过氧化二异丙苯在空气中的非等温热分解动力学  

Thermal Decomposition Non-Isothermal Kinetics of Dicumyl Peroxide in Air

作　　者：丁阿平[1] 蒋军成[1] 陈发明[1] 

机构地区：[1]南京工业大学城市与工业安全江苏省重点实验室,江苏南京210009

出　　处：《华侨大学学报（自然科学版）》2010年第2期183-186,共4页Journal of Huaqiao University(Natural Science)

基　　金："十一五"国家科技支撑计划重点项目(2007BAK22B04)

摘　　要：采用热重-微分热重(TG-DTG)技术,研究过氧化二异丙苯在动态空气气氛中的热分解过程.运用Starink法,Madhusudanan-Krishnan-Ninan(MKN)法和Achar-Brindley-Sharp-Wendworth(ABSW)法分析非等温动力学数据,推断出过氧化二异丙苯热分解动力学模式为收缩球状R3模型,得到其反应的动力学方程为dα/dt=Aexp(-E/RT)×3(1-α)2/3,热分解反应的活化能E为117.32 kJ.mol-1,活化自由能ΔG≠为123.12 kJ.mol-1,活化焓ΔH≠为113.69 kJ.mol-1,活化熵ΔS≠为-21.41 J.(mol.K)-1.The thermal decomposition of dicumyl peroxide was studied in the flow air atmosphere by thermogravimetry- differential thermogravimetry （TG-DTG） method. The non-isothermal kinetic data were analyzed by the Starink method, the Madhusudanan-Krishnan-Ninan （MKN） method and the Achar-Brindley-Sharp-Wendworth （ABSW） method. The possible reaction mechanisms were suggested by comparing with the kinetic parameters. The thermal decomposition mechanism of dicumyl peroxide in nitrogen was controlled by interface reaction R3. The kinetic equation for thermal decomposition of dicumyl peroxide can be expressed as dα/dt=Aexp（-E/RT） × 3 （1-α）^2/3. The activation energy E for this reaction is 117. 32 kJ · mol^-1 , the entropy of activation △S^≠ is -21.41 J ·（mol · K）^-1 , the enthalpy of activation △H^≠ is 113. 69 kJ · mol^-1 , the free energy of activation △G^≠ is 123. 12 kJ · mol^-1.

关 键 词：过氧化二异丙苯 热重-微分热重 热分解 非等温动力学 

分 类 号：O625.22[理学—有机化学] TQ013[理学—化学]