Kinetic Features of Aerosol Formation in the Branched Chain Process of Dichlorosilane Oxidation under Static Conditions: I. Initiated Ignition

It is found experimentally that the initial pressure of aerosol formation progressively decreases with an increase in the initial concentration of dichlorosilane in the initiated ignition of dichlorosilane mixtures with oxygen at 293 K. The dependence of the maximal aerosol concentration on the total pressure is S-shaped. A generalized kinetic scheme is proposed that qualitatively describes the regularities observed in the experiments. The most important calculated parameters are the heat evolved in the chain process and the dependence of the pressure of the saturated vapor of a new phase on temperature. It is shown that the specific features of branched-chain processes under nonisothermic conditions determine the kinetic regularities of new phase formation. The optimal range of pressures is recommended for obtaining particles with as low dispersivity as possible.     

乙烯中低温点火动力学机理研究

为了研究乙烯中低温燃烧的点火特性,用公开报道的可用于乙烯燃烧的反应动力学机理,模拟了乙烯的点火延时,发现现有机理难于描述乙烯中低温点火延时.根据敏感度分析,找到了对全温度段乙烯点火起重要作用的C₂H₃+O₂=CH₂CHO+O和C₂H₃+O₂=CH₂O+HCO反应,以及对低温点火起关键作用的HO₂参与的反应.通过引入最新报道的关键反应的动力学参数和添加新的反应通道,修正了UCSD机理,使乙烯中低温燃烧的点火延时模拟值更接近实验值.用修正机理模拟点火延时时,出现了低温燃烧的一阶点火和中温燃烧的负温度效应,进一步采用敏感度分析和物质产率分析,解释了这些现象,指出C₂H₄+HO₂反应可以有效缩短低温点火延时,HO₂的生成和消耗是影响乙烯低温一阶点火的主要原因,C₂H₃消耗反应是出现负温度效应的重要原因.     

Ignition with low-temperature plasma: Kinetic mechanism and experimental verification

The results of experiments and calculations performed at the Laboratory of Physics of Nonequilibrium Systems, Moscow Institute of Physics and Technology from 1996 to 2008 to demonstrate the efficiency of low-temperature plasma in initiation of combustion of gas mixtures over a wide range of initial conditions are surveyed. In the studies reviewed, a method for quantitative analysis of kinetic processes during ignition of combustible gas mixtures by nonequilibrium plasma was developed.     

气相色谱法测定点火剂中的三乙基硼

建立气相色谱法测定某点火剂中三乙基硼含量的方法。由于三乙基硼化学活性高,定量困难,采用惰性氛围控制和溶剂稀释的方式,以甲苯为稀释溶剂,三乙基硼可与溶剂很好地分离,并在5~50 mg/m L范围内呈现良好的线性,相关系数r=0.999 2,方法的检出限为0.16μg/m L。采用外标法定量,测定三乙基硼标准溶液的回收率为99.13%~100.19%,测定结果的相对标准偏差小于2%(n=7)。该方法可用于点火剂中三乙基硼含量的质量控制。     

Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

A detailed chemical kinetic model for oxidation of CH₃OH at high pressure and intermediate temperatures has been developed and validated experimentally. Ab initio calculations and Rice–Ramsperger–Kassel–Marcus/transition state theory (RRKM/TST) analysis were used to obtain rate coefficients for , , , and . The experiments, involving CH₃OH/O₂ mixtures diluted in N₂, were carried out in a high‐pressure flow reactor at 600–900 K and 20–100 bar, varying the reaction stoichiometry from very lean to fuel‐rich conditions. Under the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, whereas increasing pressure shifted the ignition temperature toward lower values. Model predictions of the present experimental results, as well as rapid compression machine data from the literature, were generally satisfactory. The governing reaction pathways have been outlined based on calculations with the kinetic model. Unlike what has been observed for unsaturated hydrocarbons, the oxidation pathways for CH₃OH under the investigated conditions were very similar to those prevailing at higher temperatures and lower pressures. At the high pressures, the modeling predictions for onset of reaction were particularly sensitive to the reaction.     

异辛烷/正庚烷/乙醇三组分燃料着火的化学动力学模型

提出一个包括异辛烷、正庚烷和乙醇的三组分燃料的着火动力学模型, 该机理包括50 个组分和193 个反应. 通过路径分析和灵敏度分析, 给出了基础燃料在高低温条件下的不同反应路径和影响氧化过程的重要基元反应. 该机理预测的单组分(异辛烷、正庚烷、乙醇)燃料、双组分基础燃料和三组分燃料的点火延迟时间与实验值有很高一致性. 本文机理包含较少的组分数与反应数, 因而可适用汽油掺烧乙醇的多维计算流体动力学(CFD)数值模拟.     

