化合物[NH_3CH_2CH_2NH_3][CuCl_4]的热稳定性及其分解动力学研究  

Study on Thermal Stability and Thermal Degradation Kinetics of [NH_3CH_2CH_2NH_3][CuCl_4]

作　　者：郭满满[1] 肖卓炳[1] 彭密军[1] 郭瑞轲[1] 

机构地区：[1]吉首大学林产化工工程湖南省重点实验室,湖南张家界427000

出　　处：《广州化工》2011年第18期44-48,共5页GuangZhou Chemical Industry

基　　金：湖南省自然科学基金资助项目(10JJ6024);湖南省科技厅资助项目(2009FJ3045)

摘　　要：利用液相法合成了[NH3CH2CH2NH3][CuCl4],并对化合物的热稳定性、热分解及其动力学进行了研究。采用TG-DTG技术研究化合物[NH3CH2CH2NH3][CuCl4]的热分解,并应用微分法(Achar法)、Coast-Redfern法、Kissinger法、Ozawa法对非等温动力学数据进行处理,发现晶体的第一步分解是二维扩散反应,n=2,机理函数积分形式g(α)=[1-(1-α)1/2]2和微分形式f(α)=(1-α)1/2[1-(1-α)1/2]-1,表观活化能Ea=192.56 kJ.mol-1,指前因子A=2.13×1016s-1。标题化合物的第二步分解是化学反应,机理函数积分形式g(α)=(1-α)-1-1和微分形式f(α)=(1-α)2,表观活化能Ea=164.70 kJ.mol-1,指前因子A=2.90×1012s-1。[NH3CH2CH2NH3] was prepared by the liquid phase method.Its thermal degradation kinetics was studied under the non-isothermal condition by TG-DTG technique.The non-isothermal kinetic datas were analyzed by means of the Achar method,Coats-Redfen method,Kissinger methed and Ozawa methed.The most possible reaction mechanisms was suggested by comparison of the kinetic parameters.The results showed that [NH3CH2CH2NH3] underwent a three-stage thermal decomposition process.The most probable kinetic mechanisms of the former two-stage thermal decomposition were two-dimensional diffusion and chemical reaction,and the corresponding mechanisms follew jander equation and reaction order.The differential and integral mechanism function were f（α）=（1-α）1/2[1-（1-α）1/2]-1,g（α）=[1-（1-α）1/2]2 at the first stage and f（α）=（1-α）2,g（α）=（1-α）-1-1 at the second stage,respectively.The activation energy Ea/（kJ·mol-1） of the former two stages were 192.56 and 164.70 and their A/（s-1） were 2.13×1016 s-1 and 2.90×1012 s-1,respectively.

关 键 词：层状钙钛矿 四氯合铜酸乙二胺 TG-DTG技术 热分解动力学 

分 类 号：TQ522.63[化学工程—煤化学工程]