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71.
By means of model calculations it could be shown for an irreversible surface reaction of 1st order that the determination of the activation energy of the desorption of the reactant or, respectively, of the surface reaction is possible by application of the method of variation of the heating rate to the desorption curve of the reactant, according to circumstances whether the ratio of the activation energy of the surface reaction and of the desorption of the reactant is greater or smaller than one.The possibilities of the kinetic evaluation are applied to the isomerization of cyclopropane on a NaX-zeolite catalyst. The resulting heat of adsorption of cyclopropane and the activation energy of the reaction agree well with the values of literature obtained by isothermal measurements in a pulse reactor.
Zusammenfassung Mit Modellrechnungen für eine irreversible Oberflächenreaktion 1. Ordnung konnte gezeigt werden, daß durch Anwendung der Methode der Variation der Heizgeschwindigkeit auf die Desorptionskurve des Ausgangsstoffes die näherungsweise Bestimmung der Aktivierungsenergie der Desorption des Ausgangsstoffes bzw. der Oberflächenreaktion möglich ist, je nachdem ob das Verhältnis der Aktivierungsenergien für die Oberflächenreaktion und der Desorption des Ausgangsstoffes größer oder kleiner als eins ist.Die Möglichkeiten der kinetischen Auswertung werden auf die isomerisierung von Cyclopropan an einem NaX-Zeoliten angewendet. Die erhaltene Adsorptionswärme für Cyclopropan und die Aktivierungsenergie für die Reaktion stimmen gut mit Literatur-werten von isothermen Messungen im Impulsreaktor überein.相似文献
72.
A. V. Kravtsov E. D. Ivanchina A. V. Kornienko 《Reaction Kinetics and Catalysis Letters》1997,61(1):161-166
A new method for computer prediction of the catalytic activity dependence on service life and technological conditions for
bifunctional Pt catalysts has been proposed. The proposed method is based on physical and chemical laws of multicomponent
hydrocarbon transformations on polymetallic catalysts and takes into account deactivation of acidic (Al) and metallic (Pt)
sites. It allows to calculate the product composition and catalytic activity level for real industrial units as a function
of their technological parameters and raw material characteristics. 相似文献
73.
Gy. Marosi R. Lágner Gy. Bertalan P. Anna A. Tohl 《Journal of Thermal Analysis and Calorimetry》1996,47(4):1155-1161
Nucleating and transcrystallization behaviour of additives in engineering PP composites and the effect of modified interfacial structure is the subject of this series of papers. The first part concentrates on polypropylene/liquid crystalline polyester blends. Increased crystallisation temperature and degree of crystallinity of polypropylene is characteristic to the blends containing different amount of LCP additive. Transcrystallization process governs the formation of crystalline structure in these systems in course of isothermal crystallisation at 132C. The nucleating effect of LCP gives rise to more uniform crystalline structure in the polypropylene phase.The financial support of the OTKA 014194 is acknowledged with gratitude. 相似文献
74.
在 pH 4.5 HAc-NaAc缓冲溶液中,钍试剂分别于- 0.36 V、- 0.60 V产生两个灵敏的极谱波。基于钒对溴酸钾氧化钍试剂的催化作用,建立了双极谱波测量的催化动力学极谱法。钒浓度在0.7~15μg/L与△I(△I1+ I2)呈线性关系,检测限为0.5μg/L。研究了极谱波性质及电极反应机理。本法简便、灵敏、准确,已用于直接测定水中痕量钒。 相似文献
75.
76.
在量子化学对SiH与H2O和H2S反应计算的基础上,运用统计热力学和Wigner校正的Eyring过渡态理论,计算了上述两反应在200~2000 K温度范围内的热力学函数、平衡常数、频率因子A和速率常数随温度的变化。计算结果表明,两反应在低温下具有热力学优势,而在高温下具有动力学优势。比较两反应的计算结果发现,在相同的温度下,SiH与H2O反应比SiH与H2S反应放热较多,但速率常数却较小。SiH与H2O反应和前文报道的SiH与HF反应的比较表明,SiH与H2O反应放热较少,而且在相同温度下,速率常数也较小。 相似文献
77.
根据Fe(Ⅲ)、Mo(Ⅵ)对H2O2氧化邻氨基酚的催化反应速率不同,结合流动注射停留技术,建立了同时测定Fe(Ⅲ)、Mo(Ⅵ)的速差动力学分光光度法.测定铁和钼的线性范围分别为0.1~2.5μg/mL和0.5~15μg/mL.除W(Ⅵ)的允许量较小外,其它离子不干扰测定.用本法测定了合成样液中铁和钼含量,结果满意. 相似文献
78.
This work presents a study of the thermal
degradation of ultra-high molecular mass polyethylene (UHMWPE) stabilized
with natural (α-tocopherol and carvacrol) and synthetic antioxidants.
Thermogravimetric analysis in dynamic mode was used to determine the apparent
activation energies of different samples. The stabilization of UHMWPE with
low concentrations (around 0.3%) of α-tocopherol is enough to obtain
an efficient thermal performance of the polymer. Carvacrol is also a good
stabilizer for UHMWPE, but at higher concentration than in the case of α-tocopherol.
The comparison of apparent activation energy between samples with natural
and synthetic antioxidants in similar concentration shows that α-tocopherol
is a better stabilizer in terms of their thermal performance. 相似文献
79.
Alan P Marchand Bishwajit GangulyCarolina I Malagón Huiguo LaiWilliam H Watson 《Tetrahedron》2003,59(10):1763-1771
Diels-Alder cyclodimerization of 1,2,3,4,5-pentachlorocyclopentadiene (1) affords 2a as the exclusive reaction product. Diels-Alder cycloaddition of 1 to norbornadiene also proceeds stereoselectively to produce a single [4+2] cycloadduct, 4c. The structures of 2a and 4c were established unequivocally via application of single crystal X-ray crystallographic techniques. The origins of the observed diastereofacial selectivity in each of these cycloaddition processes have been investigated by application of semiempirical (AM1 Hamiltonian) and ab initio (Hartree-Fock 3-21G*) calculations. The computational results thereby obtained, which are based upon consideration of the kinetically favored transition state for each of the two cycloaddition reactions studied, are consistent with experiment. These semiempirical and ab initio methods also have been used to investigate the mechanisms of the Diels-Alder reactions that have been used to prepare aldrin and isodrin (7 and 8, respectively). The results thereby obtained suggest that isodrin formation via Diels-Alder cycloaddition of cyclopentadiene to 1,2,3,4,7,7-hexachloronorbornadiene proceeds with kinetic control of product stereochemistry. 相似文献
80.
An approximate kinetic‐energy functional of the generalized gradient approximation form was derived following the “conjointness conjecture” of Lee, Lee, and Parr. The functional shares the analytical form of its gradient dependency with the exchange‐energy functionals of Becke and Perdew, Burke, and Ernzerhof. The two free parameters of this functional were determined using the exact values of the kinetic energy of He and Xe atoms. A set of 12 closed‐shell atoms was used to test the accuracy of the proposed functional and more than 30 others taken from the literature. It is shown that the conjointness conjecture leads to a very good class of kinetic‐energy functionals. Moreover, the functional developed in this work is shown to be one of the most accurate despite its simple analytical form. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献