2-氢七氟丙烷的热分解性能和机理  

Thermal Decomposition Properties and Mechanism of 2-H-Heptanuoropropane

作　　者：冒爱琴[1] 孙文起[2] 丁梦玲[1] 丁赔赔 俞海云[1] 潘仁明[3] 

机构地区：[1]安徽工业大学材料科学与工程学院,安徽马鞍山243002 [2]安徽工业大学化学与化工学院,安徽马鞍山243002 [3]南京理工大学化工学院,江苏南京210094

出　　处：《过程工程学报》2015年第6期1039-1043,共5页The Chinese Journal of Process Engineering

基　　金：安徽省高校省级优秀青年人才基金重点资助项目(编号:2013SQRL022ZD);安徽省自然科学基金资助项目(编号:1508085SMB209)

摘　　要：采用密度泛函理论(DFT)中的B3LYP/6-31G(d,p)和MP2/6-31G(d,p)算法计算了C_3HF_7热解反应的焓变、中间态分子模型及活化能.结果表明,反应温度对C_3HF_7分解有明显影响,800℃的热分解产物主要为C_3F_6,伴随一定量C_3HF_5,CHF_3和(CF_3)2C=CF_2及痕量产物C_2F_4,C_3F_8,C_2HF_5与C_4F_8.热解主要产物C_3F_6主要来自C_3HF_7发生H转移反应,伴随H转移反应生成CF_3C:CF_3与CF_3CF:卡宾,F转移反应生成CF_2:卡宾和CF_3CH:自由基,相互反应生成第二、第三和第四产物C_3HF_5,CHF_3和(CF_3)2C=CF_2;C-F和C-C键断裂生成的自由基与卡宾结合,生成痕量产物C_2F_4,C_3F_8,C_2HF_5和C_4F_8.Enthalpy, transition-state molecules and barrier heights of decomposition reaction of 2-H-heptanuoropropane（C3HF7） were studied with B3LYP/6-31G（d, p） and MP2/6-31G（d, p） methods. Theoretical computation shows that the reaction temperature has obvious effect on the thermal decomposition of C3HF7, and the pyrolysis products include the main product C3F6, a certain amount of C3HF5, CHF3 and（CF3）2C=CF2, and trace concentrations of C2F4, C3F8, C2HF5 and C4F8 at 800 ℃. The decomposition of C3HF7 into C3F6 is the most important initiation mechanism, with the H transfer reaction to CF3C：CF3 and CF3CF：CF3CF：carbine and F transfer reaction to CF3 CH and CF2：radicals, some products including C3HF5, CHF3 and（CF3）2C=CF2 form, and the trace concentrations of C2F4, C3F8, C2HF5 and C4F8 originate from the combination between the radicals of C-F and C-C bond fission and carbine.

关 键 词：2-氢七氟丙烷 热分解 理论计算 机理 

分 类 号：X932[环境科学与工程—安全科学] O643[理学—物理化学]