIV), showed that the cloud overran
the ambient air which caused the approaching dense fluid deflected away from the wall with significant vertical velocities
and downstream-moving separation, and the air trapped under the head resulted in the density inversion which introduced further
intricacy to the turbulent structure of the head. Instabilities at the upper free shear layer due to density and velocity
discontinuity rolled into periodic array of vortices which engulfed a considerable amount of air as they were convected backwards
over the head, but the incorporation of heavy and light fluids was completed with the appearance of microscales after the
collapse on the stratified layer. Analyses of the cloud head at different downstream locations also revealed that its size
remained unchanged when the speed of advance was constant, allowing the rate of change of the cloud volume being modeled with
the rate of spreading.
Contours of concentration obtained from digitized PIV pictures confirmed the kinematic features of the mixing revealed by
the velocity field and that the concentration values within the large structures were higher than those at the upper part
of the stratified layer. Motivated by the experimental observations, a semi-empirical analysis was presented to describe the
results and based on local values of the Richardson and Reynolds numbers.
Received: 4 October 1995 / Accepted: 4 July 1996 相似文献
2.
Thompson RS Guler LP Nelson ED Yu YQ Kenttämaa HI 《The Journal of organic chemistry》2002,67(15):5076-5084
The 1,3-dioxolane-2-phosphenium ion, 1,3-benzodioxole-2-phosphenium ion, and o-biphenylenephosphenium ion are reported to react in a stereoselective manner with cis- and trans-1,2-diaminocyclohexanes in the gas phase in a Fourier transform ion cyclotron resonance mass spectrometer. Elimination of NH3 from an addition product was observed only for the trans isomer. Several reaction mechanisms were experimentally and computationally examined (B3LYP/6-31G(d)//HF/6-31G(d) + ZPVE level of theory). The most plausible mechanism is initiated by addition of one of the amino groups to the electrophilic phosphorus atom followed by proton transfer between the amino groups. A change to a diaxial conformation for the trans isomer facilitates anchimeric assistance by the now nucleophilic phosphorus atom as the C-N bond breaks to release NH3. Intramolecular proton transfer competes with the conformational change and ultimately leads to ethylene glycol elimination. The transition states for the critical steps of these two reactions are calculated to be nearly equal in magnitude, which rationalizes the observation of both reactions for the trans-diamine. In contrast, the adduct of the cis isomer can eliminate NH3 via a concerted 1,2-hydride shift without a need for a conformational change. However, the barrier associated with this reaction was found to be substantially greater than for proton transfer between the N- and O-atoms. The latter reaction dominates and ultimately leads to ethylene glycol elimination. 相似文献
3.
Huang Y Guler L Heidbrink J Kenttämaa H 《Journal of the American Chemical Society》2005,127(11):3973-3978
Gas-phase reactivity of five differently substituted positively charged phenyl radicals was examined toward six amino acids by using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR). The reactivity of the radicals studied was determined by the electrophilicity of the radical, which can be characterized by the radical's electron affinity (EA). The larger the electron affinity of the radical, the higher the overall reaction rate. In addition to the expected H-atom abstraction, several unprecedented reaction pathways were observed, including NH2 abstraction, SH abstraction, and SCH3 abstraction. These reaction pathways dominate for the most electrophilic radicals, and they may not follow radical but rather nucleophilic addition-elimination mechanisms. Hydrogen abstraction from glycine was also investigated theoretically. The results indicate that hydrogen abstraction from alphaC of glycine is both kinetically and thermodynamically favored over the NH2 group. The ordering of transition state energies for hydrogen abstraction from the alphaC and NH2 groups was found to reflect the radicals' EA ordering. 相似文献
4.
4-Morpholinoacetophenone thiosemicarbazone, MAPT, and its nickel(Ⅱ) and copper(Ⅱ) complexes have been prepared and characterized by elemental analysis, magnetic susceptibility, spectral methods (FT-IR, ^1H NMR) and cyclic voltammetry. Electrochemical behaviors of the complexes have been studied by cyclic voltammetry in DMF media showing metal centered reduction processes for both of them. The redox properties, nature of the electrode processes and the stability of the complexes were discussed. [Cu(MAPT)2]Cl2 complex shows Cu(Ⅱ)/Cu(Ⅰ) couple and quasi-reversible wave associated with the Cu(Ⅲ)/Cu(Ⅱ) process. The reduction/oxidation potential values depend on the structures of complexes. Also, the antimicrobial activities of these complexes were determined against S. aureus, E. coli and B. subtilis. 相似文献
5.
Özlem Sarıöz Osman Serindaĝ Meysun İ. Abdullah 《Phosphorus, sulfur, and silicon and the related elements》2013,188(7):1785-1795
Functionalized bis(amino)phosphines of the type PhP(NHR)2 ( 1a–c ) and aminophosphines of the type Ph2PNHR ( 2a–c ) have been synthesized by treating PhPCl2 or Ph2PCl with corresponding primary amines of H2N-R where R = -CH2SO3H, -C6H4SO3H, and benzo-15-crown-5. The molybdenum(0) complex of the aminophosphine ( 3 ) has been obtained by reacting cis-[Mo(CO)4(bipy)] with aminophosphine ( 2c ). The synthesized aminophosphines, bis(amino)phosphines, and the molybdenum(0) complex have been characterized by IR, 1H NMR, 31P NMR, and MS spectroscopic techniques and by elemental analysis. 相似文献
6.
