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111.
在碱性介质中用分光光度法研究了二过碲酸合铜(Ⅲ)配离子(DTC)氧化乙二醇一乙醚(EGE)的反应动力学及机理。反应速率表明:反应对DTC为准一级,对EGE为分数级;在保持准一级条件([EGE]》[DTC])下,表观速率常数随着OH-浓度的增加而增大,随着TeO42-浓度的增加而减小;有负的盐效应。据此提出了包括配离子和EGE形成络合物的前期平衡的反应机理,由假设反应机理推出的速率方程能很好的解释全部实验现象,进一步求得速控步的速率常数和活化 相似文献
112.
Monir Uddin Antonis G. Hatzidimitriou Maria Lalia-Kantouri Chris Tsiamis 《Structural chemistry》1997,8(2):131-139
The infrared and electronic excitation spectra of a series of new nickel(II) chelates containing an-diimine (or nitrogenous base, enR) and the anion of a-dione (1,3-ketoenol or 1,3-ketoester,H) were obtained in the solid state and in solution. The composition and the overall structure of the new chelates in the solid state depends on ligand concentration, the substituents within the-dionato moiety and the counterion present. The IR and electronic excitation spectra of [Ni(enR)2
]NO3 and [Ni(enR)(O2NO)] indicate, in conjunction with other physicochemical measurements, bidentate coordination of the ligands, while the spectral shifts reveal replacement of the (O,O)nitrato group by basic solvents. The existence of the nickel(II) in an octahedral environment is confirmed by an X-ray structure analysis of [Ni(dpamH)2acac]NO3 · CH3OH (monoclinic, space groupP2l/n, a=17.296(1),b=7.462(1),c=21.604(3) å,=95.65(1),Z=4, R=0.0534,Rw=0.0600), where dpamH denotes the 2,2-dipyridylamine. 相似文献
113.
114.
Zusammenfassung In der vorliegenden Arbeit wird eine Methode zur Retentionsindex-Bestimmung beschrieben, die von einem kubischen Zusammenhang zwischen Bruttoretentionszeit-Differenzen der Referenzhomologen und der Kohlenstoffzahl ausgeht. Hieraus ergeben sich direkt die Nettoretentionszeiten. Der Fehler der Totzeitbestimmung entfällt bei dieser Methode. Mit den so gewonnenen Nettoretentionszeiten erhält man über einen kubischen Zusammenhang zwischen 1g ts=f(C) die Retentionsindices. Extrapolationen und Interpolationen sind über 300 Retentionsindexeinheiten mit einem mittleren Fehler von ±0,02 Retentionsindexeinheiten möglich. Das Verfahren bietet sich für eine automatische Berechnung der I-Werte mittels on-line-Datenverarbeitung an.
Cubic calculation of retention indices without determining the dead-time tm
Summary The method for the calculation of retention indices described here is based on a third order relationship between the logarithm of differences of unadjusted retention times of homologues and the carbon number. From this adjusted retention times are directly calculated. A determination of the dead-time is not necessary thus avoiding the errors connected with this factor. A cubic equation for the logarithm of the adjusted retention time lg ts as a function of carbon number Cn is used for the retention index calculation. Extrapolations and interpolations can be done over a range of 300 index units with an average deviation of ±0.02 i.u.. The method offers the possibility of an automated on-line calculation of retention indices by computer merely on the basis of unadjusted retention times.相似文献
115.
116.
J. -C. Cheng F. -H. Li L. Guo S. Y. Zhang 《Applied Physics A: Materials Science & Processing》1995,61(4):441-446
A complete theoretical treatment for the determination of thermal diffusivity of superlattices by the mirage technique has been performed. An effective medium approximation model of the thermal conductivity and thermal diffusivity of both sublayers is presented, which is different from the simple models with the thermal diffusivity or thermal conductivity in series or parallel. The numerical calculation of the transverse component of the probe beam deflection in the mirage effect shows that the results obtained from the complete thermal-wave theory and the medium approximation model, for the optically and thermally thick superlattices, are in good agreement with each other. However, the further study on the thermally thin superlattices shows that either the series or the parallel model of the thermal conductivity should be chosen according to whether the thermal impedance of the superlattice is larger or less than that of substrate, respectively. 相似文献
117.
G. Alberti G. Bellettini M. Cassandro E. Presutti 《Journal of statistical physics》1996,82(3-4):743-796
We consider an Ising spin system with Kac potentials in a torus of d,d>-2, and fix the temperature below its Lebowitz-Penrose critical value. We prove that when the Kac scaling parameter vanishes, the log of the probability of an interface becomes proportional to its area and the surface tension, related to the proportionality constant, converges to the van der Waals surface tension. The results are based on the analysis of the rate functionals for Gibbsian large deviations and on the proof that they -converge to the perimeter functional of geometric measure theory (which extends the notion of area). Our considerations include nonsmooth interfaces, proving that the Gibbsian probability of an interface depends only on its area and not on its regularity. 相似文献
118.
D. H. Fremlin R. A. Johnson E. Wajch 《Proceedings of the American Mathematical Society》1996,124(9):2897-2903
A space Borel multiplies with a space if each Borel set of is a member of the -algebra in generated by Borel rectangles. We show that a regular space Borel multiplies with every regular space if and only if has a countable network. We give an example of a Hausdorff space with a countable network which fails to Borel multiply with any non-separable metric space. In passing, we obtain a characterization of those spaces which Borel multiply with the space of countable ordinals, and an internal necessary and sufficient condition for to Borel multiply with every metric space.
119.
It is shown that, given a lower semicontinuous convex integrandf satisfying a suitable integrability condition, there exists a sequence of Lipschitz simple integrands which Mosco converges tof and such that the sequence of conjugate integrands Mosco converges tof
*. Moreover, this sequence can be chosen so that the sequence of associated integral functionals, respectively defined onL
1(X) andL
(X
*), Mosco converges as well.We wish to thank Professor Erik J. Balder for interesting remarks on the first version of this work. 相似文献
120.
N. H. Tea R. -C. Yu M. B. Salamon D. C. Lorents R. Malhotra R. S. Ruoff 《Applied Physics A: Materials Science & Processing》1993,56(3):219-225
We have performed thermal conductivity measurements on C60 and C70 crystals grown by sublimation. For single crystal C60, the thermal conductivity k is 0.4 W/m K at room temperature and is nearly temperature independent down to 260K. We observed a sharp orientational phase transition at 260K, indicated by a 25% jump in k. Below 90K, k is time dependent, which manifests itself as a shoulder-like structure at 85K. The temperature and time dependence of k below 260K can be described by a simple model which accounts for the thermally activated hopping of C60 molecules between two nearly degenerate orientations, separated by an energy barrier of 240 meV. It is found that solvents have a strong influence on the physical properties of C70 crystals. For solvent-free C70 crystal, k is about constant above 300K. There is a broad first-order phase transition in k at 300K with a 25% jump. We associate this transition with the aligning of the fivefold axes of the C70 molecules along the c-axis of the hexagonal lattice. Upon further cooling, k increases and is time independent. 相似文献