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The rate of the Wolff-Kishner reaction of benzophenone hydrazone in butyl carbitol increases as the cation of the alkoxide base is varied in the order K>Na>Li>Mg. The replacement of butyl carbitol by 1-decanol also accelerates the reaction, and an additional increase is caused by the presence of crown ether. On the basis of changes in the activation parameters, it is concluded that the reactivity of the hydrazone anion increases as the contact ion pair becomes more fully solvated and dissociated. 相似文献
55.
The interaction of AlR2(BHT)(OEt2) and AlMe(BHT)2 with methylmethacrylate (MMA) leads to the formation of the Lewis acid-base complexes AlR2(BHT)(MMA) [R = Me (1), Et (2)] and AlMe-(BHT)2(MMA) (3), respectively. The molecular structure of 1 has been determined by X-ray crystallography. The decrease in the C=O and C=C stretching frequencies in the IR spectrum, and downfield shift in the 13C NMR spectrum of the - and γ-carbons of the MMA, when compared to free MMA, is presented with respect to the activator ability of sterically crowded aryloxide compounds of aluminum to aluminum-porphyrin catalyzed (Inoue) polymerization of MMA. 相似文献
56.
A study was carried out on the composition and nature of the stabilizing additive on the activity of nickel-containing composites
based on zirconia in the methane steam conversion. The methane conversions were 91–99% on Ni/ZrO2(Y, Sc, Ce) at 700–800 °C. 相似文献
57.
过渡金属酞等配合物(MPC)用手均相液相氧化中作催化剂已有不少报导,象许多均相催化剂一样,MPC用于均相反应存在着难于从反应体系中分离出来的问题.把均相配合物催化剂固载在无机氧化物如硅股或有机高分子载体上是解决这一问题的一种方法.我们曾尝试把MP。固载在分子筛载体和硅胶载体上,并用ESR研究其对O2的活化作用[1,2].本文报导MPc通过共价键键联固载在SiO2上,并研究其对O2的活化作用.1实验部分1.1试剂HSIC13为日本东京化成株式会社产品,二级试剂·发烟硫酸(SO。质量分数大于20%)为分析纯试剂.PCl5为化学纯试… 相似文献
58.
N. A. Yakovleva S. N. Klyamkin O. A. Veremeeva A. A. Tsikhotskaya 《Russian Chemical Bulletin》2005,54(1):135-140
Using heat conducting Tian—Calvet calorimetry and volumetric measurements, the first hydrogen absorption—desorption cycles in the LaNi5-H2 and CeNi5-H2 systems were studied. The pressure—composition isotherms were plotted, the equilibrium pressures of hydrogen along the absorption and desorption branches and in the region of hysteresis for different activation steps were determined, and the enthalpies of phase transitions α → β and β → α were calculated. The profiles of the heat evolution curves were analyzed. It was concluded that the mechanism of the reactions studied changes upon activation.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 134–139, January, 2005. 相似文献
59.
On the basis of the structures and properties of the ClO/ClO? system obtained at the density functional theory (DFT) (UB3LYP) level, employing the 6‐311+G(3df) standard basis set, the electron transfer reactivity of this system is investigated. The results indicate that there are five possible stable coupling complexes that correspond to the generous minima on the global potential energy surfaces (PES). The most stable coupling complex is planar EC4, in which there is a O? O linkage with two trans‐Cl atoms. Their stabilization energies are calculated to be 20.57 (EC1: C1), 20.54 (EC2: C2, 2B), 20.69 (EC3: C1), 20.70 (EC4: Cs, 2A′), and 20.69 (EC.5: C2h, 2Bu) kcal/mol at the B3LYP/6‐311+G(3df) level; with the correction of the basis set superposition error (BSSE), the stability order of these encounter complexes is EC4 > EC.5 > EC3 > EC1 > EC2. Based on the five encounter complexes, five coupling modes are designed for the study of the electron transfer reactivity of this system. The dissociation energy curves at the activated states and the corresponding activation energies of these five coupling modes are obtained and are compared at the B3LYP/6‐311+G(3df) and MP2/6‐311+G* levels. The inapplicability of DFT methods has also been discussed in this article in predicting the energy curves, especially with a long contact distance, in which DFT methods give the abnormal behavior for the dissociations of the complexes caused by the “inverse symmetry breaking” problem. On the basis of the golden rule of the time‐dependent perturbation theory, the electron transfer reactivity and the contact distance dependence of the various electron transfer kinetics parameters (e.g., activation energy, coupling matrix element) have been analyzed at the UMP2(full)/6‐311+G* level. The electron transfer can take place over a range of contact distances, but the most effective coupling distance corresponds to only a small range. The coupling orientation analyses also indicate that the most favorable coupling mode to the electron transfer does not always correspond to the most stable encounter complex mechanism. Some highly energetic coupling modes are more favorable for the electron transfer. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
60.
Heating rate effect on the DSC kinetics of oil shales 总被引:1,自引:0,他引:1
M. V. Kök 《Journal of Thermal Analysis and Calorimetry》2007,90(3):817-821
This research was aimed to investigate the combustion and kinetics of oil shale samples (Mengen and Himmetoğlu) by differential
scanning calorimetry (DSC). Experiments were performed in air atmosphere up to 600°C at five different heating rates. The
DSC curves clearly demonstrate distinct reaction regions in the oil shale samples studied. Reaction intervals, peak and burn-out
temperatures of the oil shale samples are also determined. Arrhenius kinetic method was used to analyze the DSC data and it
was observed that the activation energies of the samples are varied in the range of 22.4–127.3 kJ mol−1 depending on the oil shale type and heating rate. 相似文献