Kinetic analysis of temperature-programmed surface reactions on porous catalysts

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.

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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.

     

Computer modeling for analysis of complex reaction kinetics

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.     

基于双波测量的催化动力学极诸法测定钒

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。     

2,6-二氯靛酚钠动力学分光光度法测定西红柿及草莓中的抗坏血酸

本文提出用2，6－二氯靛酚纳（以下简写DIS）作氧化剂动力学分光光度测定L－抗坏血酸的新方法。DIS与L－抗坏血酸混合．在固定时间间隔于611nm处测得吸光度A值的变化（△A／△t）与抗坏血酸含量成线性关系。线性范围为0～12mg／L。在样品处理时采用偏磷酸作为提取剂，以减缓抗坏血酸被氧化的速度结果表明，该方法有较高灵敏度，且操作简便，试剂易得，容易推广，是测定水果和蔬菜中L-抗坏血酸的好方法。     

次甲基硅SiH与H2X(X=O,S)反应的热力学及动力学性质研究

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。     

停留—催化反应速差动力学法同时测定Fe,Mo

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．     

Thermal characterization of UHMWPE stabilized with natural antioxidants

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.     

二溴硝基偶氮氯膦催化动力学光度法测定痕量钴的研究

研究了在ｐＨ７．０磷酸盐介质中，钴催化Ｈ２Ｏ２氧化二溴硝基偶氮氯膦色反应，建立了催化光度法测定痕量钴的新方法，其检出限为５×１０＾－７ｇ／Ｌ，在０．５－３２μｇ／Ｌ范围内，钴与ｌｇ呈良好的关系。     

Kinetic determination of trace levels of selenium(IV) and total selenium by Nile Blue A/hydrogen peroxide method

A kinetic method for the determination of selenium(IV) traces is proposed, based on its inhibitory action on the oxidation of Nile Blue A by hydrogen peroxide in phosphate buffer (pH 10.5). A linear dependence was established between the rate of the proposed indicator reaction and selenium concentration in the range 9.5 × 10^–2-1.58 ng cm^–3. The experimental conditions of maximal selenium effect were established. Selenium, determined by the tangent method, was determined at concentrations over the range 0.22–1.26 ng cm^–3, with relative standard deviations up to 4.5%. The reaction rate was followed spectrophotometrically. The effect of foreign ions on the accuracy of this method was also investigated. The method was applied to the determination of selenium in pharmaceutical preparations and wheat flour.     

Polymer crystallization dynamics,as reflected by differential scanning calorimetry. Part 2: Numerical simulations

With the aid of a model for the kinetics of polymer crystallization, as put forward in previous publications, the shape of DSC-curves and their position on the temperature scale were simulated for various conditions of heat transfer in the apparatus. It turns out that the outcome is very dependent on the assumptions made with respect to these heat transfer conditions. For the ideal condition — no temperature differences between sample, pan and furnace — an invariable shape is predicted for the DSC-curves. They only shift to lower temperatures with increasing cooling rates. For more realistic conditions, the curves not only shift but become broader and their maxima decrease. They show a more familiar appearance. These calculations are very involved, however, A simple balance equation is shown to yield equivalent results, if a dimensionless characteristic number like the Nusselt number remains considerably smaller than one. This number contains an effective heat transfer coefficient between sample and furnace which, surprisingly, should not be too high. Apparently, the heat capacity of the pan does not play an important role under these conditions. This is investigated in Appendix II. Appendix I describes the procedure of the numerical simulations.