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61.
Ivona R. Radović Mirjana Lj. KijevčaninEmila M. Djordjević Bojan D. DjordjevićSlobodan P. Šerbanović 《Fluid Phase Equilibria》2008
The densities of binary mixtures of (1-propanol, or 1-butanol, or 2-butanol, or 1-pentanol + chlorobenzene) have been measured at temperatures 288.15, 293.15, 298.15, 303.15, 308.15 and 313.15 K and atmospheric pressure while for the system (2-methyl-2-propanol + chlorobenzene) measurements were performed at the same pressure and temperatures 303.15, 308.15, 313.15, 318.15 and 323.15 K. All measurements were performed by means of an Anton Paar DMA 5000 digital vibrating-tube densimeter. Excess molar volumes VE were determined and fitted by the Redlich–Kister equation. It was observed that in all cases, VE increase with rising of temperature. The values of limiting excess partial molar volumes have been calculated, as well. The obtained results have been analysed in terms of specific molecular interactions present in these mixtures taking into consideration effect of the chain length of alcohols, degree of branching in the chain, relative position of the alkyl and OH group in an alcohol and the effect of temperature on them. In addition, the correlation of VE binary data was performed with the Peng–Robinson–Stryjek–Vera cubic equation of state (PRSV CEOS) coupled with the van der Waals (vdW1) and CEOS/GE mixing rule introduced by Twu, Coon, Bluck and Tilton (TCBT). Also, the possibility of cross prediction between VE and VLE by means of the NRTL parameters of GE model available in literature and those incorporated in the TCBT model was tested. 相似文献
62.
Kerry J. Adams Thomas D. McGrath Georgina M. Rosair Andrew S. Weller Alan J. Welch 《Journal of organometallic chemistry》1998,550(1-2)
Analysis of the structures of 8,8-(PPh3)2-8,7-nido-RhSB9H10 and 9,9-(PPh3)2-9,7,8-nido-RhC2B8H11 by RMS misfit calculations has confirmed that these rhodaheteroboranes possess nido 11-vertex cluster geometries in apparent contravention of Wade's rules. However, examination of the molecular structures of both species shows that the {RhP2} planes are inclined by ca. 66° with respect to the metal-bonded SB3 or CB3 faces, and that two weak ortho-CHRh agostic interactions occupy the vacant co-ordination position thereby created. As a consequence of these agostic bonds the Rh atom, and hence the overall cluster, is provided with an additional electron pair, meaning that their nido structures are now fully consistent with Wade's rules. The chelated diphosphine compound 8,8-(dppe)-8,7-nido-RhSB9H10 is similar to the PPh3 compound in showing the same agostic bonding. Attempts to prepare a bis-P(OMe)3 analogue result in ligand scavenging and the formation of 8,8,8-{P(OMe)3}3-8,7-nido-RhSB9H10. Similarly, reaction between Cs[6-arachno-SB9H12] and RhCl(dmpe)CO does not result in CO loss but in formation of 8,8-(dmpe)-8-(CO)-8,7-nido-RhSB9H10, shown to exist as a mixture of two of three possible rotamers. Deprotonation of 8,8-(PPh3)2-8,7-nido-RhSB9H10 and 8,8-(dppe)-8,7-nido-RhSB9H10 with MeLi yields the anions [1,1-(PPh3)2-1,2-closo-RhSB9H9]− and [1,1-dppe-1,2-closo-RhSB9H9]−, respectively, with octadecahedral cage structures. It is argued that anion formation causes the agostic bonding to be `switched-off' and results in the cluster adopting the closo architecture predicted by Wade's rules. This structural change is fully reversible on reprotonation, and if reprotonation of [1,1-(dppe)-1,2-closo-RhSB9H9]− is carried out in MeCN, the product 8,8-(dppe)-8-(MeCN)-8,7-nido-RhSB9H10 forms. Interestingly, 8,8-(dppe)-8-(MeCN)-8,7-nido-RhSB9H10 reconverts to 8,8-(dppe)-8,7-nido-RhSB9H10 on standing in CDCl3, suggesting that the agostic bonding is sufficiently strong to displace co-ordinated MeCN. All new compounds are fully characterised by multinuclear NMR spectroscopy and, in many cases, by single crystal X-ray diffraction. 相似文献
63.
