(1. 昆明理工大學(xué) 冶金與能源工程學(xué)院，昆明 650093；
2. 非常規(guī)冶金省部共建教育部重點(diǎn)實(shí)驗(yàn)室，昆明 650093；
3. 省部共建復(fù)雜有色金屬清潔利用國家重點(diǎn)實(shí)驗(yàn)室，昆明 650093)
摘 要: 采用同步熱分析法研究氯釕酸銨(NRC)在氬氣氣氛中、不同升溫速率(5、10、15和20 ℃/min)下的熱分解機(jī)理，利用非模型法(FWO、KAS、Friedman和Starink方法)、模型法和Z(α)主圖法研究NRC的熱分解反應(yīng)動力學(xué)。結(jié)果表明，NRC的熱分解過程分為兩個(gè)階段，第一階段熱分解反應(yīng)在310~380 ℃范圍內(nèi)進(jìn)行，質(zhì)量損失率為30%~40%，產(chǎn)物為(NH3)4Ru3Cl12、NH3和HCl氣體，熱分解反應(yīng)的表觀活化能為254.45 kJ/mol，指前因子的對數(shù)值為46.67 min-1，熱分解動力學(xué)模型為氣體擴(kuò)散體積收縮模型，并得出其機(jī)理函數(shù)表達(dá)式為g(α)=1-(1-α)1/3；第二階段熱分解反應(yīng)發(fā)生在380~430 ℃，質(zhì)量損失率為28%~39%，熱分解產(chǎn)物為N2、HCl氣體和單質(zhì)Ru，熱分解反應(yīng)的表觀活化能為222.59 kJ/mol，指前因子的對數(shù)值為39.55 min-1，熱分解動力學(xué)模型為隨機(jī)成核隨后生長模型，并得其機(jī)理函數(shù)表達(dá)式為g(α)=[-ln(1-α)]1/2。
關(guān)鍵字: 氯釕酸銨；熱分解；非等溫動力學(xué)；動力學(xué)三因子
（1. Faculty of Metallurgy and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China;
2. Key Laboratory of Unconventional Metallurgy, Ministry of Education, Kunming 650093, China;
3. State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization Co-constructing by Province, Kunming 650093, China）
Abstract: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 (NH3)4Ru3Cl12, NH3 and HCl gases. The apparent activation energy of the thermal decomposition reaction is 254.45 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 N2, 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.
Key words: diammonium hexachlororuthenate; thermal decomposition; non-isothermal kinetics; kinetic triplet
