氯钌酸铵的热分解特性及动力学  

Thermal decomposition characteristics and kinetics of diammonium hexachlororuthenate

作　　者：龚斯宇 刘鹏 刘秉国[1,2,3] 宇文超[1,2,3] 董希志 董恩华 GONG Si-yu;LIU Peng;LIU Bing-guo;YUWEN Chao;DONG Xi-zhi;DONG En-hua(Faculty of Metallurgy and Energy Engineering,Kunming University of Science and Technology,Kunming 650093,China;Key Laboratory of Unconventional Metallurgy,Ministry of Education,Kunming 650093,China;State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization Co-constructing by Province,Kunming 650093,China)

机构地区：[1]昆明理工大学冶金与能源工程学院,昆明650093 [2]非常规冶金省部共建教育部重点实验室,昆明650093 [3]省部共建复杂有色金属清洁利用国家重点实验室,昆明650093

出　　处：《中国有色金属学报》2022年第8期2421-2432,共12页The Chinese Journal of Nonferrous Metals

基　　金：国家自然科学基金资助项目(51961020)。

摘　　要：采用同步热分析法研究氯钌酸铵(NRC)在氩气气氛中、不同升温速率(5、10、15和20℃/min)下的热分解机理,利用非模型法(FWO、KAS、Friedman和Starink方法)、模型法和Z(α)主图法研究NRC的热分解反应动力学。结果表明,NRC的热分解过程分为两个阶段,第一阶段热分解反应在310-380℃范围内进行,质量损失率为30%-40%,产物为(NH_(3))_(4)Ru_(3)Cl_(12)、NH_(3)和HCl气体,热分解反应的表观活化能为254.45kJ/mol,指前因子的对数值为46.67 min^(-1),热分解动力学模型为气体扩散体积收缩模型,并得出其机理函数表达式为g(α)=1-(1-α)^(1/3);第二阶段热分解反应发生在380-430℃,质量损失率为28%-39%,热分解产物为N_(2)、HCl气体和单质Ru,热分解反应的表观活化能为222.59 kJ/mol,指前因子的对数值为39.55min^(-1),热分解动力学模型为随机成核随后生长模型,并得其机理函数表达式为g(α)=[-ln(1-α)]^(1/2)。The thermal decomposition mechanism of diammonium hexachlororuthenate (NRC) in argon atmosphere at different heating rates (5,10,15 and 20℃/min) was studied by synchronous thermal analysis method,and the thermal decomposition kinetics of NRC was studied by the non-model method (FWO,KAS,Friedman and Starink method),model method and Z(α) master-plot method.The results show that the thermal decomposition process of NRC is divided into two stages.The first stage of the thermal decomposition reaction is carried out in the temperature range of 310-380℃,the mass loss rate is 30%-40%,and the products are(NH_(3))_(4)Ru_(3)Cl_(12),NH_(3) and HCl gases.The apparent activation energy of the thermal decomposition reaction is254.45 kJ/mol,the logarithmic value of the preexponential factor is 46.67 min^(-1),the thermal decomposition kinetic model is the gas diffusion volume contraction model,and the mechanism function expression is g(α)=1-(1-α)^(1/3).The second stage of thermal decomposition reaction occurrs at 380-430℃,and the mass loss rate is 28%-39%.The thermal decomposition products were N_(2),HCl and Ru.The apparent activation energy of the thermal decomposition reaction is 222.59 kJ/mol,and the logarithmic value of the preexponential factor is 39.55 min^(-1).The kinetic model of thermal decomposition is random nucleation followed by growth model,and the mechanism function expression can be obtained as g(α)=[-ln(1-α)]^(1/2).

关 键 词：氯钌酸铵 热分解 非等温动力学 动力学三因子 

分 类 号：TF838[冶金工程—有色金属冶金]