【摘要】 合成了高氯酸镨和咪唑(C3H4N2),DL-α-丙氨酸(C3H7NO2)混配配合物晶体.经傅立叶变换红外光谱、化学分析和元素分析确定其组成为[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3.使用具有恒温环境的溶解-反应量热计,以2.0mol?L-1HCl为量热溶剂,在T=(298.150±0.001)K时测定出化学反应PrCl3?6H2O(s)+2C3H7NO2(s)+C3H4N2(s)+3NaClO4(s)=[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3(s)+3NaCl(s)+5H2O(1)的标准摩尔反应焓为?rHm=(39.26±0.11)kJ?mol-1.根据盖!斯定律,计算出配合物的标准摩尔生成焓为?fHm{[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3(s),298.150K}=(-2424.2±!3.3)kJ?mol-1.采用TG-DTG技术研究了配合物在流动高纯氮气(99.99%)气氛中的非等温热分解动力学,运用微分法(Achar-Brindley-sharp和Kissinger法)和积分法(Satava-Sestak和Coats-Redfern法)对非等温动力学数据进行分析,求得分解反应的表观活化能E=108.9kJ?mol-1,动力学方程式为dα/dt=2(5.90×108/3)(1-α)[-ln(1-α)]-1exp(-108.9×103/RT).更多还原

【Abstract】 The crystal of a mixed ligand complex of praseodymium perchlorate with imidazole (C3H4N2)and DL-α-alanine (C3H7NO2) was synthesized and characterized. The empirical formula of the crystal wasdetermined to be [Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3 by FT-IR spectrum, chemical analysis and elemen-tal analysis. The enthalpy of reaction of PrCl3?6H2O(s)+2C3H7NO2(s)+C3H4N2(s)+3NaClO4(s)=[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3(s)+3NaCl(s)+5H2O(l) in 2.0 mol?L-1 HCl solvents was determinedto be ?rHm =(39.26±0.11) kJ?mol-1 by a solution-reaction isoperibol calorimeter at T=(298.150±0.001) !K. According to Hess’s Law, the standard molar enthalpy of formation of the title complex was derived,?fHm {[Pr(C3H7NO2)2(C3H4N2)(H2O)](ClO4)3(s), 298.150 K} = ( - 2424.2 ! ± 3.3) kJ?mol - 1 . Thenon-isothermal thermal decomposition kinetics of the complex in flow atmosphere of high purity nitrogen(99.99%) was studied by TG-DTG techniques. The non-isothermal kinetics parameters were analyzed bymeans of differential (Achar-Brindley-shap and Kissinger method) and integral (Satava-Sastak andCoats-Redfern methods) methods, respectively. The apparent activation energy of the thermal decompositionreaction was obtained to give: E=108.9 kJ?mol-1, and the kinetic equation may be expressed as: dα/dt=2(5.90×108/3)(1-α)[-ln(1-α)]-1exp(-108.9×103/RT).更多还原