Kinetic Features of Decomposition of Benzoyl Peroxide in Superbasic Media

Kinetics of decomposition of benzoyl peroxide in superbasic media comprising mixtures of a dipolar aprotic solvent and a strong ionic base is studied. The process occurs in two steps through formation of intermediate perbenzoate anion. The contribution of ionic reactions is controlled by the polarity and dielectric constant of the solvent. The decomposition products are molecular oxygen and an alkali metal benzoate or perbenzoate. These products can be alkylated with butyl bromide in superbasic media.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 5, 2005, pp. 803–808.Original Russian Text Copyright © 2005 by Lyavinets.     

Effect of a Gas Discharge on the Ignition in the Hydrogen-Oxygen System

A kinetic model is constructed for ignition initiated by nonequilibrium gas-discharge plasma in the hydrogen-oxygen system. The model takes into account the effect of the electric field on the dissociation of molecules and on the buildup of active radicals, excited species, and charged species (electrons and positively and negatively charged ions). It is demonstrated by mathematical modeling that the induction period depends strongly on the reduced strength of the electric field (electron temperature). Four reduced kinetic networks are considered, and various components and reactions are shown to exert an effect on the nonthermal initiation of ignition in the H₂-O₂ system by low-temperature plasma.     

Features of Behavior of Isotactic Polypropylene Films upon Pervaporation

The most important aspects of the large-tonnage synthesis of isotactic polypropylene represent a commercial secret. After polypropylene synthesis is completed, catalysts and other substances involved in the formation of the final product pass into the category of worthless and unknown impurities. This circumstance determines the peculiarities and difficulties of studying the behavior of impurities in polypropylene films. In this paper, the interaction of hydrophobic and hydrophilic probe liquids with polypropylene films (membranes) containing such impurities has been studied using pervaporation at different temperatures. The supramolecular structure of the polypropylene films has been successively modified by one- and two-sided hexane sorption. This procedure has decreased the apparent activation energy of permeability during pervaporation of water and acetone. It has been shown that, in the long run, the transmembrane convective pervaporation stream of acetone displaces hydrophobic and hydrophilic impurities from the polypropylene films.     

Gas formation upon γ-irradiation of cement material

The effect of ionizing radiation on cement material was studied over a dose range of up to 2 MGy. Hydrogen is the main gaseous product. Its initial yield is ～0.8 molecule/100 eV. Incorporation of nitrates into the cement compound leads to an almost complete suppression of hydrogen formation. Simulation results show that the cement is characterized by the process of transfer of ionizing-radiation energy between water and the solid components.     

正癸烷燃烧机理及航空煤油点火延时动力学模拟

以单一正癸烷作为国产航空煤油的单组分替代模型, 应用自有的碳氢燃料反应机理生成程序ReaxGen-Combustion构建了燃烧反应的详细机理. 以国产煤油在加热型激波管上的燃烧实验为参考, 对比研究了文献报道的3组分替代模型(模型Ⅰ)、2组分替代模型(模型Ⅱ)以及本文的单组分替代燃烧反应机理(模型Ⅲ)在预测我国航空煤油点火延时特性方面的实用性. 结果表明, 温度在1052~1538 K时, 模型Ⅰ预测的点火延时与实验值相差较大; 模型Ⅲ在温度高于1176 K时的预测值与实验值符合较好, 在1052~1176 K之间时则相差较大; 模型Ⅱ与模型Ⅲ预测值符合很好, 由于前者考虑了低温反应机理, 因而对1052~1176 K区间的预测精度与模型Ⅲ相比有所改善. 计算还发现, 模型Ⅱ中添加的20%(质量分数)1,2,4-三甲基苯对高温段点火延时未产生明显影响.     

Fast Temperature Programming in Gas Chromatography using Resistive Heating

The features of a resistive-heated capillary column for fast temperature-programmed gas chromatography (GC) have been evaluated. Experiments were carried out using a commercial available EZ Flash GC, an assembly which can be used to upgrade existing gas chromatographs. The capillary column is placed inside a metal tube which can be heated, and cooled, much more rapidly than any conventional GC oven. The EZ Flash assembly can generate temperature ramps up to 1200°/min and can be cooled down from 300 to 50°C in 30 s. Samples were injected via a conventional split/splitless injector and transferred to the GC column. The combination of a short column (5 m×0.25 mm i. d.), a high gas flow rate (up to 10 mL/min), and fast temperature programmes typically decreased analysis times from 30 min to about 2.5 min. Both the split and splitless injection mode could be used. With n-alkanes as test analytes, the standard deviations of the retention times with respect to the peak width were less than 15% (n = 7). First results on RSDs of peak areas of less than 3% for all but one n-alkane indicate that the technique can also be used for quantification. The combined use of a short GC column and fast temperature gradients does cause some loss of separation efficiency, but the approach is ideally suited for fast screening as illustrated for polycyclic aromatic hydrocarbons, organophosphorus pesticides, and triazine herbicides as test compounds. Total analysis times – which included injection, separation, and equilibration to initial conditions – were typically less than 3 min.     

