模拟热谱曲线法（Ⅲ）——可逆反应

可逆反应是一类重要的复合反应，建立其相应的热动力学研究法有重要意义．刘劲松等[1]建立了可逆反应热动力学的对比进度研究法，曾宪诚等[2]建立了二种可逆反应热动力学无量纲参数研究法．本文根据热动力学理论和文献[3]的基本原理，建立了热导式量热体系的几类（2－2型、2－1型、1－2型）可逆反应通用的模拟热谱曲线研究法．该法无需标定热动力学体系的冷却常数，直接从一张热谱图上同时解析出可逆反应的kf、kb、K，方法更为简便，实用性强，在化学、生化反应的热动力学研究中具有广泛的应用前景．应用该法在15℃、25℃下研究了硝基乙烷…     

热动力学研究的新进展

根据变化过程的放（吸）热速率研究过程动力学规律并融热化学与化学动力学于一体的分支学科称为热动力学。本文回顾了国内外学者在各种量热体系中研究热动力学的进展情况，着重介绍了最近五年中热动力学在化学反应、酶促反应和生物代谢过程研究中的应用，并预测了热动力学在未来十年中的发展趋势。     

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)     

平行反应的热动力学研究法

根据热动力学基本理论, 推导了平行准一级反应和平行准一二级反应的热动力学方程, 建立了热谱解析平行反应动力学参数的热动力学研究法, 并利用该法研究了两个模拟平行反应体系的热动力学, 实验结果验证了方法的正确性.     

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.     

线粒体体外代谢热动力学模型及其演化优化研究

导出了线粒体体外代谢的热动力学方程，探讨了它和指数模型的关系，将演化计算技术引入生物热化学领域，用ＭＴＤ方程和演化计算技术，对文献报导的八种鱼肝线粒体体外代谢的热动力学参数进行了全局优化。     

酶促反应抑制动力学的微量热法研究——氟离子对漆树漆酶催化…

提出一个适合各类可逆性抑制的热动力学方程，并根据各量之间的关系提出了可逆竞争性抑制、非竞争抑制、反竞争性抑制的热动力学判据以及计算表观米氏常数Ｋｍ，ａｐｐ和抑制常数Ｋｉ等酶促反应生化常数的热动力学公式，并实验应用于ＮａＦ对漆树漆酶催化氧化邻苯二胺抑制向量热法温室，实验初步得出此抑制为非竞争性抑制，求出其Ｋｍ，ａｐｐ，Ｋｉ值。     

模拟热谱曲线法(Ⅱ)──不可逆连串-级反应的热动力学研究

研究连串反应的动力学有十分重要的意义，文献［1，2]建立了两种连串一级反应的热动力学研究法．我们在前文[1]的基础上，建立了模拟热谱曲线法．该法可以直接从热导式量热计的热谱曲线上解析出连串一级反应中两步反应的速率常数．应用该法测定了邻苯二甲酸二乙酯和丁二酸...     

热动力学对比进度法V. 连续一级反应的热动力学研究法

本文导出了连续一级反应动力学和热动力学的对比进度方程, 建立了连续一级反应热动力学的数学模型。根据该模型, 可由一次实验的热谱数据同时解析出两步反应的速率常数和摩尔反应焓。采用热导式热量计研究了己二酸二乙酯皂化反应的热动力学, 实验结果验证了本文热动力学模型的正确性。     

热分析动力学数据处理方法的研究进展

综述了最近几年来用热分析法研究固相反应动力学的数据处理方法的新进展，指出了现有方法的成功与局限性，介绍了几种新的动力学处理方法及一种新的热分析技术。     

Coupled thermogravimetric-IR techniques and kinetic analysis by non-isothermal decomposition of Cd<Superscript>2+</Superscript> and Co<Superscript>2+</Superscript> vinyl-phosphonates

The thermal behavior of Cd²⁺ and Co²⁺ vinyl-phosphonates was studied using two different experimental strategies: the coupled TG–EGA (FTIR) technique by decomposition in nitrogen, respectively, air, and the kinetic analysis of TG data obtained in dynamic air atmosphere at four heating rates. The both compounds exhibited a good thermal stability: in nitrogen, only an endothermic dehydration step was observed. In air the Cd²⁺ salt presents the same dehydration step whereas by the Co²⁺ salt two simultaneous processes take place dehydration, respectively, thermooxidative destruction of the vinyl group. The kinetic analysis of the TG data was performed with the Flynn–Wall–Ozawa, Friedman’s, and modified non-parametric kinetic methods. By means of the coupled techniques, some spectroscopic arguments on the reaction mechanism were obtained. The values of the activation energy by the three methods are in good agreement and support the two different suggested mechanism.     

Prediction of thermal stability of fresh and aged parchment

The hyphenated thermal analysis-mass spectrometry technique (TA-MS) was applied for the investigation of the thermal behavior of reference and aged parchment samples. The kinetic parameters of the process were calculated independently from all recorded TA and MS signals. The kinetic analysis showed the distinct dependence of the activation energy on the reaction progress. Such behavior is characteristic for the multistage mechanism of the reaction. The comparison of the kinetic parameters calculated from the different signals i.e. TG, DSC, MS for H₂O, NO and CO₂, however, indicated that they were differently dependent on the aging of the sample. For the parchment samples, the aging almost does not change the kinetics of the decomposition calculated from the DSC data: the influence of aging seems to be too negligible to be detected by these techniques. On the other hand, the much more sensitive mass spectrometric technique applied to the kinetic analysis allowed monitoring of visible changes in the thermal behavior of the parchment samples due to the aging process. The influence of aging was especially visible when the MS signals of water and nitric oxide were applied for the determination of the kinetic parameters. The applied method of the kinetic analysis allowed also the prediction of the thermal behaviour of reference and aged parchment samples under isothermal and modulated temperature conditions. Presented results have confirmed the usefulness of thermoanalytical methods for investigating behaviour of such complicated systems as leather or parchment.     

