Experimental and quantum-chemical investigation of thermolysis of adamantyl-substituted organosilicon peroxides

The kinetics and mechanism of thermal decomposition of adamantyl-containing organosilicon peroxides in a solution inn-nonane were studied. The relationship between the structure of the peroxide and the rate and mechanism of thermolysis was established. The effect of the peroxide structure on the electronic characteristics of the peroxide bond was studied by the MNDO method. The heterolytic rearrangement occurring during the decomposition of peroxides was analyzed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya No. 7, pp. 1317–1320, July, 1998.     

Thermal decomposition of mechanically activated arsenopyrite

The changes in specific surface area and structure disorder of mechanically activated arsenopyrite were investigated. The rate of nonoxidative decomposition of mechanically activated arsenopyrite was increased almost 10-times when compared with nonoxidative decomposition of a non-activated sample. An empirical linear relationship was found (r=0.996) between the rate constant of decomposition and the ratio of specific surface to transmission of the absorption band of arsenopyrite at $\bar \nu = 370 cm^{ - 1} $ . This relationship enables us to arrange the reaction 4FeAsS→4FeS+As₄ among structure-sensitive reactions.     

Some Criteria for Deciding upon the Support Effect

Criteris for deciding upon the support effect by the thermal decomposition of precursor/support systems are discussed. Instead of the linear relationship between lgA and E, two new criteria determined by the calculated rate maximum were suggested. Dimensionless criteria based on the rate, conversion and temperature values at the inflexion point of the TG diagram lead to a parameter able to describe the support effect in a synthetic and quantitative manner. The experimental data were the TG-curves for the decomposition of ammonium metavanadate, molybdic acid and ammonium phosphomolybdate, supported on carborundum and silica. This revised version was published online in August 2006 with corrections to the Cover Date.     

Computational techniques applied to the study of the oxidation kinetics of iron and molybdenum cyanocomplexes by peroxynitrous acid

The oxidation kinetics of iron and molybdenum cyanocomplexes by peroxynitrous acid were studied by computational techniques. The rate constants of ONOOH decomposition and substrate oxidation were calculated by fitting the experimental data to the solution of the ordinary differential equations mechanism. There is a linear relationship between the rate constants which is solved by varying the initial concentration of one of the reactive species. The rate constants of the steps involved in ONOOH decomposition were also determined following the same procedure and considering a linear relationship between the rate constants. The results are consistent with the values previously found using the conventional method of integration, and they validate the prior steady state assumption. Copyright © 2008 John Wiley & Sons, Ltd.     

The relationship between differential thermal analysis data and the detonation characteristics of polynitroaromatic compounds

The thermal stabilities of 37 polynitroaromatic compounds are specified by means of non-isothermal DTA. The initial temperatures of the exotherms T_D, as well as the Piloyan decomposition activation energies, E, of the compounds are determined.A relationship is derived between ET^?1_D and the detonation characteristics of the compounds being measured. It is shown that allocation of the measured compounds to separate forms of the determined relationship is, in addition to thermochemical factors, also determined by the electron configuration and steric conditions in the reaction center of the given molecule.     

天然气水合物浆体分解对其在垂直管中流动特性影响的研究

针对天然气水合物浆体开采提升过程中水合物分解的问题,采用Euler多相流模型以及Finite-Rate/Eddy-Dissipation模型对天然气水合物浆体垂直管输的固-液两相流动以及气-液-固三相流流动特性进行研究。结果表明,受天然气水合物分解产生的气体影响,天然气水合物颗粒的速度分布、体积浓度分布均随高度的变化呈现出波动-均匀-波动的规律;水合物分解对浆体管道运输具有减阻作用,并提出天然气水合物浆体分解工况下,其流动速度不应低于3m·s~(-1);通过对管道的阻力特性分析,拟合出水合物分解下的水力提升阻力损失与流速的关系式,为天然气水合物浆体管道的经济提升参数提供指导。     

Characterization of the liquid product recovered through pyrolysis of PMMA-ABS waste

Thermal decomposition of waste polymethylmethacrylate-acrylonitrile-butadiene-styrene (PMMA-ABS) blend has been carried out using analytical and lab-scale pyrolysis methods in order to identify the substantial components appearing in the liquid product. Additionally decomposition characteristics of the blend have been investigated regarding the possible interrelation between the two components during the pyrolysis. The interactions between PMMA and ABS seem to modify the decomposition characteristics of the ABS, resulting in a lower degradation temperature than that of pure ABS. Moreover the simultaneous decomposition results in recombination of the products yielding new volatile compounds. During batch pyrolysis relatively high amount of gas production was observed, that is in contradiction with the results obtained by analytical pyrolysis and the data found in the literature where pyrolysis of the PMMA as well as the ABS was reported to yield low amount of gas products. The liquid product retrieved from thermal decomposition has been analyzed with respect to the possible utilization as a propellant. Hence aside from the investigation of contained elements and compounds, determination of density, viscosity, research octane number (RON), calorific value, and gaseous emissions has been carried out as well. The relatively high yield (65 wt%), and outstanding compression tolerance (RON = 110.2) observed at the pyrolysis oil make it a feasible fuel admixture.     

