双核铕-苯甲酸邻菲咯啉三元络合物非等温热分解动力学研究  

Studies on the Thermal Decomposition Non-isothermal Kinetics of Binuclear Europium Benzoate Ternary Complex with 1,10-Phenanthroline

作　　者：张建军[1] 王瑞芬[2] 王淑萍[2] 白继海[3] 

机构地区：[1]河北师范大学实验中心,石家庄050016 [2]河北师范大学化学学院,石家庄050091 [3]河北科技师范学院计算机系,昌黎066600

出　　处：《分析化学》2004年第10期1371-1374,共4页Chinese Journal of Analytical Chemistry

基　　金：河北省自然科学基金 (No .2 0 2 14 0 ;No .2 0 3 14 8);河北省教育厅自然科学基金 (No .2 0 0 112 1);河北师范大学自然科学基金(No .L2 0 0 1Y12 )资助项目

摘　　要：采用TG DTG和DTA技术研究了Eu2 (BA) 6(PHEN) 2 (BA :苯甲酸根离子 ;PHEN :1,10 邻菲咯啉 )在静态空气中的热分解过程 ,根据TG曲线确定了热分解过程中的中间产物及最终产物 ,运用Acher法、Mad husudanan Krishnan Ninan (MKN)法和Flynn Wall Ozawa法对非等温动力学数据进行分析 ,推断出第一步热分解反应的动力学方程为dα/dt=Aexp(-E/RT) (1-α) 2 ,第一步热分解反应的活化能为 135kJ/mol,活化自由能ΔG为 14 9kJ/mol,活化焓ΔH为 12 9kJ/mol,活化熵ΔS为 - 33J/ (mol·k) ,同时用等温TG法得到失重 10 %为寿终指标的寿命方程为lnτ =- 2 2 .6 6 +1.6 4 6× 10 4/T。The thermal decomposition of Eu-2 (BA)(6) (PHEN)(2) (BA=C6H5COO, benzoate; PHEN=C12H8N2, 1,10-phenanthroline) was studied in static air by thermogravinietry-differential thermogravinietry (TG-DTG) and differentical. thermal analysis (DTA) methods. The intermediate and residue for each step of decomposition were identified from TG curve. The non-isothermal. kinetic data were analyzed by the Achar method, the Madhusudanan-Krishnan-Ninan (MKN) method and the Flynn-Wall-Ozawa method. The possible reaction mechanisms were suggested by comparing with the kinetic parameters. The kinetic equation for the first stage can be expressed as: dalpha/dt=Aexp(-E/RT) (1-alpha)(2). The activation energy E for this step reaction is 135 kJ/mol, the entropy of activation DeltaS is -33 J/(mol.K), the enthalpy of activation DeltaH is 129 kJ/mol, the free energy of activation DeltaG is 149 kJ/mol the lifetime equations at weight-loss of 10% was deduced as lntau=-22.66+1.646x10(4)/T by isothermal thermogravimetric analysis.

关 键 词：苯甲酸 邻菲咯啉 铕络合物 非等温动力学 热分解反应 复合发光材料 

分 类 号：O643.1[理学—物理化学]