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991.
We have shown the Lennard-Jones (LJ) phase diagram for a slit-shaped nanopore by molecular simulations and thermodynamically
predicted the results with no adjustable parameter. With this success, LJ phase diagrams are predictable. In this study, the
freezing of an LJ CH4 capillary condensate under a tensile condition in a nonstructural carbon nanopore with a cylindrical geometry was examined
using molecular dynamics (MD) simulation. We employ a unit cell in contact with a bulk vapor phase, which is useful for the
determination of the bulk vapor pressure in equilibrium with the molecules in a pore. The MD simulation results show liquid-solid
(amorphous) phase transitions with a variation in the bulk vapor pressure. The frozen particles are arranged in concentric
circular regions along the wall similar to those reported by Maddox and Gubbins. The freezing points are determined from the
variations in density, enthalpy, arrangement, and structural functions. The obtained liquid-solid coexistence points are found
to exhibit a significant dependence of the freezing point on the equilibrium bulk vapor pressure, forming an extraordinarily
skewed curve on the p-T diagram, in contrast to the bulk phase coexistence that is represented by an almost vertical line.
The origin of the significant dependence is considered to be the Laplace effect on the capillary condensate similar to the
case with a slit-shaped pore. A simple model, which the authors earlier presented for slit-shaped nanopores, successfully
predicted the p-T relation of the freezing point for cylindrical nanopores as well. 相似文献
992.
Comparison of equilibrium and nonequilibrium models of a CSTR with total condenser focused on the multiple steady states and
dynamic behaviour was carried out. The steady-state behaviour of the model system, MTBE synthesis from methanol and isobutene
in a reactive distillation column, was studied in terms of the input parameters, i. e. feed flow rate of methanol or butenes, reflux ratio, and mass of catalyst. The dynamic behaviour of the system during the
start-up was investigated and perturbations of manipulated variables were found to cause transitions between the parallel
steady states.
Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May
2006. 相似文献
993.
John A. Pojman Jason Willis Dionne Fortenberry Victor Ilyashenko Akhtar M. Khan 《Journal of polymer science. Part A, Polymer chemistry》1995,33(4):643-652
Several properties of propagating fronts of addition polymerization were studied. A power function could be fit to the velocity dependence on initiator concentration, but not with the exponents predicted by current models or in agreement with other published work. Bubbles from the volatile by-products of initiator decomposition were found to affect the front velocity and curvature. The front velocity for triethylene glycol dimethacrylate polymerization was found to depend linearly on temperature over a moderate range. The conversion of methacrylic acid in fronts varied greatly with initiator type and concentration. Benzoyl peroxide produced much lower conversion than t-butyl peroxide, but fronts with tBPO propagated slower. A dual initiator system of BPO and tBPO produced rapidly propagating fronts with good conversion but the contribution of each initiator to the velocity was not additive. The possibility of chain branching was considered. The apparent molecular weight distributions were very broad, often trimodal, and found to depend on initiator type and concentration as well as the tube diameter. The temperature profiles were measured and found to be very sharp for BPO and broader for tBPO but both had front temperatures in excess of 200°C, indicating a high ceiling temperature. © 1995 John Wiley & Sons, Inc. 相似文献
994.
Summary The distribution equilibria of cationic compounds in reversed-phase chromatographic systems (ion-pair chromatography) have
been studied on the basis of their effect on a detectable mobile phase component. The solid phase was a polystyrene-divinylbenzene
copolymer and the detectable component, a quaternary ammonium ion, 1-methylpyridine. The solutes were mono- and divalent amines
and quaternary ammonium ions.
The cations can be retained by ion-pair adsorption and ion exchange. Expressions for the ion-pair retention of the solutes
and the mobile phase cation (system peak) have been developed assuming Langmuir distribution of ion pairs to a solid phase
with one kind of binding site. The validity of the expressions has been tested by evaluation of ion-pair distribution constants
using non-linear curve fitting techniques. Good agreement for the constants of common ion pairs was obtained from different
kinds of capacity ratio expressions.
Ion exchange retention can appear beside ion-pair retention, and it has been observed in the pH range 1.6–6.1. The effect
depends not only on cations in the mobile phase, but also on the nature of the buffering systems. 相似文献
995.
