Heterogeneous reaction mechanism of gaseous HNO<sub>3</sub> with solid NaCl: a density functional theory study

doi:10.1007/s11783-016-0836-z

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 Cl⁻_out is reduced after the surface reconstruction, which assists Cl⁻_out 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

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.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-016-0836-z
https://academic.hep.com.cn/fese/EN/Y2016/V10/I5/3

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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