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。     

Thermal stability of ketoprofen��active substance and tablets

Simultaneous thermoanalytical techniques were used for the characterization of the thermal decomposition of ketoprofen??active substance and tablets. DTA and DSC curves showed that ketoprofen melts before the decomposition. A kinetic study regarding the ketoprofen??active substance??s thermal decomposition was performed under non-isothermal conditions and in a nitrogen atmosphere at five heating rates: 2.5, 5, 7.5, 10 and 15 °C min^?1. The kinetic parameters of thermal decomposition process were obtained from TG/DTG curves using the following differential methods: Friedman isoconversional, Chang, respectively, integral methods: Flynn?CWall?COzawa, Kissinger?CAkahira?CSunose, Coats?CRedfern and Madhusudanan. The careful treatment of the kinetic parameters obtained in certain thermal conditions was confirmed to be necessary as well as a different strategy of experimental data processing.     

Kinetic approach to partially overlapped thermal decomposition processes

Practical usefulness of the kinetic deconvolution for partially overlapped thermal decomposition processes of solids was examined by applying to the co-precipitated basic zinc carbonate and zinc carbonate. Comparing with the experimental deconvolutions by thermoanalytical techniques and mathematical deconvolutions using different statistical fitting functions, performance of the kinetic deconvolution based on an accumulative kinetic equation for the independent processes overlapped partially was evaluated in views of the peak deconvolution and kinetic evaluation. Two-independent kinetic processes of thermal decompositions of basic zinc carbonate and zinc carbonate were successfully deconvoluted by means of the thermoanalytical measurements in flowing CO₂ and by applying sample controlled thermal analysis (SCTA). The deconvolutions by the mathematical curve fittings using different fitting functions and subsequent formal kinetic analysis provide acceptable values of the mass-loss fractions and apparent activation energies of the respective reaction processes, but the estimated kinetic model function changes depending on the fitting functions employed for the peak deconvolution. The mass-loss fractions and apparent kinetic parameters of the respective reaction processes can be optimized simultaneously by the kinetic deconvolution based on the kinetic equation through nonlinear least square analysis, where all the parameters indicated acceptable correspondences to those estimated through the experimental and mathematical deconvolutions. As long as the reaction processes overlapped are independent kinetically, the simple and rapid procedure of kinetic deconvolution is useful as a tool for characterizing the partially overlapped kinetic processes of the thermal decomposition of solids.     

Thermal stability of piroxicam

The application of thermal method is of great importance regarding the pharmaceutical problems such as the control of raw materials, the determination of purity, the qualitative and quantitative analysis of drug formulation, tests of thermal stability and compatibility and the determination of kinetic parameters etc. The purpose of a kinetic investigation is to calculate the kinetic parameters and the determination of the kinetic model for the studied process. The results are further used to predict the system’s behaviour in various circumstances. A kinetic study regarding the piroxicam—active substance’s thermal decomposition was performed under isothermal conditions and nitrogen atmosphere, for the temperature steps: 200, 205, 210, 215 and 220 °C. The TG/DTG data were processed by three differential methods: isothermal—isoconversional, Friedman’s isothermal isoconversional and isothermal model-fitting. The obtained results are in good accord between them, as well as with those obtained under non-isothermal conditions from a previous work and confirm the necessity of the kinetic parameters determining in different thermal conditions, by the adequate calculation methods.     

电荷转移盐(C_3H_5N_2H)_3[PMo_(12)O_(40)]的合成与热分解及光致变色反应动力学

用磷钼酸与咪唑合成了一种新的杂多酸-有机电荷转移盐(C3H5N2H)3[PMo12O40]。通过元素分析、红外光谱、固体漫反射光谱、电子自旋共振及热分析等测试技术对其进行了表征,用单扫描法(Achar法和Coats-Redfern法)对合成化合物的TG分析结果进行了非等温热分解动力学研究。推断结果表明,合成化合物的第1步热分解为球对称的三维扩散机理(n=2),其动力学方程为dα/dt=1.58×108[1-(1-α)1/3]-1(1-α)2/3exp(-40931.0/T),求得分解反应的表观活化能E=340.30kJ/mol,指前因子A=1.05×108s-1。标题化合物对紫外光具有光致变色性质,用固体漫反射光谱研究了其光致变色反应动力学。结果显示,其光致变色反应表现为一级或准一级动力学,速率常数k=9.80×10-5s-1。     

Determination of kinetic parameters for the thermal degradation of polymers by the quasilinearization technique

The thermal degradation of polymers is explored generally by the experimental technique of thermogravimetry (TG). Existing mathematical methods for processing dynamic TG data to obtain kinetic parameters for non-linear models require data obtained at a constant rate of temperature rise and employ one or more graphical techniques, which are time-consuming and lead to some inaccuracy. A recently developed numercial approach to the determination of kinetic parameters which avoids the forementioned problems and provides a rapid, flexible, systematic, and accurate technique is the Bellman-Kalaba method of quasilinearization.     

由热重数据计算动力学参数

热重法(TG)是一种动态测量技术,可在程序升温或降温情况下对给定物质或体系提供一个连续的,以温度或时间为函数的重量变化曲线,所以由它跟踪反应能给出反应动力学的有关信息。这种非等温法与早期使用的等温法相比,有快速、连续和需要较少实验数据等优点,近年来在动力学研究方面得到广泛应用,但还只限于研究下列几种类型的简单