In a recent publication [J. Acker, K. Bohmhammel, J. Phys. Chem. B 106 (2002) 5105], the reactions between transition metal silicides and hydrogen chloride were studied by isothermal calorimetric measurements. The obtained apparent activation energies and pre-exponential factors show clearly a linear dependence that is attributed to the compensation effect. An isokinetic temperature of 696.9 +/- 22.1 K was determined. According to Larsson's model of selective energy transfer, a characteristic frequency of 969.3 +/- 46.5 cm(-1) is calculated. The occurrence of the compensation effect is discussed in terms of chemisorption, precursor formation, and the involvement of surface species in essential reaction steps. (C) 2003 Elsevier B.V. All rights reserved.
Reactivity of Intermetallic Compounds: A Solid State Approach to Direct Reactions of Silicon
作者:Jörg Acker、Klaus Bohmhammel
DOI:10.1021/jp0130315
日期:2002.5.1
work is focused on a new approach to describe, quantify, and compare the reactivity of various transition metal silicide phases toward hydrogen chloride. Thermodynamic and kinetic parameters are obtained from isothermal calorimetric studies of these reactions. The reactivity of the silicide phases is discussed in terms of reaction start temperatures, rate constants, and apparent activation energies. Negative
Kinetic study of the reaction between copper(I) chloride and commercial silicon or silicides
作者:B. Gillot、H. Souha、D. Viale
DOI:10.1007/bf01142049
日期:——
The reaction of CuCl with silicon containing as impurities Al, Fe, Ca and Ti or with some silicides (Si2Ca, Si2Fe, Si2Ti) has been investigated in the temperature range 250–310 °C. For the reaction between CuCl and commercial Si, it has been found that at 282 °C, the aluminium promotes the reaction between Cu3Si and CuCl while its rate of consumption is greatly decreased by the presence of iron impurity
CuCl 与含有杂质 Al、Fe、Ca 和 Ti 的硅或与一些硅化物(Si2Ca、Si2Fe、Si2Ti)在 250-310°C 的温度范围内的反应已经进行了研究。对于CuCl和商品Si的反应,发现在282°C时,铝促进了Cu3Si和CuCl之间的反应,而铁杂质的存在会大大降低其消耗率。这两种杂质的共同作用提高了形成的铜硅合金的数量。在硅化物存在下,与 CuCl 的反应导致形成高度分散的铜。
Reaction Pathway of Combustion Synthesis of Ti<sub>5</sub>
Si<sub>3</sub>
in Cu-Ti-Si System
The reaction pathway of combustion synthesis (CS) of Ti5Si3 in Cu–Ti–Si system was explored through a delicate microstructure and phase analysis on the resultant products during differential thermal analysis (DTA). The formation of Cu–Si eutectic liquids plays a key role in the reaction pathway, which provides easy route for reactant transfer and accelerates the occurrence of complete reaction. Cu
通过在差热分析 (DTA) 过程中对所得产物进行精细的微观结构和相分析,探索了 Cu-Ti-Si 系统中 Ti5Si3 燃烧合成 (CS) 的反应途径。Cu-Si共晶液体的形成在反应途径中起着关键作用,为反应物转移提供了简便的途径,加速了完全反应的发生。Cu 最初通过固态扩散反应与 Si 反应形成 Cu3Si,然后在~802°C 的共晶点进一步与 Cu 反应形成 Cu-Si 液体;然后 Ti 溶解到周围的 Cu-Si 液体中并导致形成 Cu-Ti-Si 三元液体;最后,Ti5Si3 通过溶液-反应-沉淀机制从饱和液体中沉淀出来。
Active site formation in the direct process for methylchlorosilanes
作者:W BANHOLZER
DOI:10.1016/0021-9517(86)90268-x
日期:1986.10
The direct process for methylchlorosilane production was studied in a laboratory-scale fluidized bed reactor. The silicon was found to have discrete sites at which silanes were produced. The density of sites was controlled by the nature of the native oxide layer over the silicon. The active sites displayed regular geometry, indicating an anisotropic silicon reaction which preferentially leaves (111)
Reactivity of Cu3Si of different genesis towards copper(I) chloride
作者:H Souha、F Bernard、E Gaffet、B Gillot
DOI:10.1016/s0040-6031(00)00365-8
日期:2000.6
Abstract A comparativestudy of the reactivity between copper(I) chloride and three types of Cu 3 Si obtained in a molten medium (Cu 3 Si-Ref) and from mechanical activation following an annealing process (Cu 3 Si-M2AP) or a self-propagating high-temperature synthesis (Cu 3 Si-MASHS) was performed by thermogravimetry under vacuum using non-isothermal and isothermal methods of kinetic measurement. It
摘要 对氯化铜 (I) 与在熔融介质中获得的三种类型 Cu 3 Si (Cu 3 Si-Ref) 和退火过程后的机械活化 (Cu 3 Si-M2AP) 或自-传播高温合成(Cu 3 Si-MASHS)是在真空下使用非等温和等温动力学测量方法通过热重法进行的。已经确定,对于三个 Cu 3 Si/CuCl 系统,在 145-215°C 温度范围内的加速和衰减阶段非常接近于 Prout-Tompkins 类型的方程,其中提出了自催化过程。Cu 3 Si-MASHS/CuCl 系统获得的表观活化能较低(63 kJ mol -1 对 68 和 78 kJ mol -1 Cu 3 Si-M2AP 和 Cu 3 Si-Ref,