物理化学学报 >> 2020, Vol. 36 >> Issue (6): 1905062.doi: 10.3866/PKU.WHXB201905062

所属专题: 热分析动力学和热动力学

综述 上一篇    下一篇

热分析动力学研究方法的新进展

任宁1,*(),王昉2,张建军3,*(),郑新芳1   

  1. 1 邯郸学院,化学化工与材料学院,河北省杂环化合物重点实验室,邯郸 056005
    2 南京师范大学,分析测试中心,南京 210023
    3 河北师范大学,分析测试中心,化学与材料科学学院,石家庄 050024
  • 收稿日期:2019-05-20 录用日期:2019-06-10 发布日期:2019-12-18
  • 通讯作者: 任宁,张建军 E-mail:ningren9@163.com;jjzhang6@163.com
  • 作者简介:任宁,2006年硕士毕业于河北师范大学。现为邯郸学院化学化工与材料学院副教授。主要研究方向为稀土配位化学及热分析动力学|张建军,河北师范大学分析测试中心研究员,主要从事热分析动力学,化学热力学与热分析及稀土配位化学等研究
  • 基金资助:
    国家自然科学基金(21803016)

Progress in Thermal Analysis Kinetics

Ning Ren1,*(),Fang Wang2,Jianjun Zhang3,*(),Xinfang Zheng1   

  1. 1 College of Chemical Engineering & Material, Hebei Key Laboratory of Heterocyclic Compounds, Handan University, Handan 056005, Hebei Province, P. R. China
    2 Center for Analysis and Testing, Nanjing Normal University, Nanjing 210023, P. R. China
    3 Testing and Analysis Center, College of Chemistry & Material Science, Hebei Normal University, Shijiazhuang 050024, P. R. China
  • Received:2019-05-20 Accepted:2019-06-10 Published:2019-12-18
  • Contact: Ning Ren,Jianjun Zhang E-mail:ningren9@163.com;jjzhang6@163.com
  • Supported by:
    the National Natural Science Foundation of China(21803016)

摘要:

“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。

关键词: 热分析动力学, 动力学方程, 等转化率法, 活化能, 阿累尼乌斯公式

Abstract:

Thermal analysis (TA) is a technology that can be applied to evaluate the relationship between the physical properties of substances and temperature changes under programmed temperature control. It has been widely used in many fields and is particularly useful for determining the thermal stability and service life of polymers and other materials, the stability of drugs, and the danger of flammable and explosive materials. Simultaneously, the mechanism of dehydration, decomposition, and degradation of inorganic materials or dissociation of complexes can be studied and the decomposition rates of environmental pollutants can be estimated. Recently, TA kinetics has become the most extensively studied topic in TA research. The main purpose of kinetic analysis is to obtain the three kinetic triplets of a reaction process, namely, activation energy Ea, pre-exponential factors A, and and mechanism function f(a). For a solid-state reaction, many mathematical models and corresponding data processing methods can be used for the study of TA kinetics. These methods can be classified as either isothermal or non-isothermal methods and further divided into integral and differential methods in the form of the kinetic equation. These equations can be divided into a single scanning rate and multiple scanning rate methods (isoconversion method) by the operation method. The isoconversion method can calculate activation energies without the mechanism function, and the complexity of the reaction can be determined by the change in activation energy as a function of conversion rate. Therefore, the International Confederation for Thermal Analysis and Calorimetry (ICTAC) recommends the isoconversion method for processing TA data. Because of the limitation of traditional isoconversion methods, novel isoconversion methods have been proposed over the past 10 years. The relationship among the existing dynamic analysis methods must be complementary, instead of competitive, because the reliability of the analysis results can be improved only through complementarity. Further efforts to popularize modern integral and differential methods with equal conversion rates are essential. Herein, the progress in isoconversion method development is briefly introduced. A novel kinetic equation and seven new isoconversion methods are reviewed, and the characteristics and limitations of these methods are discussed. In addition, the development trends and prospects of TA kinetics research methods are highlighted. We suggest that the Arrhenius formula should be modified on the basis of the relationship between the rate constant and temperature. The rate equation that is more suitable for non-isothermal and heterogeneous reactions should be used. The mechanism of multi-step solid-state reactions should be studied in depth, and unified standards must be adopted for the study of thermal decomposition kinetics. This represents imminent and important progress in the study of TA kinetics.

Key words: Thermal analysis kinetics, Kinetic equation, Isoconversion method, Activation energy, Arrhenius formula

MSC2000: 

  • O643