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为研究硝基苯气相氟代脱硝反应的热安全性,采用Gaussian98软件,运用密度泛函理论(DFT)B3LYP,在6-31G(D)基组水平上,全优化计算气相条件下氟离子对硝基苯进攻的氟代脱硝反应的微观机理,得到反应路径并通过IRC验证,并对反应过程中反应物,各中间体、过渡态、产物进行分子几何构型优化,标准热力学函数计算。理论计算研究表明:该反应属于SN2亲核取代反应;反应能垒较低,反应所需能量可以从过程R→IM1和TS3→P所释放的能量(279.06 kJ/mol,143.34 kJ/mol)中获得;与席曼反应相比较,该反应速率下降3个数量级,热安全性更高,符合化工工程设计的本质安全化要求,具有广阔的应用前景。
In order to study the thermal safety of the nitrobenzene gas-phase fluorine denitrification reaction, the fluoride ion pairs of the gas phase were fully optimized using Gaussian98 software and density functional theory (DFT) B3LYP at 6-31G (D) basis set level Nitrobenzene offensive fluorination denitration reaction of the micro-mechanism to obtain the reaction path and verified by IRC, and reactants, intermediates, transition state, the product of the molecular geometry optimization, the standard thermodynamic function calculation. Theoretical calculations show that the reaction belongs to the nucleophilic substitution reaction of SN2, and the energy barrier of reaction is low. The energy required for the reaction can be released from the processes R → IM1 and TS3 → P (279.06 kJ / mol, 143.34 kJ / mol) Compared with Schimamann reaction, the reaction rate decreased by 3 orders of magnitude and thermal safety was higher, which met the requirements of intrinsically safe chemical engineering design and had broad application prospects.