Thermal degradation of a composite solid propellant examined by DSC

The thermal decomposition of ammonium perchlorate (AP)/hydroxyl-terminated-polybutadiene (HTPB), the AP/HTPB solid propellant, was studied at different heating rates in dynamic nitrogen atmosphere. The exothermic reaction kinetics was studied by differential scanning calorimetry (DSC) in non-isothermal conditions. The Arrhenius parameters were estimated according to the Ozawa method. The calculated activation energy was 134.5 kJ mol^-1, the pre-exponential factor, A, was 2.04×1010 min^-1 and the reaction order for the global composite decomposition was estimated in 0.7 by the kinetic Shimadzu software based on the Ozawa method. The Kissinger method for obtaining the activation energy value was also used for comparison. These results are discussed here. This revised version was published online in August 2006 with corrections to the Cover Date.     

动力学抑制光度法测定氨三乙酸

氨三乙酸在分析化学中常作为配位滴定剂和掩蔽剂,在催化动力学分析中常作为活化剂。常量的氨三乙酸的测定已有工业化方法,微量氨三乙酸的测定方法极少。酸性和沸水浴条件下,微量的氨三乙酸对高碘酸钾氧化偶氮胭脂红B褪色的反应具有显著的抑制作用,据此建立     

Kinetic study of isopropanol dehydration over silicoaluminophosphate catalyst

The catalytic dehydration of isopropanol has been studied over a solid acid silicoaluminophosphate type SAPO-5. The reaction was processed varying the temperature and weight hourly space velocity, using a fixed bed continous flow reactor. The isopropanol undergoes inter- and intramolecular dehydration, forming propylene and isopropyl ether, respectively. Nevertheless, the catalyst was selective to the olefin, with an activation energy of the order of 46.1 kJ/mol.     

停流-抑制动力学荧光法测定痕量苯酚

用停流技术研究了在H2SO4介质中,苯酚抑制BrO-3氧化丁基罗丹明B荧光猝灭反应,并探讨了反应机理。基于苯酚对该反应诱导期的影响作用,建立了停流-抑制动力学荧光法测定痕量苯酚的新方法。方法的检出限为1.4×10-8g.L-1,线性范围为0.4~15.0μg.L-1,11次测定7.0μg.L-1苯酚的相对标准偏差为2.1%。本法灵敏、简便,用于测定制药废水和番茄酱样品中痕量苯酚,结果满意。     

催化动力学光度法测定槲皮素

在稀硫酸介质中,槲皮素对KBrO3氧化甲基红褪色反应有明显的催化作用。研究了该反应的最佳条件,建立了测定槲皮素的催化动力学光度法。当甲基红、硫酸、KBrO3的用量分别为0.70 mL、0.30 mL、0.25 mL,反应温度80℃,反应时间8 min时,该法测定槲皮素的线性范围为0.0~0.05 mg/L,检出限为0.002 mg/L。方法用于银杏叶和中草药鱼腥草中槲皮素含量的测定,结果满意。     

Kinetic spectrophotometric method for gold(III) determination

The kinetic spectrophotometric method for Au(III) determination was developed and validated. It was based on the catalytic effect of gold on the oxidation of methylene blue B (3,7di-(dimethyl amino)-10-dehydro-phenotiazin chloride) by ammonium peroxo-disulfate in citric buffer solution. There was the linearity of the calibration curve in the concentration range from 0.09 to 2.90 μg ml⁻¹ Au(III). The relative standard deviation was 2.50% and correlation coefficient of 0.9999. The limit of detection was determined as signal to noise ratio (3:1) and it was 5.5 ng ml⁻¹. The limit of quantification, based on signal to noise ratio 10:1 was 19.25 ng ml⁻¹. The selectivity was tested on the basis of influence of known amounts of different ions in the reaction mixture, upon the reaction rate. Kinetic and thermodynamic parameters were reported for both catalytic and non-catalytic reactions. The method was verified by Au(III) determination in anti-rheumatic drug “Tauredon” and in human urine samples, using ICP-AES as the comparative method. As the method is accurate, reliable, quick and simple it could be useful for clinical and toxicological practice.     

