模拟热谱曲线法（Ⅰ）——简单级数化学反应

提出模拟各种简单级数化学反应的普适热谱曲线方程△＝ａｔｅ＾－ｋβｔ，建立了一种新的热动力学研究法－－模拟热谱曲线法，导出了简单级数化学反应的动力学参数Ｋｎ和速率常数ｋｎ的计算式。实验说明该方法对研究慢反应及较快的反应均适用，还能用于求热动力学体系的冷却常数。     

热动力学对比参量法 --简单级数反应

根据化学反应动力学和热动力学基本理论, 建立了简单级数反应的热动力学对比参量方程, 提出了一种新的热动力学研究法--对比参量法. 利用该法可以从一张热谱图上同时解析出化学反应的速率常数、半衰期和热动力学体系的冷却常数. 实验结果验证了方法的正确性.     

热分析动力学的新进展

综述了热分析法研究非均相体系反应动力学方面的进展，评述了热分析动力学(TAK)现用方法的成功和局限，介绍了新的分析方法和新技术。     

时间参量法Ⅱ.简单级数反应的热谱面积差法

从简单级数反应的热动力学方程出发,将时间作为已知参量,提出了一种新的热动力学研究法——简单级数反应的热谱面积差法.该法不需反应进行到底便可求解化学反应的速率常数.实验结果验证了方法的正确性.     

热动力学的研究(Ⅰ)——热动力学的理论和方法

本文根据化学反应热与反应进度的对应关系,导出了热动力学体系的基本方程和热动曲线的解析表达式。并提出了一种新的热动力学研究法。     

热动力学特征对比参量法及其应用研究

基于简单级数反应的积分和微分热动力学方程，建立了热动力学特征对比参量 法的数学模型，提出了一种由特征时间参量计算特征对比参量的方法，通过几种不 同级数模型反应的热动力学研究证明了方法的正确性，并利用该法研究了过氧化氢 在磷酸盐缓冲液中氧化对苯醌反应的动力学特征，实验结果表明该反应动力学方程 可以表示为：dC(醌)/dt=kC(醌)C(H_2O_2)~0.5C(H~+)~(-0.5)     

四种苯甲酰丙酮合铜和1，1，1-三氟-3-(2-噻吩基)丙酮合铜的偶氮二吡啶长链配合物的热分析研究

用热重法(TG)研究了4种苯甲酰丙酮合铜和1，1，1-三氟-3-(2-噻吩基)丙酮合铜的偶氮二吡啶一维长链聚合配位化合物在动态氮气气氛下的热行为，结合元素分析和能谱技术，确定了各步分解的组分，并讨论了其晶体结构与热性质的关系。应用新的非线性等转化率法，并结合其他方法考察了各步分解反应的属性，进行了动力学分析，并试对传统动力学方法的适用性进行了讨论。     

自函数回归法: 连续一级反应的热动力学研究

根据热动力学基本原理,推导出了连续一级反应热动力学自函数递推方程,从而建立了一种新的连续一级反应的热动力学研究法---自函数回归法.应用该法分别研究了丁二酸二乙酯和邻苯二甲酸二乙酯皂化反应的热动力学。     

时间参量法4: 简单级数反应的双谱法

根据简单级数反应的热动力学方程,提出了一种新的热谱曲线解析方法---简单级数反应的双谱法。该法利用两张热谱曲线的特征热谱数据α~m^*,Δ~m,和t~m,便能以简单的数学形式计算出化学反应的速率常数。实验结果验证了方法的正确性。     

时间参量法4: 简单级数反应的双谱法

根据简单级数反应的热动力学方程,提出了一种新的热谱曲线解析方法---简单级数反应的双谱法。该法利用两张热谱曲线的特征热谱数据α~m^*,Δ~m,和t~m,便能以简单的数学形式计算出化学反应的速率常数。实验结果验证了方法的正确性。     

Thermoanalytical investigation of high-temperature transformations of polyimides

The results of thermoanalytical investigations of polyimides are considered. It is shown that combined application of methods of thermal analysis makes it possible not only to determine the thermal and structural characteristics of polyimide articles but also to observe the formation of polyimides, their thermal degradation and transformation into new structures under the influence of high temperatures.     

