【摘要】 应用Gaussian 03程序,采用密度泛函方法,在B3LYP/6-31G（d,p）水平下,分析Fe²⁺抑制煤中α位硫酚结构氧化的效果,从而为阻化剂的配制与优选提供数值依据。首先,根据自然键轨道理论分析煤的特征结构C₁₀H₇SH与过渡金属Fe²⁺形成配合物的成键本质,并结合分子中的原子理论分析其稳定性;然后,分别计算C₁₀H₇SH结构和[FeSH₈CC₁₀]²⁺配合物吸附O₂的反应过程,得到反应过程所需活化能,以此活化能为指标,表征Fe²⁺抑控煤中α位硫酚结构氧化的效果。计算结果表明,Fe²⁺与C₁₀H₇SH结构中的S原子间形成了配位键,根据电子密度拓扑分析得其键能E_S-Fe为-128.56 kJ/mol,C₁₀H₇SH结构吸附O₂的反应过程所需活化能为E_C=62.71 kJ/mol,[FeSH₈C₁₀]²⁺配合物吸附O₂的反应过程所需活化能与其相比增加了35.60 kJ/mol。研究表明,Fe²⁺对煤中α位硫酚结构氧化具有明显的控制作用。更多还原

【Abstract】 In this paper,we would like to present our analysis results of the inhibitive function of Fe²⁺ on a-thiophenol structure oxidation in the coal by using Gaussian 03 program based on the density functional theory（DFT） in hoping to provide a numerical basis for preparing and selecting the inhibitor at B3LYP/6- 31G（d,p） level.And,it is just for this purpose that we have,first of all,been attempting to optimize the geometries of the characteristic structure of the coal C₁₀H₇SH and its complex compound[FeSH₈C₁₀]²⁺ and work out the vibration frequencies at the same level so as to make out if they are the stationary points with no imaginary frequency.And,then,we have made an exploration of the essence of the bond forming from transition metal Fe²⁺ and C₁₀H₇SH in accordance with the natural bond orbital theory.Furthermore,we have also made an analysis of the bond structure stabilization in accordance with the atoms in molecular theory.Thus,we have made it clear how to control the oxidation and spontaneous combustion of the coal by restraining the chemical adsorption of O₂ in the coal,for the initial stage of the coal oxidation should be taken as a process of chemical adsorption of O₂ by coal.And,then,we have made the activation energy of the reaction process of O₂ adsorption by C₁₀H₇SH and[FeSH₈C₁₀]²⁺,in which it would be possible for us to make a comparison between the effect of Fe²⁺ restraining oxidation of a-thiophenol structure of the coal.Thus the results show that Fe²⁺ tends to result in a coordinated bond with S atom in C₁₀H₇SH structure,which is in accord with the topological analysis results of the electron charge density,with its bond energy being- 128.56 kJ/mol.Thus,it can be concluded that the activation energy of the reaction of O₂adsorption by C₁₀H₇SH structure proves to be equal to E_C =62.71kj/mol whereas the activation energy of the reaction of O₂ adsorption by[FeSH₈C₁0]²⁺ complex compound is E_T =98.31 kj/mol.Thus,the formulation of the complex compound tends to increase the activation energy by 35.60 kJ/mol.And,consequently,it can be found that there does exist an obvious control function of Fe²⁺ to α-thiophenol structure in the coal.更多还原