Theoretical study of the reactions between arsenic and nitrogen oxides during coal combustion
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The reactions between arsenic and nitrogen oxides (N2O, NO2, and NO) were investigated using density functional theory. The geometries of the reactants, intermediates, transition states, and products in each reaction were optimized. Frequency analysis was applied to verify those geometries, and the authenticity of each transition state was checked using intrinsic reaction coordinate analysis (IRC). The single point energy of each stationary point was calculated at the B2PLYP level, and kinetic analysis was conducted to explore each reaction mechanism in more detail. Results showed that the energy barriers to the reactions of As with N2O, NO2, and NO were 78.45, 2.58, and 155.85 kJ mol−1, respectively. For each reaction, the rate increased as the temperature was increased from 298 to 1800 K. However, temperature had only a tiny impact on the reaction of As with NO2 due to the low energy barrier involved, and the reaction rate was consistently high (>1012 cm3 mol−1 s−1), which indicates that this reaction occurs readily. On the other hand, the rate of the reaction between As and N2O or NO increased rapidly between 298 and 900 K, and then increased more gradually upon further increasing the temperature.
KeywordsCoal combustion As Nitrogen oxides Density functional theory Kinetics
Financial support was provided by the National Key R&D Program of China (no. 2016YFB0600701).
- 1.Liu G, Zheng L, Duzgoren-Aydin NS, Gao L, Liu J, Peng Z (2007) Health effects of arsenic, fluorine, and selenium from indoor burning of Chinese coal. Rev Environ Contam Toxicol 189:89–106Google Scholar
- 7.Liu H, Pan W, Wang C, Zhang Y (2016) Volatilization of arsenic during coal combustion based on isothermal thermogravimetric analysis at 600–1500 °C. Energy Fuel 30(8):6790–6798Google Scholar
- 17.Peng Y, Li J, Si W, Luo J, Dai Q, Luo X, Liu X, Hao J (2014) Insight into deactivation of commercial SCR catalyst by arsenic: an experiment and DFT study. Environ Sci Technol 48(23):13895–13900. https://doi.org/10.1021/es503486w
- 21.Awuaha JB, Dzade NY, Tiac R, Adeic E, Kwakye-Awuahad B, Catlowe CRA, Leeuwbde NH (2016) A density functional theory study of arsenic immobilization by the Al(III)-modified zeolite clinoptilolite. Phys Chem Chem Phys 18(16):11297–11305Google Scholar
- 24.Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery Jr JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Keith T, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2013) Gaussian 09, revision D.01. Gaussian, Inc., WallingfordGoogle Scholar
- 28.Marsden CJ, Smith BJ (1989) Ab initio force constants: a cautionary tale concerning nitrogen oxides. J Mol Struct THEOCHEM 187:337–357Google Scholar
- 30.Mizushima M (1972) Molecular parameters of OH free radical. Phys Rev A 5(1):143–157Google Scholar