Kinetic Features of the Formation of Gaseous Products upon Oxygen-Plasma Surface Treatment of Polyethylene, Polypropylene, Poly(ethylene terephthalate), and Polyimide Films

The results of measurements of the rates of mass loss, formation of gaseous products, and oxygen consumption during the surface treatment of polyethylene, polypropylene, poly(ethylene terephthalate), and polyimide films in a low-pressure oxygen plasma are reported. It was shown that CO₂ and H₂O were produced in the same process involving O(³ P) atoms for all polymers, and the kinetic characteristics of the process were determined. The specific features of the plasma-enhanced oxidative degradation associated with the chemical composition of repeating units of these materials are discussed.     

Kinetic Features of the Grafting of Functionally Active Monomers onto Chitosan

Russian Journal of Physical Chemistry A - The kinetics of the grafting of functionally active monomers N-methylolmorpholine, N-methylol-acrylamide, and N-methylolmethacrylamide onto chitosan...     

Kinetic Features and Mechanism of Alternating Copolymerization of lndene with Maleic Anhydride

The radical copolymerization of indene (IN) with maleic anhydride (MA) was investigated. The charge-transfer complexes (CT complexes) between comonomers were studied by means of spectrophotometric measurements. It was found that the maximum copolymerization rate occurred at a comonomer feed ratio that did not correspond to the composition of the CT complex and the composition of copolymer. It was shown that rate maximum was displaced towards an excess of IN in the solvents with strong donicity. The Acceptor Number of solvent influences neither the initial rate nor the position of the rate maximum. Some kinetic calculations were made to assess values of the cross-propagation rate constants and to elucidate the mechanism of propagation of macromolecular chains.     

Shock‐Tube Experiments and Kinetic Modeling of CH3NHCH3 Ignition at Elevated Pressures

Ignition delay times of CH₃NHCH₃/O₂/Ar mixtures are measured with a shock tube in the temperature range of 1040–1604 K. Different pressures (4, 8, and 18 atm) and equivalence ratios (0.5, 1, and 2) are investigated. A recently developed CH₃NHCH₃ kinetic model is examined, and then modified by adding the hydrogen abstractions from CH₃NHCH₃ by HO₂ and NO₂. The rate constants of the hydrogen abstraction by HO₂ are estimated by analogy to the CH₃OH + HO₂ system, and those of the hydrogen abstraction by NO₂ by analogy to the CH₃NH₂ + HO₂ system. The modified model is well validated against the present measurements. Based on this model, sensitivity analysis and reaction pathway analysis are performed to provide insight into the chemical kinetics of CH₃NHCH₃ ignition. CH₃NHCH₃ is mainly consumed by hydrogen abstractions at low temperatures, and its unimolecular decomposition becomes important at higher temperatures.     

原位傅里叶变换红外光谱跟踪等规聚丙烯在升温过程中的构象变化

自从 Natta[1]首次成功合成高分子量的等规聚丙烯 (i PP)以来 ,红外光谱就被广泛地应用于 i PP的组成和结构的表征[2～ 13] .1 988年 ,Hendra等[3] 采用逐步升温方法 ,静态观察 i PP红外光谱的构象规整谱带随温度的变化 ,发现当温度高于 1 35℃时 ,i PP分子链的活动性增加 ,样品的凝聚态结构发生了明显的变化 .然而 ,他们却未能找出产生这一现象的直接原因 .本文利用快速升温傅里叶变换红外光谱(FTIR)在线跟踪 i PP大分子在升温过程中的分子构象变化 ,并结合其它实验手段 ,阐明了上述现象来源于 i PP非晶区螺旋序列的无序化 .1　实…     

Kinetic Features of the Oxidation of Aliphatic Dialdehydes by Quinolinium Dichromate1

Kinetic data on the rates of quinolinium dichromate oxidation of glyoxal and glutaraldehyde are determined and discussed with reference to aldehyde hydration equilibria. The effect of variations in solvent composition and temperature are studied. The solvent effect is analyzed. Kinetic results support a pathway via a rate-determining oxidative decomposition of a chromate ester of an aldehyde hydrate. A cyclic transition state is suggested; being a Hückel-type system (4n + 2), this is an allowed process.