物理化学学报Issue(2)：391-398,8.DOI:10.3866/PKU.WHXB201511023
两种量热模式下物质热分解的动力学补偿效应
Kinetic Compensation Effect under Two Different Calorimetric Modes for Thermal Decomposition
摘要
Abstract
Thermal analysis calorimeters can be used with different temperature control modes. Dynamic, isothermal, isoperibolic, and adiabatic modes are commonly used. A kinetic compensation effect was discovered when the kinetic parameters were calculated using the Arrhenius equation, based on dynamic and isothermal data. To determine whether the kinetic compensation effect existed in adiabatic mode, accelerating rate calorimetry (ARC) and differential scanning calorimetry (DSC) were used to obtain thermal decomposition curves of dicumyl peroxide (DCP), 40%(w) DCP in ethylbenzene, glucose, and 45%(w) glucose in water. The apparent activation energies (E) and pre-exponential factors (A) were calculated based on the Arrhenius rate constant. An obvious kinetic compensation effect was observed in a plot of lnA vs E for a given sample at different concentrations or for the same set of ARC data analyzed with different reaction orders n. Although the calculated lnA and E values using the dynamic differential scanning calorimetry data were usual y lower than those using the adiabatic ARC data, a significant kinetic compensation effect existed between the two sets of results. This result suggested that the kinetic compensation effect existed between the activation energy and pre-exponential factor in reactions with the same or similar reaction mechanisms, regardless of the temperature control mode.关键词
动力学补偿效应/绝热模式/动态模式/活化能/指前因子Key words
Kinetic compensation effect/Adiabatic model/Dynamic model/Activation energy/Pre-exponential factor分类
化学化工引用本文复制引用
尹瑞丽,陈利平,陈网桦,吴珂,张彩星,李焓,于诚..两种量热模式下物质热分解的动力学补偿效应[J].物理化学学报,2016,(2):391-398,8.基金项目
The project was supported by the National Natural Science Foundation of China (51204099) and Science and Technology Plan Projects of Jiangsu Entry-Exit Inspection and Quarantine Bureau, China (2014KJ59).国家自然科学基金(51204099)和江苏出入境检验检疫局科技计划(2014KJ59)资助项目 （51204099）