The viscoelastic photoelastic behaviour of networks of 2-hydroxyethyl methacrylate — dodecyl methacrylate (DMA) copolymers in the main transition and rubberlike region was investigated. With increasing DMA content, photoelastic functions are quickly shifted to lower temperatures or shorter times; a detailed course of the functions suggests heterogeneity of the copolymers. Due to the existence of long side chains, optical function of all samples change the sign from positive to negative with increasing temperature. While the temperature dependences of the moduli of copolymers can be described by the two-phase Takayanagi model, the temperature dependences of optical functions cannot be described by using this model. It has been found, however, that the tempeature and time dependences of photoelastic functions can be described semiquantitatively by a three-phase model with a hypothetical statistical copolymer as the third component. The high values of the volume fraction of the hypothetical statistical copolymer found for the individual samples, suggest a considerable miscibility and a strong influence of the interphase boundary on the photoelastic behaviour of the copolymers. 相似文献
996.
Werner Unterberger Bernd Jenewein Bernhard Kl?tzer Simon Penner Wolfgang Reichl Günther Rupprechter Di Wang Di Wang Robert Schl?gl Konrad Hayek 《Reaction Kinetics and Catalysis Letters》2006,87(2):215-234
Summary The effect of hydrogen reduction on the structure and catalytic properties of “thin film”and “inverse”model systems for supported
metal catalysts is discussed. Thin film model catalysts were obtained by epitaxial growth of Pt and Rh nanoparticles on NaCl(001),
which were coated with amorphous or crystalline supports of alumina, silica, titania, ceria and vanadia. Structural and morphological
changes upon hydrogen reduction between 473 and 973 K were examined by high resolution electron microscopy. Metal-oxide interaction
sets in at a specific reduction temperature and is characterized by an initial “wetting”stage, followed by alloy formation
at increasing temperature, in the order VOx< TiOx< SiO2< CeOx< Al2O3. “Inverse”model systems were prepared by deposition of oxides on a metal substrate, e.g. VOx/Rh and VOx/Pd. Reduction of inverse systems at elevated temperature induces subsurface alloy formation. In contrast to common bimetallic
surfaces, the stable subsurface alloys of V/Rh and V/Pd have a purely noble metal-terminated surface, with V positioned in
near-surface layers. The uniform composition of the metallic surface layer excludes catalytic ensemble effects in favor of
ligand effects. Activity and selectivity, e.g. for CO and CO2methanation and for partial oxidation of ethene, are mainly controlled by the temperature of annealing or reduction. Reduction
above 573 K turned out to be beneficial for the catalytic activity of the subsurface alloys, but not for the corresponding
thin film systems which tend to deactivate viaparticle encapsulation.</o:p> 相似文献
997.
Summary The influence of the isothermal temperature, program rate, initial temperature and flow rate on retention indices was studied. The methods of Kováts, Van Den Dool and Local Lagrange Interpolation are compared. Ten experimental measurements were carried out on a capillary column coated with OV-101 stationary phase. 相似文献
998.
Rosa Caballol Josep M. Ribó Francesc R. Trull Asunción Vallés 《Monatshefte für Chemie / Chemical Monthly》1987,118(8-9):993-1010
The applicability of the MINDO/3 method is evaluated for calculations on dipyrrolic partial structures of bile pigments. It is shown that this method cannot be used for an accurate conformational analysis. However, when applying the frontier orbital model for reactivity parameters, a good picture of the HOMO and the LUMO distribution can be obtained in this type of molecules.
Reaktivität von Pyrrolpigmenten, 9. Mitt. MINDO/3-Rechnungen von dipyrrolischen Partialmodellen von Gallenpigmenten
Zusammenfassung Es werden die Einsatzmöglichkeiten von MINDO/3 für den Fall dipyrrolischer Partialstrukturen der Gallenpigmente aufgezeigt. Die Methode ist für eine genaue Konformationsanalyse nicht geeignet. Unter Verwendung der Reaktionsparameter des Frontier-Orbital-Modells läßt sich jedoch ein gutes Bild der HOMO- und LUMO-Verteilung für diesen Verbindungstyp gewinnen.相似文献
999.
本文成功地运用了三跳动力学模型,通过相关函数和超精细分裂常数的关系, 推出了电子自旋共振波谱的线宽与基本线宽T_(2,0)~(-1)、溶液中各种异构体的超精细分裂常数、配体的交换寿命等之间的关系。求出了在290 K温度下(Ph_2C_2)Co(CO)[P(OEt)_3]_2的THF溶渡中P(OEt)_3配体的交换寿命是5.6×10~(-11)秒。 相似文献
1000.
Robert Vianello 《Tetrahedron letters》2005,46(21):3711-3713
It is shown by the B3LYP/6-311+G(2d,p)//B3LYP/6-31G(d) calculations that the hexacyano derivative of aza-acepentalene is an extremely powerful superacid both in the gas phase and in DMSO as evidenced by the ΔHacid = 255.1 kcal mol−1 and pKa (DMSO) = −26.5. Its synthesis is strongly recommended, in particular, since the related conjugate base hexachloro aza-acepentalenide anion was prepared recently. 相似文献