【摘要】 通过对煤中硫赋存形态的分析,筛选出可以表示这些形态硫的有机小分子:CH3CH2SH,CH3SCH3,CH3CSCH3和C4H4S;应用Gaussian98程序,在6-31G(d)水平上,采用密度泛函B3LYP和相关能校准的MP2方法对单重态和三重态氧和这些分子及它们与氧分子结合的两种状态的复合物进行了量子化学的几何构型优化、集聚数分析和振动分析.通过计算,得到各自的总能量、熵和Gibbs自由能等热化学数据及键级、电荷密度、自旋密度等分子性质.得到由上述分子与O2形成单线态和三线态复合体的ΔG在-337·555284kJ/mol~-202·021723kJ/mol范围内.对这些数据进行分析,得出不同赋存形态硫与氧反应以SO2形式释放的难易程度,为研究煤的脱硫、固硫机理提供参考.更多还原

【Abstract】 Comparing the state of sulfur in coal,it is found that some small organic molecules,such as ethanethiol,ethyl thioether,thioacetone and thiophene could be used to describe these states.Quantum chemistry calculation,including geometrical structures optimization,the population analysis and the vibrational frequency analysis on these organic molecules,the oxygen of the singlet and triplet configurations and the complexes formed by the oxygen with those molecules was performed using Gaussian 98 program at the level of B3LYP/6-31G（d） and MP2/6-31G（d） respectively.By the calculation,the thermal energy,entropy, electronic energy, free energy,charge density and spin density were obtained.The change （ΔF） of the electronic and thermal free energies on formed complex by oxygen （T, S） and those molecules is in the scope of 337.555 284 kJ/mol-202.021 723 kJ/mol. Comparing the data,sulfur in CH₃CH₂SH is the most easily released in the form of sulfur dioxide.It provided the reference for studying the mechanism of desulfurization of coal.更多还原