用光电化学电流法研究了铅、铅砷、铅锑和铅铋合金在4.5mol·L-1H2SO4溶液(22℃)中,以0.9V(vs.Hg/Hg2SO4)极化7h而形成的阳极膜中的氧化铅的半导体性质,合金添加剂砷、锑和铋对t-PbO(四方氧化铝)和o-PbO(斜方氧化铝)的禁带宽度没有影响,从量子效率和电位的关系可求Pb,Pb-lat%As(at%表示原子百分比,全文同),Pb-lat%Sb和Sb-lat%Bi上膜中t-Pbo的施主密度(ND)分别为9.3×1015,1.0×1016,3.1×1016和1.3×1017cm-3,平带位分别为-0.20,-0.22,-0.28和-0.08V(vs.Hg/Hg2SO4).比较VA元素砷、锑和铋对上述膜中t-Pbo的ND(从而自由电子密度)和膜中t-Pbo的生长速率的影响,可认为法添加剂砷、锑和铋对阳极膜中t-Pbo的作用符合Hauffe规则. 相似文献
64.
The eigenfunctions and energies of general dilated Hamiltonians are expanded in powers of the dilatation parameter. These expansions, augmented by stationarity and stability conditions, are used to derive exact sum rules for bound and resonance states. Particular attention is paid to Hamiltonians with potentials which depend on external parameters, such as the nuclear coordinates in molecules, and to self-consistent potentials. The sum rules can be employed in practical computations to improve the quality of the results and may also serve in analyzing the results from approximate calculations. 相似文献
65.
Wilson A. Cañas-Marín Julián D. Ortiz-Arango Uriel E. Guerrero-Aconcha Claudia P. Soto-Tavera 《Fluid Phase Equilibria》2007
The ability of Soave–Redlich–Kwong cubic equation of state (SRK EoS) to predict densities and thermodynamic derivative properties such as thermal expansivity, isothermal compressibility, calorific capacity, and Joule–Thompson coefficients, for two gas condensates over a wide range of pressures (up to 110 MPa) was studied. The predictions of the EoS were compared to Monte Carlo simulation data obtained by Lagache et al. [M.H. Lagache, P. Ungerer, A. Boutin, Fluid Phase Equilibr. 220 (2004) 221]. Two completely different alpha functions for the SRK EoS attractive term were used and their respective effects on the predictions of such properties were analyzed. Also, two different forms of the crossed terms of the attractive parameter, aij, and three expressions of the crossed terms of the repulsive parameter, bij, were combined in different ways, and predictions were carried out. Little sensitivity of the properties on the chosen alpha function, except for the calorific capacities, was found in the systems studied. The most commonly used combination rules to model phase behavior of reservoir fluids, i.e. geometric and arithmetic forms of aij and bij, respectively, predicted very deficient results for these fluids at extreme conditions, specially for density calculations. 相似文献
66.
The knowledge of hydrocarbon/water phase equilibria is important in the design and operation of equipment for petroleum transport and refining and petrochemical plants. The presence of water in a hydrocarbon mixture can affect the product quality and damage the operation equipment due to corrosion and formation of gas hydrates. Tracing the concentration of hydrocarbons in aqueous media is also important for technical purposes like preventing oil spills and for ecological concerns such as predicting the fate of these organic pollutants in the environment. 相似文献
67.
Based on the world-line formalism with a sewing method, we derive the Yang-Mills effective action in a form useful to generate the Bern-Kosower-type master formulae for gluon scattering amplitudes at the two-loop level. It is shown that four-gluon (φ4 type sewing) contributions can be encapsulated in the action with three-gluon (φ3 type) vertices only, the total action thus becoming a simple expression. We then derive a general formula for a two-loop Euler-Heisenberg type action in a pseudo-abelian su(2) also studied. 相似文献
68.
69.
In this paper a sequential stopping rule is developed for the Multistart algorithm. A statistical model for the values of
the observed local maxima of an objective function is introduced in the framework of Bayesian non-parametric statistics. A
suitablea-priori distribution is proposed which is general enough and which leads to computationally manageable expressions for thea-posteriori distribution. Sequential stopping rules of thek-step look-ahead kind are then explicitly derived, and their numerical effectiveness compared. 相似文献
70.