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1.
碳正离子的稳定性与其在反应中的活性表现是基本一致的,越稳定的碳正离子,其反应活性越高,但是,含有π体系的碳正离子在不同的反应中,稳定性与其反应的关系不同,本文通过碳正离子的PKR^+值、气态氢化合合能数据及有关反应的速率常数值来说明烷基碳正离子、苄基型及烯丙型碳正熟子、桥头炭正离子在反应中的稳定性及其与反应活性的关系。  相似文献   

2.
本文通过对正碳离子、负碳离子、自由基等主要中间体在有机化学反应中的状态分析,论述了中间体的稳定性与有机反应活性的关系。  相似文献   

3.
以轻质烷烃异构化中试放大用的丝光沸石催化剂为研究对象,运用“原位”红外反应技术和催化剂活性评价手段,并结合反应动力学参数计算,探讨了正已烷异构化反应机理。结果表明,可用五配位反应中间物种机理解释正碳离子的生成。用双分子六元环反应中间物机理能较好地解释正已烷在氢型丝光沸石(HM)上的异构化过程。对正已烷在Pd/HM上的反应过程也可用正碳离子机理结合双分子六元环中间物机理解释。  相似文献   

4.
不饱和硅碳双键化合物(硅碳烯)结构复杂,既有与烯烃相似的平面结构,又有重烯烃同系物相似的非平面结构.自1967年第一个不稳定硅碳双键中间体被发现以来,不饱和硅碳双键化合物的合成及其反应活性研究进展很快.硅碳双键化合物反应活性高,在有机合成和有机硅高分子材料等领域具有广阔的应用前景.本文对近年来不饱和硅碳双键化合物合成及其反应活性研究的最新进展进行综述.  相似文献   

5.
负氢离子转移反应(htr)是重要的催化裂化基元反应之一.利用单事件微动力学模型对脂肪烃催化裂化的评估结果,从分子层面论述了htr反应的自催化特性.结果表明:原料中1-辛烯的存在提高了正碳离子活性中心覆盖率,尤其在原料转化率低的情况下,进而产生了更高的htr反应速率.htr反应速率不受原料中烯烃加入的影响,生成叔正碳离子的htr反应速率比生成仲正碳离子的速率快近5个数量级.对裂化反应机理比率(CMR)和反应链长(CL)的考察结果表明:当原料为纯烷烃时,两者的数值相近;当原料中加入烯烃时,CMR会受到明显影响,而CL几乎保持恒定.  相似文献   

6.
在酸性介质中用氧化还原滴定法研究了铈(Ⅳ)离子在微量铱(Ⅲ)离子催化作用下,于25℃~40℃区间氧化二乙醇胺(DEA)的反应动力学.结果表明铱(Ⅲ)离子具有高效的催化效能.反应对铈(Ⅳ)离子为一级,对铱(Ⅲ)离子也为一级,对二乙醇胺的表观反应级数为正分数(nap=0.47~0.58).在氮气保护下,反应能引发丙烯腈聚合,说明在反应中有自由基产生.通过kobs与[HSO4^-]的依赖关系,找到本反应体系的动力学活性物种是Ce(SO4)^2+,并计算出平衡常数,速控步骤的速率常数及相应的活化参数.  相似文献   

7.
以柠檬酸铵为原料合成的碳点,其表面含有大量的氨基和羧基,汞离子可以与这两种官能团发生络合反应,猝灭碳点的荧光.硫离子能够和汞离子结合形成稳定的不溶物硫化汞,使得碳点的荧光重新恢复.该工作是通过制备开关型(OFF-ON型)荧光传感器检测环境中的污染物Hg2+与S2-.这种OFF-ON型的传感器,在检测S2-时选择性良好,灵敏度较高.因此,碳点作为一种新型的传感材料,因其尺寸优势具有优良的发光性能,被广泛应用于金属离子检测、阴离子传感、生物分子传感等研究领域.  相似文献   

8.
利用多孔碳(C)的限域作用制备了铌(Nb)氧化物-碳复合载体负载铂(Pt)作为氧还原反应电催化剂.该实验在多孔碳中形成铌氧化物和单质铜(Cu)的混合物(Nb OxC@Cu),并以此作为载体,通过金属铜置换铂离子最终形成多孔碳/铌氧化物负载铂催化剂(Nb OxC@Pt),并进一步探究了该催化剂对氧还原反应的催化性能.结果表明:所制备的Nb OxC@Pt催化剂表现出优异的氧还原性能,其半波电位为878 m V,比活性为0.49 m·A·cm-2,明显高于商业Pt/C催化剂.此外,该实验还发现在氢氩混合气中预处理样品可以明显提高催化剂的稳定性.该实验将新型结构的多孔碳/铌氧化物作为载体应用到电化学实验教学中,能开拓学生对电催化基础材料科学的认知.  相似文献   

