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1.
《Comptes Rendus Chimie》2015,18(3):345-350
The combination of kinetic and thermodynamic analyses can provide an in-depth knowledge of the crucial steps of catalyzed reactions. Earlier examples are recalled to stress how a reaction mechanism can be supported or rejected based on trivial reactant and product concentration analyses. The method is then applied to the important reaction of alcohol condensation, the so-called Guerbet reaction, which enables converting ethanol, a renewable feedstock, into higher alcohols. Important conclusions regarding the design of ethanol condensation processes can be drawn, as the main reaction mechanism occurring at high temperatures (ca. 350–420 °C) appears to be different from that proposed at low temperatures (< 250 °C). In the former case, the pathway involving acetaldehyde is negligible, and therefore a multi-step process based on ethanol dehydrogenation followed by acetaldehyde self-aldolization would be irrelevant. 相似文献
2.
3.
Alexander Zeller 《Journal of organometallic chemistry》2006,691(21):4379-4385
The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (kH/kD = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active. 相似文献
4.
A multi-exposure of color fringes method has been developed to improve the capture speed of a conventional color CCD camera. In the method, four groups of projected fringe patterns encoded with different colors and different directions are stored in one CCD frame. Therefore the capture frequency of the conventional CCD can be improved to 200 Hz. It is available to measure the insect wings with low beating frequency, such as dragonfly, moth, or butterfly, whose beating frequency is about 30–40 Hz. We have used the method to measure the beating motion of a moth successfully. 相似文献
5.
A simple and accurate algorithm (phase scanning method) is proposed for 3D surface contouring and dynamic response determination of a vibrating object. A sinusoidal fringe pattern is projected onto a low-frequency vibrating object by a programmable liquid crystal display projector. The fringe patterns are captured by a high-speed CCD camera with a telecentric gauging lens. Phase values are evaluated point by point using phase scanning method. From the phase values of each point on the object, the contour of the specimen at different instants of vibration can be retrieved. In this paper, a small vibrating coin is used to demonstrate the validity of the method and the experimental results are compared with test results on a stationary coin using four-step phase shifting and fast Fourier transform methods. The technique is especially useful in applications where the vibrating object has a complicated shape. 相似文献
6.
The article concerns heterojunction resonant cavity-enhanced (RCE) Schottky photodiodes with GaAs in the absorption layer. The quantum efficiency and linear pulse response have thoroughly been analysed. For the first time, the response of a heterojunction photodiode has been modelled by the phenomenological model for a two-valley semiconductor. The results obtained have shown that the satellite valleys, as well as the parasitic time constant, significantly influence the response and, accordingly, have to be taken into account when analysing and optimizing RCE photodetectors. 相似文献
7.
表面活性剂对均相沉淀法制备单晶Ce2O(CO3)2¢H2O微粉形貌及
形成机理的影响 总被引:2,自引:0,他引:2
在尿素及硝酸铈的混合溶液中分别加入表面活性剂CTAB、 PEG19000、OP-10,利用均相沉淀法合成了不同形貌的CeO2超细前驱体Ce2O(COa)2·H2O,采用X射线衍射及透射电子显微镜等测试手段,对产品的物相和形貌进行了表征.实验结果表明,所得产品均为斜方晶系的单晶Ce2O(CO3)2·H2O,且表面活性剂的加入使晶体的晶化程度明显提高;添加不同的表面活性剂得到不同形貌尺寸的产物: 阳离子型表面活性剂CTAB对Ce2O(CO3)2·H2O晶体的形貌影响不大,所得产物尺寸变小,且分散性得到一定的改善;非离子型表面活性剂对所得产物的形貌影响显著.加入PEG19000和OP-10分别得到了形状排列有序的、尺寸较均匀的、较规则无团聚的微米棒及具有紧密结合中心的发散状的花样微粒.不同形貌前驱体的形成与晶粒形成生长机理的改变有关. 相似文献
8.
本文报道四甲基膦酸二甲庚酸萃淋树脂(CL-P_(350)从硝酸溶液中吸附鳞的性能和机理研究。实验结果表明,吸附平衡服从Langmuir经验等温式。测得吸附物分子中P(350)与Re(Ⅶ)的摩尔比为2:1。Re(Ⅶ)是以形式被树脂吸附,其吸附机理属于综合反应:并测定了吸附过程的热力学函数。 相似文献
9.
利用光学显微镜对中碳钢退火孪晶的形态及形成机制进行了研究。退火孪晶是中碳钢过热组织的特征之一。其形态分穿晶型和中止型,分别按横向、纵向机制形核长大。退火孪晶有利于晶粒细化 相似文献
10.
许镇 《天津理工大学学报》1988,(2)
本文提出了旋转坐标系的概念,从而不仅可将文献对低付机构的运动分析方法运用到含有高付的凸轮一连杆机构中,而且不必“高付低代”,即可进行机构在一个运动循环中的运动分析。本文编制了程序设计框图和程序,并通过实例给出了部分计算结果及线图。该程序设计框图和子程序“SUB”对其他机构运动分析具有一定的通用性。 相似文献