Utilization of Derivatograph for Study of Synthesis of New Inorganic Pigments

In our laboratory, the synthesis of new inorganic pigments is followed by thermal analysis using a Derivatograph apparatus. The first information about the temperature region of the formation of the pigments investigated is provided by thermal analysis. The main attention is directed to the preparation of high-temperature colour pigments, lightfastness colour pigments, anticorrosive pigments, new ecological inorganic pigments and luminescent pigments. All inorganic pigments are useful for colouring of ceramic glazes, enamels, plastics, paints, cements and other building systems. The synthesis of all these pigments is based on temperature calcination of starting materials. Tens of new inorganic pigments have been prepared thanks to methods of thermal analysis. These synthesis are described in more than 100 Czech patents. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermoanalytische methoden in der chemischen verfahrensentwicklung

Thermal analysis methods are used in process development for the investigation of chemical kinetics, for the evaluation of thermal hazards and for the determination of caloric design data. For these applications heat-flow methods are preferably used.This paper gives a survey of methods and instruments, and then presents a new “bench scale heat-flow calorimeter”. The use of this new instruments is illustrated by investigations on the formation of a Grignard compound and on the isomerisation of trimethyl-phosphite.     

Synthesis and thermal degradation kinetics of cellulose esters

Polymers that are biodegradable currently achieve high interest in material science since they offer reductions of landfill space during waste management as well as new end-user benefits in various fields of applications. In this work, cellulose esters such as cellulose benzoate, cellulose succinate and cellulose cinnamate were prepared using dimethylaminopyridine along with dimethylaminopyridine-p-toluene sulfonic acid catalyst. Films of cellulose esters were cast from solution. Cellulose esters were characterized by spectral methods such as infrared, nuclear magnetic resonance, thermal method such as thermogravimetric analysis. Various methods of kinetic analysis were compared in the case of thermal degradation of the cellulose and cellulose esters. Copyright­© 2003 John Wiley & Sons, Ltd.     

Kinetic Analysis and Modeling of Thermal Decomposition of Ammonia Borane

Ammonia borane (AB; NH₃BH₃) is one of the most promising materials for hydrogen storage applications, mainly due to its high gravimetric hydrogen storage capacity of 19.6 wt%. In this paper, we present an exclusive kinetic analysis of AB thermolysis. Three methods are used for kinetic analysis of the thermal decomposition of AB, namely the Kissinger method, isoconversional model‐free fitting method, and solid‐state kinetics model–based method. Finally, a need to device a new model for thermal kinetics of AB was observed and hence a new kinetic model for AB thermolysis is proposed.     

Quantitative Size Exclusion Chromatography: Assessing New Developments

Abstract

Methods of assessing new technology are achieving increased importance because rapid technological changes cause obsolescence of evaluations before they are completed. Users now must often evaluate the specific version of the new technology that they receive. Four major areas are used here to provide examples of assessment methods: high resolution columns, coupled concentration-molecular weight-differential viscometer detectors, flow rate monitoring using a thermal pulse flowmeter and determination of Mark-Houwink constants from polydisperse standards. Specific methods of assessment examined centre about error analysis and sensitivity analysis. Several of the methods use the conventional calibration curve. The idea of correction priority (i.e. thoroughly examining the most fundamental significant corrections first) is emphasized.     

Evaluation of the stability of substituted InF3 glasses by differential thermal analysis

The thermal properties and devitrification behaviour of substituted InF₃ glasses were studied by means of differential thermal analysis. A comparison of various simple quantitative methods to assess the level of stability of multicomponent fluoride glass systems was also made. Most of these methods are based on critical temperatures. In this paper, a new parameter,k _d(T), is introduced to the stability criteria. The stabilities of several substituted InF₃ glasses were evaluated experimentally and correlated with the activation energies of crystallization via this new kinetic criterion and compared with those evaluated by other criteria.     

Thermal kinetic studies on the decompositions of cefuroxime lysine in different atmospheres and heating rates

The thermal decomposition of a new antibiotic agent, cefuroxime lysine, was investigated by thermogravimetry analysis/derivative thermogravimetry and differential scanning calorimetry (DSC) methods in anoxic and oxidative environments. The influence of heating rates (including 5, 10, 15, and 20 °C/min) on the thermal behavior of cefuroxime lysine was revealed. By the methods of Kissinger and Flynn–Wall–Ozawa, the thermal kinetic parameters of activation energy and pre-exponential factor for the exothermic processes under non-isothermal conditions were calculated using the analysis of corresponding DSC curves.     

Development of a model for compensating the influence of temperature gradients within the sample on DSC-results on phase change materials

The use of phase change materials (PCMs) in thermal storage is not a new concept, but engineers are continually finding new ways to utilize them in a wide range of applications. A PCM takes advantage of high latent heat in the phase change process to store large amounts of heat while undergoing only a small change in temperature. This property makes PCMs suitable for thermal storage purposes in a wide range of engineering applications. Due to the nature of these applications, it is vital to have a precise knowledge of the thermal characteristics of any PCM. Unfortunately, due to the low thermal conductivities and high latent heats found in PCMs, current measuring tools such as differential scanning calorimetry, provide inconsistent results. This paper conjectures that these errors come from the effects of low thermal diffusivity samples as well as improper data analysis methods.