催化动力学光度法测定痕量苯酚

研究了在硫酸介质中苯酚对Ｉ＾－１催化Ｃｅ＾４＋－Ａｓ（Ⅲ）反应的抑制作用及其动力学条件。建立了用催化动力这光度法测定痕量苯酚的新方法，结果表明，在０．００１ｍｏｌ／ＬＣｅ（ＳＯ４）２，０．００１２５ｍｏｌ／Ｌ，Ａｓ２Ｏ３，０．０１ｍｇ／Ｌ，ＫＩ，０．０１２５ｍｏｌ／Ｌ，Ｈ２ＳＯ４和０．１３％（ｗ／ｖ）ＮａＣｌ溶液中测定苯酚，其表面摩尔吸光系数为２．１×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，线性范围     

Thermogravimetric characterization of styrene–divinylbenzene copolymers containing alpha-isopropylaminophosphonic acid groups

A commercial styrene–divinylbenzene copolymer was functionalized by multistep reactions with alpha-isopropylaminophosphonic acid groups. Three different functionalized copolymers were obtained in which the phosphonic groups are in meta (1E), para (2E), and ortho (3E) positions. The thermal behavior was studied using the TG/IR hyphenated technique and kinetic analysis of thermo-oxidation under nonisothermal conditions. The evolved gas analysis confirms the partial thermo-oxidative degradation of polymeric materials, with significant preservation of the aromatic ring. The kinetic analysis was performed by three methods: Friedman, Flynn–Wall–Ozawa, and nonparametric kinetic.     

催化动力学光度法测定芦丁

在氢氧化钠介质中,芦丁对高碘酸钾氧化偶氮胂Ⅲ褪色反应有明显的催化作用,据此建立了测定芦丁含量的催化动力学光度法.最大吸收波长为590nm,该方法的线性范围为0.03～1.0mg/L.对实验数据进行回归处理的线性方程为ΔΑ=0.4485c(芦丁)+0.0011,相关系数为r=0.9985,检出限为0.0167mg/L.该方法简便,快速,灵敏度高,用于实际样品的测定,结果令人满意.     

动力学电位法测定硼

本文根据硼酸，苯乙醇酸，孔雀绿形成三元离子缔合型配合物的反应，用孔雀绿离子选择性电极监测反应速率，在最佳实验条件下，用固定时间法，电位变化与硼量在０．２－５．０μｇ／ｍＬ范围呈线性关系，用於测定标准钢样和玻璃标样中的硼，结果与标准值十分接近。     

阻抑动力学光度法测定水中微量的银

研究了银阻抑高碘酸钾氧化玫瑰桃红R的褪色反应，建立了阻抑动力学光度法测定痕量银的新方法。找到了最佳试验条件，该方法线性范围为0～2．0μg／mL，应用于水中银的测定，结果满意。     

表面活性剂增敏催化光度法测定痕量亚硝酸根

基于稀磷酸介质中,溴化十六烷基吡啶对亚硝酸根催化溴酸钾氧化吡罗红B褪色反应的增敏作用,建立了测定亚硝酸根的表面活性剂增敏催化动力学光度法。加入溴化十六烷基吡啶,灵敏度增大2.2倍。测量亚硝酸根的线性范围为0.005-0.15 mg/L,检出限为0.004/L。用于水及蔬菜中痕量亚硝酸根的测定,结果满意。     

阻抑动力学光度法测定食品中的痕量铜

研究了铜阻抑高碘酸钾氧化玫瑰桃红R的褪色反应 ,建立了阻抑动力学光度法测定痕量铜的新方法 ,找到了最佳试验条件。该法线性范围为 0～ 0 0 0 8μg/mL ,检出限为 0 3 9× 1 0 - 3μg/mL ,应用于食品中铜的测定 ,结果满意     

Kinetic Resolution of Allylic Alcohols Promoted by Electrophilic Selenium Reagents

Abstract

The first example of a kinetic resolution process promoted by an electrophilic selenium reagent is reported. Racemic allylic alcohols react with half equivalents of a selenenylating agent in methanol leading to the regiospecific formation of the corresponding addition products with a very high level of facial selectivity (98% de). The unreacted alcohol can be recovered in a optically enriched form (92% ee).     

