草酸镧动力学和热分析的等转换和模型拟合方法:动力学参数之间的非线性关系

H. Nayak
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引用次数: 0

摘要

采用无模型和拟合动力学方法对草酸镧的非等温和等温热分解数据进行了分析。当使用Coat-Redfern(CR)方程应用于非等温数据时,广泛使用的模型拟合方法对等温和非等温数据都有很好的拟合效果,但会产生非常模糊的Arrhenius参数值。这些值不能与等温实验所得的值相比较。另一方面,以等转换方法为代表的无模型策略,如Flynn-Wall-Ozawa (FWO)和Kissinger-Akahira-Sunose (KAS),在等温和非等温实验中都强调活化能随转换程度的适当变化。无模型方法被推荐为从等温和非等温数据中获得一致动力学信息的可靠方法。尽管它们的线性相关,动力学参数不表现出等速行为。因此,利用非线性补偿法,动力学三胞胎之间的更大的关联进行了检查。
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Isoconversional and Model-fitting Approaches to Kinetic and Thermoanalytic Study of Lanthanum Oxalate: Nonlinear Relationship between Kinetic Parameters
The data for the nonisothermal and isothermal thermal decompositions of lanthanum oxalate have been analysed using the model-free and model-fitting kinetic techniques. When applied to nonisothermal data using the Coat-Redfern(CR) equation, the widely used model-fitting approach that results excellent fitting for both isothermal and nonisothermal data but produces very ambiguous values of the Arrhenius parameters. These values cannot be compared to those obtained from isothermal experiments. On the other hand, the model-free strategy represented by the iso-conversional method, such as Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS), emphasize propertionate  variation of the activation energy with the degree of conversion for both isothermal and nonisothermal experiments. The model free approach is recommended as a reliable way for obtaining consistent kinetic information from both isothermal and non-isothermal data. Despite their linear correlation, the kinetic parameters do not exhibit isokinetic behaviour. Thus, utilising Nonlinear Compensation Law, a greater association between kinetic triplets was examined.
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