噻吩结构与O_2反应机理的理论研究

为研究煤自燃的反应机理,利用Gaussian 03程序,采用密度泛函理论(DFT)方法,在B3LYP/6-311G水平下研究煤结构中噻吩型有机硫与O2反应机理。由计算结果可知,反应物的初始连接方式有3种,其中Path 1的反应物经过过渡态TS1异构化为中间体IM1是无需克服势垒的放热过程,这说明煤中的噻吩结构无需从外界吸收热量,与氧气接触即可被氧化。此反应主要有6条反应路径,其中,Path 2是反应的主要反应路径,其速控步骤为过渡态TS6,需要克服的势垒为117.06 kJ/mol,其产物P2(C4H4O+SO)是反应的主要产物。

Theoretical study on the mechanism of the thiophene structure with O2 reaction

In order to study the reaction mechanism of coal spontaneous combustion，the calculations were performed with the Gaussian 03 program.At the B3LYP/6-311G level，the reaction mechanism of thiophene type organic sulfur in coal structure with O2 was studied by using density functional theory(DFT) method.The calculations show that initial connection of the reactant has three forms，the reactant of path 1 in it is readily isomerized to the intermediate IM1 through the transition state TS1，this process is exothermic process without overcome potential barrier，it show that thiophene type organic sulfur in coal contact with oxygen to be oxidized without absorbing heat from outside；this reaction has six reaction paths，the path 2 is the main reaction path，its rate-controlling step is the transition state TS6，its reaction energy barrier is 117.06 kJ/mol，P2(C4H4O+SO) is the main product.