Suzhou Dai , Yonggao Yin , Yikai Wang , Bowen Cao , Maurizio Peruzzini , Francesco Barzagli
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引用次数: 0
摘要
氨基甲酸铵(AC)的热化学反应在低品位热利用方面具有巨大潜力。然而,对反应动力学的认识不足限制了其进一步应用。因此,我们利用多个加热程序实验的动力学数据,采用无模型热分析方法和模型拟合热分析方法,对 AC 分解的动力学机理进行了详细研究。各种方法得出的结果是一致的,支持了交流电分解是一个单步控制的多步反应的概念。活化能 E、预指数 A 和最可能的反应模型分别被确定为 56.38 kJ∙mol-1, 2.75 × 106 s-1, f(α)=(1-α)0.7811 。反应机理可推测为在固体 AC 表面迅速生成大量成核点,并在这些成核点上发生表面反应,反应界面的运动控制着反应速率。因此,建立并评估了交流电分解的动力学方程,并预测了不同温度条件下的吸热比功率。
Study on the thermal decomposition kinetics of ammonium carbamate for low-grade heat utilization
The thermochemical reaction of ammonium carbamate (AC) holds significant potential for low-grade heat utilization. However, the insufficient understanding of reaction kinetics limits its further applications. Therefore, a detailed study on the kinetic mechanism of AC decomposition was conducted using both the model-free and model-fitting thermal analysis methods with kinetic data from multiple heating program experiments. The results obtained from various methods are consistent, supporting the concept that AC decomposition is a single-step controlled multi-step reaction. The activation energy E, preexponential factor A, and most probable reaction model were determined to be 56.38 kJ∙mol−1, 2.75 × 106 s−1, f(α)=(1-α)0.7811, respectively. The reaction mechanism can be hypothesized as involving the rapid generation of numerous nucleation sites on the surface of solid AC, where surface reactions occur, with the movement of reaction interface governing the reaction rate. Consequently, a kinetic equation accounting for the AC decomposition was developed and evaluated, and the heat absorption specific power under different temperature conditions was predicted.
期刊介绍:
Thermochimica Acta publishes original research contributions covering all aspects of thermoanalytical and calorimetric methods and their application to experimental chemistry, physics, biology and engineering. The journal aims to span the whole range from fundamental research to practical application.
The journal focuses on the research that advances physical and analytical science of thermal phenomena. Therefore, the manuscripts are expected to provide important insights into the thermal phenomena studied or to propose significant improvements of analytical or computational techniques employed in thermal studies. Manuscripts that report the results of routine thermal measurements are not suitable for publication in Thermochimica Acta.
The journal particularly welcomes papers from newly emerging areas as well as from the traditional strength areas:
- New and improved instrumentation and methods
- Thermal properties and behavior of materials
- Kinetics of thermally stimulated processes