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应用断流分光光度计(Stopped-Flow Spectrophotometer)研究了镍(II)与N-(对位取代苯基)氨基乙酸-(ρ-RC6H4NHCH2COOH, R=CH3O, CH3, H, Cl, 简写为NROH或HL)在25℃及30%(v/v)乙醇溶液中生成配合物的反应动力学. 实验结果表明, 不仅氨基酸配体的负离子(NRO^-或L^-)具有较高的反应活性, 而且两性离子(HN^+RO^-或^+HL^-)也是有效的反应配体. 反应按双途径进行, 即按Eigen-Tamm机理进行的NRO^-途径和以质子迁移为速率控制步骤的两性离子途径. 两性离子的反应活性(以log kHL^±表示)与配体的碱性强度(pK2)之间呈现直线自由能关系. 并发现镍(II)配合物的离解反应速率常数(log k-L^-)与配体的碱性强度(pK2)和配合物的稳定常数(log KNiL^N^i)之间均存在直线自由能关系. 相似文献
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《Composite Interfaces》2013,20(7):647-655
Composites based on the blends of polyurethane and poly(methyl methacrylate) of various composition were synthesized in situ in the presence of various amounts of nanoparticles (fumed silica). From thermophysical measurements it was found that, during reaction, phase separation and evolution of two phases occur. The temperature transitions in the systems and their positions depend on the blend composition and on various amounts of nanoparticles. Using scanning differential calorimetry from the changing of heat capacity increments the fraction of an intermediate region between two main phases has been estimated. For the first time it was observed that in nanocomposites in the temperature region between two main relaxation transitions, there appears a third transition, which was related to the adsorption layers formed by both components at the interface of the nanoparticles. The appearance of such intermediate regions increases essentially the fraction of an interfacial region in the system. 相似文献
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基于平面构型的阴离子基团可能具有大的倍频效应的观点,以固相反应法在LiBO2:CdCO3=1:1摩尔比,反应温度600~620℃,空气气氛中合成了α-LiCdBO3,α-LiCdBO3在高于620℃时开始转变成β-LiCdBO2,此β-多型体在867±5℃异元熔融而分解,考查了α-LiCdBO2的合成条件及其粉末倍频效应,测得α-LiCdBO3的SHG(Second harmonic generation)强度是ADP(NH4H2PO4)的三倍,β-LiCdBO3无倍频效应。 相似文献
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In this paper a theoretical treatment of adsorptive-complex wave is given for the case of a linear variation of the electrode potential. The reaction system of CAEL mechanism is expressed as follows: 相似文献
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某些过渡金属钌配合物非线性光学性能的从头算和密度泛函理论研究 总被引:5,自引:1,他引:5
实验发现金属钌的某些配合物具有大的非线性光学性能。我们的理论研究表明 金属钌配合物[Ru(NH_3)_4L~DL~A]~(n+) (n = 2,3;L~D,L~A =吡啶衍生物配体) 的非线性光学性能取决于推电子基团L~D的给电子能力以及拉电子基团L~A的受电子 能力,L~D和L~A的推拉电子越强越有利于提高配合物的二阶非线性光学系数β,因 此带正电荷的L~A能大幅度提高β值。虽然增加共轭体系的长度有利于提高β值, 但在Ru的配合中,吡啶环间或吡淀环与苯环间不一定要保持共面也会有大的β值。 DFT和ab initio方法的计算结果对比表明,对于含过渡金属Ru的化合物,在HF水平 上难以得到满意的结论,由从头算有限场方法计算得到的β值偏小,而用TDDFT方 法能得到可与实验值符合较好的结果。 相似文献
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The mechanism of the electroreduction of Te(IV) has been studied, it is (TeO3)2- + 3H2O + 4e = (Teads)0 + 6OH- (1) (Teads)0 + H2O + 2e = (Hte)- + OH- (Teads)0 + 2e = Te2- The reaction scheme can generally be expressed as follows: ACcordingly, the equation of adsorptive current is give: i = 0.629 n2**2F**i/RT \n\(D0)1/2m2/3t7/6 \Pn\/(1+\Pn\)**2 (C0)* where \Pn\ = bAtA,7exp n2F/RT (E-E0)/& When \Pn\ = 1 the current reaches the maximum, ip = 0.157 n2**2F**2/RT \n\(D0)1/2m2/3t7/6(C0)* This equation shows that the peak current ip is proportional to m2/3t7/6, the ratio of potential change v and the concentration of the substance O being reduced. The half wave width, w1/2, can be obtained from the equation (6) in the form of the following expression W1/2 = 3.52RT/n2F The theoretical conclusions are in good agreement with experimental data for the adsorptive wave of tellurium in 0.25M NH3-NH4cl solution. The diffusion coefficient value determined agrees with that obtained by other polarographic method reported in the literature. 相似文献
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The kinetics of the metal exchange reactions between (5-R-phen)copper(II) (R = Me, H, Cl, and NO2) and Ni(II) was studied at 25?and ionic strength 1.0 mol dm-3 or pH 2.3-3.5. The rate of the exchange reactions was measured by a spectrophotometer. The reactions appeared to proceed through 3 different pathways which involved H+ attack and Ni attack as well as a pH- and Ni-independent dissociation of the complexes. The kinetics conforms to the following rate law: d[Ni(5-R-phen)]/dt = (kp + kH[H+] + kNi[Ni2+])[(Cu(5-R-phen)2+]. The reaction rate of the 3 pathways increased with decreasing basicity of the ligand. Some linear free energy relationships were found to exist between the reactivity of these Cu(II) complexes and the base strength of the ligand 5-R-phen. The mechanisms of the reactions are discussed. 相似文献
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