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在G3XMP2//B3LYP/6-311+G(3df,2p)水平上对CH3SO3裂解反应的机理进行了研究,获得了6条通道(10条路径),并构建了其势能剖面.同时采用单分子反应理论计算了各个通道在温度200-3000K区间的速率常数.研究结果表明,在计算温度范围内,CH3SO3裂解反应的主产物为P1(CH3+SO3),产物P2(CH3O+SO2)和P3(HCHO+HOSO)仅在温度大于3000K时对总产物有贡献,而产物P4(CHSO2+H2O)、P5(CH2SO3+H)和P6(CHSO3+H2)贡献相对较少.将裂解反应总的速率常数拟合为ktotal=1.40×1012T0.15exp(-7831.58/T).此外,根据统计热力学原理,预测了所有物种的生成焓(ΔfH298K,ΔfH0K)、熵(S298K)和热容(Cp,298-2000K),计算的结果与实验值较接近.
The mechanism of cleavage of CH3SO3 at G3XMP2 // B3LYP / 6-311 + G (3df, 2p) was studied, and six channels (10 paths) were obtained and their potential energy profiles were constructed. The reaction rate constant of each channel in the temperature range of 200-3000K was calculated by reaction theory.The results show that the main products of CH3SO3 cleavage reaction are P1 (CH3 + SO3), P2 (CH3O + SO2) and P3 HCHO + HOSO) only contributed to the total product when the temperature was above 3000K, while the products P4 (CHSO2 + H2O), P5 (CH2SO3 + H) and P6 (CHSO3 + H2) contributed relatively less.The total rate constant In addition, the enthalpies of formation (ΔfH298K, ΔfH0K), entropy (S298K) and heat capacity (Cp, 298-2000K) of all species were predicted according to the principle of statistical thermodynamics for the ktotal = 1.40 × 1012T0.15exp ), The calculated result is close to the experimental value.