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Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2016, Vol. 10 Issue (5) : 3     https://doi.org/10.1007/s11783-016-0836-z
RESEARCH ARTICLE
Heterogeneous reaction mechanism of gaseous HNO3 with solid NaCl: a density functional theory study
Nan ZHAO,Qingzhu ZHANG(),Wenxing WANG
Environment Research Institute, Shandong University, Jinan 250100, China
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Abstract

We studied the heterogeneous reaction mechanism of gaseous HNO3 with solid NaCl.

HCl is released from heterogeneous reactions between gaseous HNO3 and solid NaCl.

Water molecules induce surface reconstruction of NaCl to facilitate the reaction.

Sea salt particles containing NaCl are among the most abundant particulate masses in coastal atmosphere. Reactions involving sea salt particles potentially generate Cl radicals, which are released into coastal atmosphere. Cl radicals play an important role in the nitrogen and O3 cycles, sulfur chemistry and particle formation in the troposphere of the polluted coastal regions. This paper aimed at the heterogeneous reaction between gaseous HNO3 and solid NaCl. The mechanism was investigated by density functional theory (DFT). The results imply that water molecules induce the surface reconstruction, which is essential for the heterogeneous reaction. The surface reconstruction on the defective (710) surface has a barrier of 10.24 kcal·mol−1 and is endothermic by 9.69 kcal·mol−1, whereas the reconstruction on the clean (100) surface has a barrier of 18.46 kcal·mol−1 and is endothermic by 12.96 kcal·mol−1. The surface reconstruction involved in water-adsorbed (710) surface is more energetically favorable. In comparison, water molecules adsorbed on NaCl (100) surface likely undergo water diffusion or desorption. Further, it reveals that the coordination number of the Clout is reduced after the surface reconstruction, which assists Clout to accept the proton from HNO3. HCl is released from heterogeneous reactions between gaseous HNO3 and solid NaCl and can react with OH free radicals to produce atomic Cl radicals. The results will offer further insights into the impact of gaseous HNO3 on the air quality of the coastal areas.

Keywords Seasalt particles      NaCl      HNO3      Heterogeneous reaction      Reaction mechanism      Density functional theory     
This article is part of themed collection: Understanding the processes of air pollution formation (Responsible Editors: Min SHAO, Shuxiao WANG & Armistead G. RUSSELL)
Corresponding Author(s): Qingzhu ZHANG   
Issue Date: 09 May 2016
 Cite this article:   
Nan ZHAO,Qingzhu ZHANG,Wenxing WANG. Heterogeneous reaction mechanism of gaseous HNO3 with solid NaCl: a density functional theory study[J]. Front. Environ. Sci. Eng., 2016, 10(5): 3.
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http://journal.hep.com.cn/fese/EN/10.1007/s11783-016-0836-z
http://journal.hep.com.cn/fese/EN/Y2016/V10/I5/3
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Qingzhu ZHANG
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Fig.1  The most stable configurations of HNO3-NaCl, H2O-NaCl and HNO3-H2O-NaCl adsorption systems. The distances are in angstrom. Purple ball: Na; green ball: Cl; blue ball: N; red ball: O; white ball: H
Fig.2  Configuration of the transition state and the configurations before and after the water diffusion on the flat (100) surface. The distances are in angstrom. All color settings are the same as Fig. 1. TS1: the transition state
Fig.3  Configuration of the transition state and the configurations before and after the surface reconstruction of the water-adsorbed (100) surface. The distances are in angstrom. All color settings are the same as Fig. 1. TS4: the transition state
Fig.4  Configurations of the reactant state, intermediate, transition state and the product state for the reaction of HNO3 on the step of the reconstructed (710) surface. The distances are in angstrom. All color settings are the same as Fig. 1. TS6 and TS7: transition states. IM1: the intermediate
Fig.5  Configurations of the reactant state, intermediate, transition state and the product state for the reaction of HNO3 on the stoichiometric (100)-like plane of the reconstructed (710) surface. The distances are in angstrom. All color settings are the same as Fig. 1. TS8 and TS9: transition states. IM2: the intermediate
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