Kinetic study of low-pressure H2 multipole discharge

This paper is devoted to the study of kinetic equilibrium among electrons, H₂ molecules, H atoms, and positive H⁺, H ₂ ⁺ , and H ₃ ⁺ ions in a multipole discharge working under low-pressure (1- to 15-m Torr) and moderated current conditions. In such a discharge used either as a H⁺ or a H^– ion source or for plasma-surface interactions, the dependence of the densities of these species versus experimental parameters is of a great interest. In the present situation, the electron energy distribution function (e.e.d.f.) is largely nonmaxwellian. The kinetic model that determines the densities of the plasma species is self-consistently coupled to the e.e.d.f. calculated through the use of the Boltzmann equation. The influence of the main processes, volume ones, and those involving plasma walls is emphasized. An attempt is made to use the profiles of Balmer lines obtained experimentally in order to determine absolute concentrations of H atoms and H ₂ ⁺ ions. Results derived from the experiment are compared to results of the model. Such an analysis of Balmer line shapes appears to be an interesting way to determine, by anin situ nonintrusive method, the absolute concentration of H atoms.     

催化动力学分光光度法测定痕量甲醛

在稀硫酸溶液中,甲醛对溴酸钾氧亚甲蓝褪色反应有催化作用,研究其动力学条件,建立了测定痕量甲醛的动力学光度分析方法。结果表明,该法线性范围为0.00～0．80μg·L^-,检出限3．315×10^-8g·mL^-1。该法用于食用菌、杏仁和漆料的浸泡液中痕量甲醛的测定,标准加入回收率为96．7％～104．2％     

Kinetic study of the heterogeneous Si/H system under low-pressure plasma conditions by means of mass spectrometry

The kinetics of the silicon/hydrogen low-pressure discharge system have been measured using a flow technique and mass spectrometry. Results show that at long residence times the system operates under a partial chemical equilibrium even though it is not at thermodynamic equilibrium. The present work indicates that the decisive parameter controlling the structural properties of the deposit (i.e., the formation of either amorphous or microcrystalline silicon) is the departure of the system from the partial chemical equilibrium.     

Kinetic method for the study of xylan hydrolysis by xylan hydrolases

Summary The Somogyi-Nelson colorimetric method was used in a new manner more suitable for evaluating the kinetics of the enzyme hydrolysis of xylan catalyzed by xylan hydrolases. The values of the Michaelis parameters (Km=5.56 g l^–1 andV=2.94 · 10^–5 M s^–1) were determined.

---

Eine kinetische Methode zur Untersuchung der Hydrolyse von Xylan durch Xylan-Hydrolase

Zusammenfassung Die kolorimetrische Methode nach Somogyi-Nelson wurde nach einem neuen Verfahren zur Verfolgung der Kinetik der hydrolytischen Spaltung von Xylan, katalysiert durch Xylan-Hydrolasen vonAspergillus oryzae, angewandt. Es wurden die Michaelis-Parameter (Km=5.56 g l^–1 undV=2.94 · 10^–5 M s^–1) bestimmt.

     

催化动力学光度法测定痕量邻苯二胺

痕量邻苯二胺能灵敏催化溴酸钾氧化结晶紫褪色。研究了该反应的最佳试验条件,建立了一种测定痕量邻苯二胺的新方法。该法测定线性范围为0.0~2.0μg/L,检出限为8.7×10-7μg/L。用于环境水样中邻苯二胺的测定,结果满意。