9.
用CH4、NH3和H2为反应气体,利用等离子体增强热丝化学气相沉积系统在沉积有碳膜的Si上制备了碳纳米尖端.用原子力显微镜表征了碳膜,结果表明碳膜是凸凹不平的膜,有许多凸起.在生长碳纳米尖端的过程中,由于既有含碳离子在凸起上的沉积,又有氢离子和含氮离子对凸起的刻蚀,根据有关离子沉积和溅射刻蚀的理论,理论分析了离子轰击碳膜凸起碳纳米尖端的形成.  相似文献   

10.
离子晶体格能是相互分离的气态正负离子结合成一摩尔离子晶体时所释放出的能量。其理论计算涉及多种方法,本文试图进行讨论,并对某些实际应用进行归纳。 一、晶格能的计算 品格能是离子晶体中离子间结合力(离子键强度)大小的一个量度。晶格能越大,离子晶体越稳定。由于离子晶体是由正负离子靠静电引力相结合,假设离子是电荷被集中在球心处的点电荷,则可根据静电吸引理论计算。  相似文献   

11.
Language markedness is a common phenomenon in languages, and is reflected from hearing, vision and sense, i.e. the variation in the three aspects such as phonology, morphology and semantics. This paper focuses on the interpretation of markedness in language use following the three perspectives, i.e. pragmatic interpretation, psychological interpretation and cognitive interpretation, with an aim to define the function of markedness.  相似文献   

12.
何延凌 《科技信息》2008,(4):258-258
Language is a means of verbal communication. People use language to communicate with each other. In the society, no two speakers are exactly alike in the way of speaking. Some differences are due to age, gender, statue and personality. Above all, gender is one of the obvious reasons. The writer of this paper tries to describe the features of women's language from these perspectives: pronunciation, intonation, diction, subjects, grammar and discourse. From the discussion of the features of women's language, more attention should be paid to language use in social context. What's more, the linguistic phenomena in a speaking community can be understood more thoroughly.  相似文献   

13.
理论推导与室内实验相结合,建立了低渗透非均质砂岩油藏启动压力梯度确定方法。首先借助油藏流场与电场相似的原理,推导了非均质砂岩油藏启动压力梯度计算公式。其次基于稳定流实验方法,建立了非均质砂岩油藏启动压力梯度测试方法。结果表明:低渗透非均质砂岩油藏的启动压力梯度确定遵循两个等效原则。平面非均质油藏的启动压力梯度等于各级渗透率段的启动压力梯度关于长度的加权平均;纵向非均质油藏的启动压力梯度等于各渗透率层的启动压力梯度关于渗透率与渗流面积乘积的加权平均。研究成果可用于有效指导低渗透非均质砂岩油藏的合理井距确定,促进该类油藏的高效开发。  相似文献   

14.
As an American modern novelist who were famous in the literary world, Hemingway was not a person who always followed the trend but a sharp observer. At the same time, he was a tragedy maestro, he paid great attention on existence, fate and end-result. The dramatis personae's tragedy of his works was an extreme limit by all means tragedy on the meaning of fearless challenge that failed. The beauty of tragedy was not produced on the destruction of life, but now this kind of value was in the impact activity. They performed for the reader about the tragedy on challenging for the limit and the death.  相似文献   

15.
正The periodicity of the elements and the non-reactivity of the inner-shell electrons are two related principles of chemistry,rooted in the atomic shell structure.Within compounds,Group I elements,for example,invariably assume the+1 oxidation state,and their chemical properties differ completely from those of the p-block elements.These general rules govern our understanding of chemical structures and reactions.Using first principles calcula-  相似文献   

16.
We have developed an adiabatic connection to formulate the ground-state exchange-correlation energy in terms of pairing matrix linear fluctuations.This formulation of the exchange-correlation energy opens a new channel for density functional approximations based on the many-body perturbation theory.We illustrate the potential of such approaches with an approximation based on the particle-particle Random Phase Approximation(pp-RPA).This re-  相似文献   

17.
正The electronic and nuclear(structural/vibrational)response of 1D-3D nanoscale systems to electric fields gives rise to a host of optical,mechanical,spectral,etc.properties that are of high theoretical and applied interest.Due to the computational difficulty of treating such large systems it is convenient to model them as infinite and periodic(at least,in first approximation).The fundamental theoretical/computational problem in doing so is that  相似文献   

18.
For molecular systems,the quantum-mechanical treatment of their responses to static electromagnetic fields usually employs a scalar-potential treatment of the electric field and a vector-potential treatment of the magnetic field.Although the potential for each field separately is associated with the choice of an(unphysical)origin,the precise choice of the origin for the electrostatic field has little consequences for the results.This is different for the  相似文献   

19.
<正>"The Journal of Shanghai Normal University:Mathematics"is published by Shanghai Normal University as regular issues of The Journal of Shanghai Normal University each year from 2014 in English.The editors-in-chief of the issues are professors Yuhao Cong and Maoan Han.The Journal of Shanghai Normal University was started in 1958 with  相似文献   

20.
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