Heterogeneous reaction mechanism of gaseous HNO3 with solid NaCl: a density functional theory study

Nan ZHAO, Qingzhu ZHANG, Wenxing WANG

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Front. Environ. Sci. Eng. ›› 2016, Vol. 10 ›› Issue (5) : 3. DOI: 10.1007/s11783-016-0836-z
RESEARCH ARTICLE

Heterogeneous reaction mechanism of gaseous HNO3 with solid NaCl: a density functional theory study

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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.

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Keywords

Seasalt particles / NaCl / HNO3 / Heterogeneous reaction / Reaction mechanism / Density functional theory

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Nan ZHAO, Qingzhu ZHANG, Wenxing WANG. Heterogeneous reaction mechanism of gaseous HNO3 with solid NaCl: a density functional theory study. Front. Environ. Sci. Eng., 2016, 10(5): 3 https://doi.org/10.1007/s11783-016-0836-z

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Acknowledgements

This work was supported by the National High Technology Research & Development Program of China (No. 2012AA06A301) and the National Natural Science Foundation of China (Grant Nos. 21337001 and 21177076).

Electronic Supplementary Material

ƒSupplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s11783-016-0836-zand is accessible for authorized users.

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2016 Higher Education Press and Springer-Verlag Berlin Heidelberg
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