CAJ | 학술논문

采用基于密度泛函理论的量子化学方法研究了气化法制备不溶性硫黄过程中硫黄(S8)的开环裂解机理，建立了可能的反应路径，通过过渡态理论，计算了各个基元反应的活化能与反应速率常数，并对各个基元反应进行了动力学模拟计算，得到气体硫黄产物分布。研究结果表明，硫黄 S8优先裂解成?S2?和?S6?，反应能垒为209.45 kJ·mol?1，气态硫黄S8开环裂解后生成产物主要为?S2?、?S4?和?S6?，与蒸汽密度法得到的组成分布相似，为进一步研究不溶性硫黄分子结构及聚合机理提供了参考方向。
채용기우밀도범함이론적양자화학방법연구료기화법제비불용성류황과정중류황(S8)적개배렬해궤리，건립료가능적반응로경，통과과도태이론，계산료각개기원반응적활화능여반응속솔상수，병대각개기원반응진행료동역학모의계산，득도기체류황산물분포。연구결과표명，류황 S8우선렬해성?S2?화?S6?，반응능루위209.45 kJ·mol?1，기태류황S8개배렬해후생성산물주요위?S2?、?S4?화?S6?，여증기밀도법득도적조성분포상사，위진일보연구불용성류황분자결구급취합궤리제공료삼고방향。
Quantum chemical method based on density functional theory (DFT) was used to study the ring-open reaction mechanism of sulfur during the preparation of insoluble sulfur by gasification method. The probable reaction path was built. By the transition state theory, the activation energy and reaction rate constant were calculated for each elementary reaction. The kinetics of each elementary reaction was calculated to determine the product composition of sulfur ring-open reaction. As the result showed that the ring-open reaction of S8 generated?S2? and?S6? preferentially, the reaction barrier was about 209.45 kJ·mol?1. The main product of S8ring-open reaction were?S2?,?S4? and?S6?. The calculated values were in agreement with the experiment results based on steam density method. The result provided reference for the study of molecular structure and polymerization mechanism of insoluble sulfur.