Citation: Lyu Longmei, Geng Lin, Wen Mingjie, Qiao Zhangyu, Kou Weihua, Wang Yan, Tian Shaobo, Wang Rui. Study on the Atmospheric Reaction of NO₂ with HSO:Mechanism and Kinetics[J]. Chemistry, ;2019, 82(6): 534-541, 503. shu

Study on the Atmospheric Reaction of NO₂ with HSO:Mechanism and Kinetics

Shaanxi Key Laboratory of Catalysis, School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong 723000

Corresponding author: Wang Rui, wangrui830413@163.com
Received Date: 16 October 2018
Accepted Date: 30 March 2019

Figures(5)

The mechanism for the reaction between NO₂ and HSO was investigated at the CCSD(T)/aug-cc-pVTZ //B3LYP/aug-cc-pVTZ level on both the singlet and triplet potential energy surfaces (PESs). The results showed that there are three hydrogen abstraction reaction channels on both singlet [R1 HN(O)O+¹SO), R2 (cis-HONO+¹SO), and R3 (trans-HONO+¹SO)] and triplet [R6 (HN(O)O+³SO), R7(cis-HONO+³SO), and R8(trans-HONO+³SO)] PESs, as well as two oxygen abstraction reaction channels on both singlet [R4 (NO+HS(O)O)and R5(H+SO₂+NO)] and triplet [R9(HS(O)O+NO) and R10 (H+SO₂+NO)] on the triplet PESs. Among these channels, Channel R2 (cis-HONO+¹SO) on the singlet PESs is the favorable channel. The rate constants of above reaction channels were evaluated using classical transition state theory (TST) and Wigner correction. The calculated results showed that the reaction channel of cis-HONO+SO formations is favorable and its rate constant, at 298K, is 7.78×10^-13cm³·molecule^-1·s^-1, which is in good agreement with experimental value (9.6×10^-12cm³·molecule^-1·s^-1). Water molecule catalyzed R2 (cis-HONO+¹SO) occurs through two different channels of NO₂+H₂O…HSO and NO₂+H₂O…HSO (HSO+NO₂…H₂O), where the barriers of the two channels respectively are enhanced by 49.97 kcal·mol^-1 and 20.67 kcal·mol^-1 than that of the naked reaction of R2, indicating that the effect of water molecules on the NO₂+HSO reaction can be neglected in the actual atmospheric environment.
- NO₂,
- HSO,
- Singlet and triplet PES,
- Reaction mechanism,
- Rate constant
1. [1]
  T L Zhang, R Wang, H Chen et al. Phys. Chem. Chem. Phys., 2015, 17(22): 15046~15055.
2. [2]
  R Atkinson, D L Baulch, R Cox et al. Atmos. Chem. Phys., 2004, 4(6): 1461~1738.
3. [3]
  R Atkinson, D L Baulch, R A Cox et al. J. Phys. Chem. Ref. Data, 1992, 21(6): 1125~1568.
4. [4]
  W B DeMore, S P Sander, D M Golden et al. Jet Propuls. Lab. Publ., 1997, 97(4): 1~266.
5. [5]
  R Atkinson, D L Baulch, R A Cox, et al. IUPAC Subcommittee on gas kinetic data evaluation for Atmospheric Chemistry, 2001, 20.
6. [6]
  S S Brown, A R Ravishankara, H Stark. J. Phys. Chem. A, 2000, 104(30): 7044~7052.
7. [7]
  N S Wang, C J Howard. J. Phys. Chem., 1990, 94(25): 8787~8794.
8. [8]
9. [9]
  L F Chen, D Han, J H Tao et al. J. Remote Sens., 2009, 13(3): 343~354.
10. [10]
  B Langmann, A Heil. Atmos. Chem. Phys., 2004, 4(8): 2145~2160.
11. [11]
  G S Tyndall, A R Ravishankara. Int. J. Chem. Kinet., 2010, 23(6): 483~527.
12. [12]
  R Atkinson, D L Baulch, R A Cox et al. J. Phys. Chem. Ref. Data, 1989, 21(2): 115~150.
13. [13]
  R Atkinson, D L Baulch, R A Cox et al. J. Phys. Chem. Ref. Data, 1997, 26(6): 1329~1499.
14. [14]
  K V Gothelf, K A Jørgensen. Chem. Rev., 1998, 98(2): 863~909.
15. [15]
