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排序方式: 共有407条查询结果,搜索用时 15 毫秒
1.
The reaction of B2H4 with acetylene has been studied by the MNDO method. It is shown that the reaction is exothermic and proceeds in two steps. The first step is the formation of a three-center -complex and this is the rate-determining step of the reaction. The second step is the rearrangement of the -complex to the product and this step requires a very small amount of activation energy. The activation barrier for the diboration reaction is 12.8 kcal/mol.The proposed mechanism is significantly different from those proposed earlier and explains all experimental data relating to this reaction. 相似文献
2.
Rita Kakkar Mallika Pathak Preeti Chadha 《International journal of quantum chemistry》2005,102(2):189-199
The rearrangement of vinylidene to acetylene has been studied in detail by the density functional method, using Becke's three‐parameter exchange functional and the gradient‐corrected functional of Lee, Yang, and Parr. The rearrangement of the anion, as well as that of fluoro‐substituted systems, has also been investigated, in order to determine the effect of fluorine substitution on the activation barrier to the 1,2‐hydrogen shift, as well as the relative migratory aptitudes of hydrogen and fluorine. Natural bond orbital analysis is invoked to gain insight into the mechanisms of the rearrangements. Basis size effects are also discussed, particularly in relation to anionic systems. The need to include diffuse functions in geometry optimizations of anionic systems is reinforced by the present calculations. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
3.
铜基催化剂的结构、物性及其对混合碳四选择加氢反应的催化性能 总被引:2,自引:0,他引:2
用XRD,XPS,SEM和H2-TPR等手段研究了铜基负载型催化剂的结\r\n构和物性及其对混合碳四加氢脱炔的催化性能.结果表明,在负载铜催\r\n化剂中加入一定量的Co可提高催化剂的加氢脱炔活性,而Co含量较少时\r\n加入少量的Ce也能提高催化剂的活性和选择性.Cu和Co之间存在着相互\r\n协同作用,使得活性组分在催化剂表面偏析,CuO在催化剂表面呈非晶\r\n相分散状态,催化剂颗粒粒径变小,催化剂更容易被还原,从而改善了\r\n催化剂的催化性能. 相似文献
4.
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7.
研究了过渡金属催化的炔烃衍生物的异构化反应.从α,β-炔酮、2-炔酸酯和2-炔酸酰胺可以生成相应的(E,E)-共轭双烯酮、双烯酸酯和双烯酸酰胺.首次从2-炔醇异构化为相应的2-烯酮或2-烯醛.这一反应具有简单、高产率和立体选择性的优点.假设反应烯经过连二烯中间体,然后再异构化成产物,这一反应提供了方便而有潜在应用价值的方法以制备天然产物合成时的重要中间体. 相似文献
8.
Plasma Thermal Conversion of Methane to Acetylene 总被引:2,自引:0,他引:2
Fincke J. R. Anderson R. P. Hyde T. Detering B. A. Wright R. Bewley R. L. Haggard D. C. Swank W. D. 《Plasma Chemistry and Plasma Processing》2002,22(1):107-138
This paper describes a re-examination of a known process for the direct plasma thermal conversion of methane to acetylene. Conversion efficiencies (% methane converted) approached 100% and acetylene yields in the 90–95% range with 2–4% solid carbon production were demonstrated. Specificity for acetylene was higher than in prior work. Improvements in conversion efficiency, yield, and specificity were due primarily to improved injector design and reactant mixing, and minimization of temperature gradients and cold boundary layers. At the 60-kilowatt scale cooling by wall heat transfer appears to be sufficient to quench the product stream and prevent further reaction of acetylene resulting in the formation of heavier hydrocarbon products or solid carbon. Significantly increasing the quenching rate by aerodynamic expansion of the products through a converging–diverging nozzle led to a reduction in the yield of ethylene but had little effect on the yield of other hydrocarbon products. While greater product selectivity for acetylene has been demonstrated, the specific energy consumption per unit mass of acetylene produced was not improved upon. A kinetic model that includes the reaction mechanisms resulting in the formation of acetylene and heavier hydrocarbons, through benzene, is described. 相似文献
9.
R. S. Mitchenko A. A. Shubin T. V. Krasnyakova 《Theoretical and Experimental Chemistry》2006,42(5):314-319
A heterogeneous catalyst for the hydrochlorination of acetylene by gaseous HCl is formed as a result of mechanical treatment
of the solid salt K2PtCl4 in an atmosphere of acetylene, ethylene, or propylene by the formation of π complexes of platinum(II) as active centers in
the surface layer under these conditions. The controlling stage of the catalytic reaction is chloroplatination of the π-coordinated
acetylene by the HCl molecule. The reaction takes place as a concerted process, in which an intermediate β-chlorovinyl derivative
of platinum(II), a complex of platinum with a coordination vacancy[PtCl
3
*
]−, and a new molecule of HCl are formed simultaneously with cleavage of the H—Cl and Pt—Cl bonds in the metal complex adjacent
to the π-acetylene complex. The catalytic cycle closes with rapid dissociation of the organoplatinum intermediate by the action
of HCl, giving the final product and the initial complex [PtCl4]2−.
__________
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 5, pp. 306–311, September–October, 2006. 相似文献
10.
Joongjai Panpranot Songphol Aungkapipattanachai Thanapon Sangvanich Pawin Boonyaporn Piyasan Praserthdam 《Reaction Kinetics and Catalysis Letters》2007,91(2):195-202
N2O pretreatment has shown to result in enhancement of the performance of fresh commercial Pd-Ag/α-Al2O3 catalyst during selective acetylene hydrogenation. However, it showed no effect for the used and regenerated catalysts probably
due to changes int he metal arrangement on the catalyst surface after regeneration. 相似文献