Ring-open reaction mechanism of sulfur S8 based on density functional theory

doi:10.11949/j.issn.0438-1157.20150274

CIESC Journal ›› 2015, Vol. 66 ›› Issue (10): 3919-3924.DOI: 10.11949/j.issn.0438-1157.20150274

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Ring-open reaction mechanism of sulfur S₈ based on density functional theory

WANG Rongjie^1,2, SHEN Benxian¹, MA Jian¹, ZHAO Jigang¹

1 State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
2 Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, Xinjiang, China

Received:2015-03-09 Revised:2015-04-25 Online:2015-10-05 Published:2015-10-05
Supported by:
supported by the Sinopec Scientific and Technological Development Projects(LQJS1109QT0005).

基于密度泛函的硫黄S₈开环裂解机理

王荣杰^1,2, 沈本贤¹, 马健¹, 赵基钢¹

1 华东理工大学化学工程联合国家重点实验室, 上海 200237;
2 石河子大学化学化工学院, 新疆生产建设兵团化工绿色过程重点实验室, 新疆石河子 832003

通讯作者: 赵基钢
基金资助:
中石化科技开发项目(LQJS1109QT0005)。

Abstract

Abstract:

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 S₈ ring-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.

Key words: insoluble sulfur, ring-open, reaction mechanism, density functional theory, numerical simulation

摘要：

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。

关键词: 不溶性硫黄, 开环裂解, 反应机理, 密度泛函, 数值模拟

CLC Number:

O641

WANG Rongjie, SHEN Benxian, MA Jian, ZHAO Jigang. Ring-open reaction mechanism of sulfur S₈ based on density functional theory[J]. CIESC Journal, 2015, 66(10): 3919-3924.

王荣杰, 沈本贤, 马健, 赵基钢. 基于密度泛函的硫黄S₈开环裂解机理[J]. 化工学报, 2015, 66(10): 3919-3924.

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Ring-open reaction mechanism of sulfur S₈ based on density functional theory

基于密度泛函的硫黄S₈开环裂解机理

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