Theoretical and Experimental Investigations of The Decomposition of 10-methylacridinium Halides

10-Methylacridinium chloride, bromide and iodide were prepared in crystalline forms (the first two salts as monohydrates) and subjected to thermogravimetric investigations. Decomposition of the compounds is initially accompanied by the liberation of water (in case of monohydrates), halomethanes and acridine molecules. As decomposition proceeds, side reactions occur which are reflected in a complex pattern of thermogravimetric curves. TG traces corresponding to the initial decomposition stage were used to determine the kinetic characteristics of the thermal dissociation of the salts. MNDO/d, AM1 and PM3 methods were employed independently to examine reaction pathways and to predict thermodynamic and kinetic barriers for the thermal decomposition of the compounds. These data were subsequently supplemented with theoretically determined crystal lattice energies, which enabled the relevant characteristics for the decomposition of crystalline phases to be predicted. The theoretically predicted characteristics are qualitatively comparable with those originating from thermogravimetric investigations, which allows one to believe that both are valid. This revised version was published online in August 2006 with corrections to the Cover Date.     

丁香油-β-环糊精包合物中残存态环糊精的热分解动力学

采用双外推法确定了丁香油-β-环糊精(CD)包合物中残存态β-CD最可能的热分解机制. 基于Flynn-Wall-Ozawa方法对残存态β-CD热分解反应过程的计算结果发现, 活化能(Ea)变化曲线可划分为三个阶段. 第一和第三阶段的曲线轮廓近似平行, 并且都被推定为按照Avrami-Erofe’ev A1.5模型发生热分解反应. 但是在曲线的第二阶段, 出现了一个Ea值近似相等的平台. 为此, 采用确定反应级数的方法考察了该阶段的热分解过程. 研究表明, 反应级数随着温度升高呈现规律性的降低, 表明在这个阶段残存态β-CD分解反应的复杂性. 最后, 比较了游离态β-CD和残存态β-CD在分解过程中红外光谱的变化情况. 结果显示, 它们在1000 cm-1以下的谱图轮廓存在明显差异, 这与计算给出的二者具有不同Ea值的结果是一致的.     

Analysis of the Thermokinetics Under Dynamic Conditions by Relative Rate of Thermal Decomposition

A novel parameter of the relative rate of thermal decomposition has been defined on the basis of an analysis of equation relating the logarithm of the conversion degree on the temperature. The dependence of this parameter on temperature in the dynamic conditions has been analyzed and discussed. The dependence of the relative rate of thermal decomposition is a linear relationship involving two coefficients. These coefficients can be related to the enthalpy and activation energy. The parameter developed has been used for the analysis of a series of consecutive reactions of thermal decomposition of calcium oxalate monohydrate. This revised version was published online in August 2006 with corrections to the Cover Date.     

Effect of sulfur-containing phenols and amines on the decomposition of hydroperoxides

The effect of polyphenol sulfides (PPS) and dithiolthione, the sulfur-containing derivative of acetone anil, on the decomposition of cumyl andn-decyl hydroperoxides (DHP) studied. The decomposition of cumyl hydroperoxide (CHP) in the presence of PPS is a complex multistep autocatalytic process during which an efficient catalyst for CHP decomposition is formed from the initial PPS. The PPS catalyst for CHP decomposition is deactivated in the reaction with peroxy radicals. Kinetic characteristics of the reaction between polyphenol sulfides and CHP are determined. Dithiolthione catalytically decomposes CHP and reacts with n-decyl hydroperoxide DHP in the stoichiometric ratio     

Polytypic transformations during the thermal decomposition of cobalt hydroxide and cobalt hydroxynitrate

The isothermal decomposition of cobalt hydroxide and cobalt hydroxynitrate at different intervals of temperature leads to the formation of Co₃O₄. The phase evolution during the decomposition process was monitored using powder X-ray diffraction. The transformation of cobalt hydroxide to cobalt oxide occurs via three phase mixture while cobalt hydroxynitrate to cobalt oxide occurs through a two phase mixture. The nature of the sample and its preparation method controls the decomposition mechanism. The comparison of topotactical relationship between the precursors to the decomposed product has been reported in relation to polytypism.     

