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Theoretical research on reaction of solid sulfur allotropes with elemental mercury
Chemical Engineering Journal ( IF 13.3 ) Pub Date : 2020-09-24 , DOI: 10.1016/j.cej.2020.127113
Ruize Sun , Mingyu Yu , Guangqian Luo , Xian Li , Hong Tian , Hong Yao

Element sulfur has proven to be active material for hazardous elemental mercury (Hg0) removal. However, the underlying mechanism of elemental sulfur reacting with Hg0 was still unclear. Generally, solid elemental sulfur exists mainly composed of crown-shaped S8 molecules and traces of S6, S7, and S9 molecules. This research employed quantum chemical calculations and electronic wavefunction analysis to investigate the reaction between branched and cyclic Sn isomers (n=6-9) with Hg0 at the molecular level. Thermodynamic data and kinetics were also computed. It was found that Hg0 react with branched Sn isomers would proceed spontaneously with heat release by analyzing reaction Gibbs free energies and enthalpies. Reaction rate constants of branched Sn molecules are several orders of magnitude higher than those of cyclic Sn molecules. Moreover, the electronic wavefunction analysis was conducted. The Mayer bond order along the reaction pathway could characterize Hg-S and S-S bonds breaking and formation quantitively. Localized molecular orbitals isosurface maps reflect Hg-S bonds show typical σ bond characteristics in the products. Localized orbital locator color-filled maps reveal electrons begin to concentrate in the region between Hg and S atoms as reactions proceeding forward. In summary, this research would help develop sulfur contained adsorbents with superior Hg0 removal performance in the future.



中文翻译:

固体硫同素异形体与元素汞反应的理论研究

元素硫已被证明是用于除去有害元素汞(Hg 0)的活性材料。但是,元素硫与Hg 0反应的潜在机理仍不清楚。通常,固态元素硫主要由冠状的S 8分子和痕量的S 6,S 7和S 9分子组成。这项研究利用量子化学计算和电子波函数分析研究了Hg 0在分子水平上的支链和环状S n异构体(n = 6-9)的反应。还计算了热力学数据和动力学。发现Hg 0与支链S反应通过分析反应吉布斯自由能和焓,n个异构体会自发释放热量。支链S n分子的反应速率常数比环状S n分子的反应速率常数高几个数量级。此外,进行了电子波函数分析。沿着反应路径的Mayer键顺序可以定量表征Hg-S和SS键的断裂和形成。局部分子轨道等值面图反映Hg-S键显示典型σ产品的粘结特性。局部轨道定位器的彩色填充图显示,随着反应的进行,电子开始集中在Hg和S原子之间的区域中。总而言之,这项研究将有助于将来开发出具有优异的Hg 0去除性能的含硫吸附剂。

更新日期:2020-09-24
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