活化能
化学
热分解
赤铁矿
反应机理
热重分析
分解
等温过程
反应速率
二茂铁
速率决定步骤
热力学
动能
反应级数
物理化学
化学工程
动力学
无机化学
催化作用
反应速率常数
有机化学
矿物学
电化学
物理
电极
量子力学
工程类
作者
Meenakshi Chakraborty,Sukumar Kundu,A. Bhattacharjee
出处
期刊:RSC Advances
[The Royal Society of Chemistry]
日期:2023-01-01
卷期号:13 (50): 34972-34986
摘要
Thermal decomposition of a mixture of ferrocene carboxaldehyde and oxalic acid dihydrate in O2 atmosphere produced rod-like hematite nanomaterial. The decomposition reaction was complex as evident from the overlapped multistep reaction steps in the non-isothermal thermogravimetry (TG) profiles obtained in the 300-700 K range. A peak deconvolution method was applied to separate the overlapped reaction steps. The multistep TG profiles were successfully deconvoluted, which showed that the decomposition occurs in six individual steps. However, it was found that only the last three reaction steps were responsible for the production of hematite. To estimate the activation energy values for these thermal reactions, six model-free integral isoconversional methods were used. The activation energy value significantly depends on the extent of conversion in each step; however, the nature of its dependence significantly different for each step. The most probable stepwise reaction mechanism functions for the solid-state reactions were obtained using the master plot method. The reaction mechanism was found to be different for different steps. Utilizing the activation energy and reaction mechanism function, the reaction rates of decomposition for each step were determined. To substantiate the validity of the assumed kinetic models, the experimental conversion curves were compared with the constructed ones, and the agreement was quite reasonable. The conversion-dependent thermodynamic parameters were obtained utilising the estimated kinetic parameters. Role of the co-precursor in the thermal reaction of the precursor was plausibly revealed. The present study describes how the use of a co-precursor significantly enhances the thermal decomposition of the precursor, how hematite nanomaterials can be synthesized from a co-precursor driven solid state reaction at low temperatures, and how the kinetic calculations facilitate the understanding of the solid-state reaction process. This study proposes the use of a suitable combination of precursor and co-precursor for solid-state thermal synthesis of iron-based nanoparticles using organo-iron compounds as precursor and also illustrates the effective application of the thermal analysis technique to understand the decomposition reaction.
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