热分析动力学研究方法的新进展

"非等温动力学"作为热分析动力学研究的核心,已经被广泛应用于化学、化工、冶金、地质、药物和环保等重要领域。热分析动力学研究的主要任务是确定机理函数、活化能和指前因子等动力学参数。在众多的热分析动力学研究方法中,"等转化率法"由于其可以在不涉及动力学模式函数的前提下,获得较为可靠的活化能值,因此被国际热分析与量热学协会(ICTAC)推荐使用。本文简要介绍了近十年来提出的热分析动力学研究方法,特别是等转化率方法的研究进展情况,评述了各种方法的特点与局限。同时,展望了热分析动力学研究方法未来的发展趋势。     

碳质与金属催化剂热催化裂解甲烷产氢研究进展

甲烷裂解制氢方法具有产氢纯度高和清洁无污染的特点,被认为是当前最有前景的制氢方法之一.现阶段甲烷裂解制氢的研究工作主要集中于制备活性与稳定性兼备的催化剂.我们综述了近年来甲烷裂解制氢反应中碳质催化剂和金属催化剂两大系列催化剂的研究进展,从载体、活性组分、助剂3个方法对目前催化剂裂解甲烷产氢性能的影响进行了系统分析,总结了反应机理和催化剂的失活与再生情况,在以上基础上对催化剂未来的发展趋势进行了展望.     

超分子中主体热分解行为的多样性分析——残存态环糊精的热分解

指出了只有在主-客体超分子化学中才能出现的主体热分解行为多样性现象, 提出了所谓的残存态主体(survived host)的概念. 残存态主体意指主-客体超分子失去客体后的产物, 它是由分子间弱相互作用所引起的主-客体包合现象的有力佐证. 以残存态环糊精(survived CD)为着眼点, 仔细比较了游离态CD、CD包合物即包结态CD与残存态CD的热分解行为差异性, 据此指出了有关文献在进行包结态CD热分解动力学计算时, 将残存态CD当成包结态CD来处理的一个概念错误.     

Theoretical investigation on the impact sensitivity of tetrazole derivatives and their metal salts

The relative orders of impact sensitivity of tetrazole derivatives and their metal salts are investigated by examining the activation energy for forming azide in the process of thermal decomposition based on PM3-SCF-MO calculations. It is found that there is a parallel relationship between the activation energy and the sensitivity and a good linear relationship between the experimental impact sensitivity of metal salts of tetrazole and the reaction activation energy. It is shown that treating the metal salts of the tetrazole derivatives as the metal derivatives of tetrazole is meaningful.     

Interaction of Pesticides with a β-Cyclodextrin Derivative Studied by Reversed-phase Thin-layer Chromatography and Principal Component Analysis

The interaction of 18 pesticides with a water-soluble -cyclodextrin polymer (BCDP) was studied by reversed-phase thin-layer chromatography and principal component analysis (PCA) was employed for the elucidation of the relationship between the relative strength of interaction and the calculated surface parameters of the guest molecules. Except for penconazole the lipophilicity of the pesticides decrease in the presence of BCDP. PCA indicated that apolar surface parameters are highly positively correlated with the strength of interaction. The data indicate that the agrochemical characteristics (adsorption, leakage, decomposition, etc) of complexed pesticide molecules can be different from those of uncomplexed onesresulting in modified efficacy.     

Rationalizing the Mechanism of Peroxyformate Decomposition: Computational Insights To Understand Solvent Influence

The heterolytic decomposition of tert-butyl peroxyformate to tert-butanol and carbon dioxide, catalyzed by pyridine, is a long-known example of a reaction whose kinetics are strongly affected by solvent polarity. From DFT and ab initio methods together with the SMD implicit solvation model, an extension on the formerly accepted mechanism is proposed. This novel proposal involves the formation of a carbonic acid ester intermediate and its further decomposition, through an unreported pyridine-mediated stepwise route. Computed barriers for this mechanism at DLPNO/CCSD(T)-def2-TZVP are in excellent agreement with experimental kinetic data across different solvents. Furthermore, the strong relationships between activation energies, geometric parameters in the transition state and the characteristics of the different solvents are also analyzed in depth.     

Interaction of Pesticides with a β-Cyclodextrin Derivative Studied by Reversed-phase Thin-layer Chromatography and Principal Component Analysis

The interaction of 18 pesticides with a water-soluble -cyclodextrin polymer (BCDP) was studied by reversed-phase thin-layer chromatography and principal component analysis (PCA) was employed for the elucidation of the relationship between the relative strength of interaction and the calculated surface parameters of the guest molecules. Except for penconazole the lipophilicity of the pesticides decrease in the presence of BCDP. PCA indicated that apolar surface parameters are highly positively correlated with the strength of interaction. The data indicate that the agrochemical characteristics (adsorption, leakage, decomposition, etc) of complexed pesticide molecules can be different from those of uncomplexed onesresulting in modified efficacy.