7.
Jing L Guler LP Nash JJ Kenttämaa HI 《Journal of the American Society for Mass Spectrometry》2004,15(6):913-919
An experimental method is described for obtaining quantitative selectivity information for H-atom abstraction by organic radicals from different sites of a substrate in the gas phase. The method is used to determine the selectivities of five different phenyl radicals toward the three different types of hydrogen atoms in ethanol. This experimental method involves studying the reactivities and selectivities of derivatives of the radicals that contain a chemically inert, charged group (distonic ions), which allows them to be manipulated in a Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer. 相似文献
8.
Abe K Abe K Adachi I Ahn BS Aihara H Akatsu M Alimonti G Aoki K Asai K Asai M Asano Y Aso T Aulchenko V Aushev T Bakich AM Banas E Behari S Behera PK Beiline D Bondar A Bozek A Browder TE Casey BC Chang P Chao Y Cheon BG Choi SK Choi Y Doi Y Dragic J Eidelman S Enari Y Enomoto R Everton CW Fang F Fujii H Fujita Y Fukunaga C Fukushima M Garmash A Gordon A Gotow K Guler H Guo R Haba J Haji T Hamasaki H Hanagaki K Handa F Hara K Hara T Hastings NC Hayashi K Hayashii H Hazumi M Heenan EM Higuchi I 《Physical review letters》2001,86(15):3228-3232
We report a determination of the B(0)(d)-&B_(0)(d) mixing parameter Deltam(d) based on the time evolution of dilepton yields in Upsilon(4S) decays. The measurement is based on a 5.9 fb(-1) data sample collected by the Belle detector at KEKB. The proper-time difference distributions for same-sign and opposite-sign dilepton events are simultaneously fitted to an expression containing Deltam(d) as a free parameter. Using both muons and electrons, we obtain Deltam(d) = 0.463+/-0.008 (stat)+/-0.016 (syst) ps(-1). This is the first determination of Deltam(d) from time evolution measurements at the Upsilon(4S). We also place limits on possible CPT violations. 相似文献
9.
Abe K Abe K Abe R Adachi I Ahn BS Aihara H Akatsu M Alimonti G Asai K Asai M Asano Y Aso T Aulchenko V Aushev T Bakich AM Banas E Behari S Behera PK Beiline D Bondar A Bozek A Browder TE Casey BC Chang P Chao Y Chen KF Cheon BG Chistov R Choi SK Choi Y Dong LY Dragic J Drutskoy A Eidelman S Eiges V Enari Y Enomoto R Everton CW Fang F Fujii H Fukunaga C Fukushima M Gabyshev N Garmash A Gershon TJ Gordon A Gotow K Guler H Guo R Haba J Hamasaki H Hanagaki K Handa F Hara K Hara T Hastings NC 《Physical review letters》2001,87(9):091802
We present a measurement of the standard model CP violation parameter sin2 phi(1) based on a 29.1 fb(-1) data sample collected at the Upsilon(4S) resonance with the Belle detector at the KEKB asymmetric-energy e(+)e(-) collider. One neutral B meson is fully reconstructed as a J/psi K(S), psi(2S)K(S), chi(c1)K(S), eta(c)K(S), J/psi K(L), or J/psi K(*0) decay and the flavor of the accompanying B meson is identified from its decay products. From the asymmetry in the distribution of the time intervals between the two B meson decay points, we determine sin2 phi(1) = 0.99+/-0.14(stat)+/-0.06(syst). We conclude that we have observed CP violation in the neutral B meson system. 相似文献
10.
Ozcan Kocyigit Ersin Guler 《Journal of inclusion phenomena and macrocyclic chemistry》2010,67(1-2):29-37
This article describes synthesis of novel Schiff base and its complexation properties with Fe(III) and Cr(III). Firstly 1,3,5-tris (formylphenoxymethyl)benzene (1, TRIPOD) with tris aldehyde groups were synthesized using the 1,3,5-trisbromomethylbenzene and 4-hydroxybezaldehyde. The compound 1 was converted to the Schiff base derivative (2, TCPIM-TRIPOD) with p-aminobenzoic acid. The prepared TCPIM-TRIPOD were reacted with four new trinuclear Fe(III) and Cr(III) complexes involving tetradenta Schiff bases N,N-bis(salicylidene)ethylenediamine-(salenH2) or bis(salicylidene)-o-phenylenediamine-(salophenH2) and characterized by means of elemental analysis carrying out infrared spectroscopy (IR), thermogravimetric analysis (TG), nuclear magnetic resonance (1H-NMR), elemental analysis and magnetic susceptibility measurement. The complexes can also be characterized as low-spin distorted octahedral Fe(III) and Cr(III) bridged by carboxylic acids. The tricarboxylic acids play a role as bridges for weak antiferromagnetic intramolecular exchange. 相似文献