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91.
用上升液滴法测定了2-乙基己基膦酸单(2-乙基己基)酯-正辛烷从硝酸介质中萃取镁、钙、锌、镍、铜和铅等二价金属离子的正向初始速率,建立了速率方程,计算出正向萃取反应的速率常数、活化能及活化熵,首次将软硬酸碱规则与金属溶萃取速率常数关联。结果表明,在萃取机理相同时,萃取速率常数的大小与金属离子的软硬酸碱标度一致,即萃取过程中,作为酸的被萃取金属离子,其硬度越大,萃取速率常数亦越大,萃取反应的活化能… 相似文献
92.
Petr Zuman 《Microchemical Journal》2002,72(3):241-250
Applications of chromatographic and atomic absorption methods are compared with those of electroanalytical techniques. The limitations of electroanalytical procedures and their advantages, such as speed, sensitivity and speciation are discussed. Among applications of polarography and voltammetry to a solution of basic problems, attention has been paid to the possibility to distinguish the degree of conjugation (e.g. of compounds containing the grouping CNNC), to a contribution to understanding of solution chemistry of mitomycin C and to processes involved in the reduction of cephalosporins. Among practical applications, the possibility to analyze suspensions, which can be carried out without separation offers advantages. Examples are interactions in suspensions of bile salts in the presence of metal (II) ions, adsorptions of various pesticides and other toxic materials on lignin and the possibility to follow alkaline cleavage of lignin in buffers pH 8-12 at 25 °C. Most of these studies would not be possible to carry out using other techniques. 相似文献
93.
Cyanobenzaldehydes (m-,o-,p-) were synthesized by oxidation of corresponding tolunitriles with molecular oxygen,catalyzed by cobalt acetate and sodium bromide. 相似文献
94.
稀土及其配合物对蛇毒磷脂酶A_2活性的影响 总被引:4,自引:0,他引:4
分别研究了三价稀土离子 (La3 + ,Eu3 + ,Dy3 + ,Yb3 + )、二乙三胺五乙酸及其衍生物二乙三胺五乙酸 -双二甲酰胺 ,二乙三胺五乙酸 -双 (异烟肼 )与稀土离子的配合物以及Tb -谷氨酰胺配合物对蛇毒磷脂酶A2 活性的影响 .浓度低于 <3μmol/L的稀土离子可以激活磷脂酶A2 ,浓度大于 5 μmol/L后稀土离子对酶活性表现出抑制作用 ;外源Ca2 + 离子的加入可以缓解稀土离子对酶活性的抑制作用 ,表明稀土离子和钙离子是竞争性地结合在酶的活性部位 ;稀土离子和二乙三胺五乙酸及其衍生物的配合物对酶活性没有明显影响 ;Tb -谷氨酰胺在浓度大于 10 μmol/L后开始抑制酶的活性 相似文献
95.
The asymmetric synthesis of the (+)-Kishi lactam and an intermediate for the preparation of the marine natural product fasicularin is reported. The keystone of this divergent synthesis is the diastereoselective azaspirocyclization of an N-methoxy γ-arylbutanoamide, which is believed to proceed through the intermediacy of an N-acylnitrenium ion. 相似文献
96.
R. A. Manzhos Yu. M. Maksimov B. I. Podlovchenko 《Russian Journal of Electrochemistry》2005,41(8):832-837
Transients of the open-circuit potential, which are observed during the interaction of formic acid with preliminarily adsorbed oxygen (Oads) on a Pt/Pt electrode in 0.5 M H2SO4, are measured. It is established, by means of the method of cathodic potentiodynamic pulses, that the slowest interaction of formic acid with Oads occurs in the region of large coverages of the electrode surface by oxygen (θO ∼1–0.8). A presumption is put forward that the process rate in this region is defined by a direct reaction of Oads with molecules of formic acid from the bulk solution. It is shown that the interaction of formic acid with Oads in the region of intermediate coverages (θO ∼ 0.8–0.2) proceeds via a mechanism of “conjugated reactions.” Transients of the open-circuit potential for formic acid are compared to transients for carbon monoxide obtained in analogous conditions. The substantially shorter overall time of potential decay in the case of CO (at the same concentrations) is caused by a faster reaction of CO with adsorbed oxygen in the region of large θO. The difference is explained by assuming that the HCOOH adsorption as opposed to CO bears a dissociative character.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 936–942.Original Russian Text Copyright © 2005 by Manzhos, Maksimov, Podlovchenko. 相似文献
97.
Summary Multipulse experiments reveal qualitative and quantitative, time-resolved information about the interaction of N2O with ZSM-5 type zeolites under conditions of catalytic applications, like the mechanism of N2O decomposition, amount and reactivity of an atomic surface oxygen species. 相似文献
98.
99.
Y. Marcus 《Journal of solution chemistry》1994,23(7):831-848
The water-structural contributions to the entropies and heat capacities of hydration of over 120 ions and the viscosity B-coefficients of nearly 80 aqueous ions are tabulated and correlated. B-coefficients for many more ions are predicted from this relationship and from their dependence on ionic size and charge. The structural entropies determine a unique scale of water structure making and breaking by the ions. 相似文献
100.
R. Acevedo T. Meruane E. Cortés S. O. Vasquez C. D. Flint 《Theoretical chemistry accounts》1994,88(2):99-110
Summary A theoretical model to calculate the vibronic intensities induced by the odd vibrational modes in centrosymmetric lanthanide complexes is developed and applied to octahedral complex ions, LnX
6
3–
, such as occur in the hexachloroelpasolites Cs2NaLnCl6. Both the crystal field and the ligand polarisation contributions are evaluated using a standard set of symmetry coordinates. For the crystal field term a truncated expansion of the intermediates states is employed rather than the more conventional closure approximation. Special care is necessary to ensure that the phases of the contributions are correctly determined since the cross-term between the ligand polarisation and crystal field contributions is signed. General equations applicable to anyf
n
complex ion are derived and an example of their application to the PrCl
6
3–
ion is given The agreement with experiment is satisfactory. 相似文献