双核[Ni2(en)2(H2O)6(pyr)]·4H2O配合物的热引导脱水:进一步的认识

N. Stojanović, Aleksandra Janićijević, A. Janićijević
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摘要

双核[Ni2(en)2(H2O)6(pyr)]·4H2O配合物在326 ~ 410 K温度范围内发生热促使脱水,呈现不对称的DSC峰。这个过程是吸热的,结果损失了10个分子的水,占样品总质量的26.8%。采用Kissinger法和等转换KAS法分别测定了表观活化能为71 kJ/mol和93 kJ/mol。通过Dollimore的分析确定了可能的反应机理。对不同升温速率下的实验DSC峰进行反褶积,表明脱水机理随升温制度的变化而变化。利用线性补偿效应,确定了不变活化能为61 kJ/mol, Arrhenius指前因子为6·107 min-1。
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THERMALLY GUIDED DEHYDRATION OF BINUCLEAR [Ni2(en)2(H2O)6(pyr)]·4H2O COMPLEX: A FURTHER INSIGHT
Thermally prompted dehydration of binuclear [Ni2(en)2(H2O)6(pyr)]·4H2O complex occurs within a 326 K to 410 K temperature region, presenting an asymmetrical DSC peak. The process is endothermal and results in the loss of 10 molecules of water accounting for 26.8% of the total mass of the sample. Values of the apparent activation energy of 71 kJ/mol and 93 kJ/mol were determined by using Kissinger's and the isoconversional KAS approach, respectively. The probable reaction mechanism was determined by Dollimore's analysis. Deconvolution of the experimental DSC peak on different heating rates shows that the mechanism of dehydration changes with the change in the heating regime. Using the linear compensation effect, values of invariant activation energy of 61 kJ/mol as well as of Arrhenius pre-exponential factor of 6·107 min-1 were determined.
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