  O Tishchenko, S Ilieva, D G Truhlar. J. Chem. Phys., 2010, 133(2): 021102.
16. [16]
  J Z Gillies, C W Gillies, F J Lovas et al. J. Am. Chem. Soc., 1989, 113(17): 6408~6415.
17. [17]
  B Qi, X H Lu, S Y Fang et al. J. Mol. Catal. A, 2011, 334(1-2): 44~51.
18. [18]
  M J Frisch, G W Trucks, J A Pople et al. Gaussian 09, revision A. 01[CP]; Gaussian Inc.: Pittsburgh, PA, 2009.
19. [19]
  R A B Bond, B S Martincigh, J R Mika et al. J. Chem. Educat., 1998, 75(9): 1158~1165.
20. [20]
  R Gutbrod, E Kraka, R N Schindler et al. J. Am. Chem. Soc., 1997, 119(31): 7330~7342.
21. [21]
  J M Anglada, V M Domingo. J. Phys. Chem. A, 2005, 109(47): 10786~10794.
1. [1]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
2. [2]
  Shuying Zhu , Shuting Wu , Ou Zheng . Improvement and Expansion of the Experiment for Determining the Rate Constant of the Saponification Reaction of Ethyl Acetate. University Chemistry, 2024, 39(4): 107-113. doi: 10.3866/PKU.DXHX202310117
3. [3]
  Anqi LI , Wenjing YANG , Xueming LI , Yanfong REN . Performance and mechanism of a foam Ti/FeCo-Fe₂O₃-CoFe₂O₄/SnO₂-Sb anode for synergistic activation of peroxymonosulfate toward degradation of organic pollutants. Chinese Journal of Inorganic Chemistry, 2026, 42(5): 944-958. doi: 10.11862/CJIC.20250323
4. [4]
  Lisen Sun , Yixi Chen , Gengfeng Zheng , Qing Han , Linping Qian . 蔗糖水解反应的旋光管设计与动力学探究. University Chemistry, 2026, 41(10): 336-343. doi: 10.12461/PKU.DXHX202510059
5. [5]
  Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
6. [6]
  Ling Fan , Meili Pang , Yeyun Zhang , Yanmei Wang , Zhenfeng Shang . Quantum Chemistry Calculation Research on the Diels-Alder Reaction of Anthracene and Maleic Anhydride: Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 133-139. doi: 10.3866/PKU.DXHX202309024
7. [7]
  Wanping Chen . Construction of Knowledge Logic and Discovery through Reasoning: Summarizing the Reaction Patterns of Reactive Metals with Oxygen. University Chemistry, 2026, 41(2): 95-102. doi: 10.12461/PKU.DXHX202503108
8. [8]
  Gengwei Zhang , Jun Cao . 化学反应动力学方程的AI辅助发现——以蔗糖水解反应为例. University Chemistry, 2026, 41(9): 396-404. doi: 10.12461/PKU.DXHX202508037
9. [9]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
10. [10]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117
11. [11]
  Yang Wang , Shuangliang Liu , Jianbo Zhao . Exploring the mechanism of Diels-Alder reaction: a computational chemistry experiment for undergraduate students. University Chemistry, 2026, 41(7): 257-265. doi: 10.12461/PKU.DXHX202504061
12. [12]
  Lijun Yang . Thoughts and Practices on Enhancing Students’ Comprehension through Visualized Instruction of Structural Chemistry. University Chemistry, 2025, 40(10): 295-302. doi: 10.12461/PKU.DXHX202411048
13. [13]
  Meng Wang , Yan Zhang , Yunbo Yu , Wenpo Shan , Hong He . High-temperature calcination dramatically promotes the activity of Cs/Co/Ce-Sn catalyst for soot oxidation. Chinese Chemical Letters, 2025, 36(1): 109928-. doi: 10.1016/j.cclet.2024.109928
14. [14]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
15. [15]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
16. [16]
  Zhi Chai , Huashan Huang , Xukai Shi , Yujing Lan , Zhentao Yuan , Hong Yan . Wittig反应的立体选择性. University Chemistry, 2025, 40(8): 192-201. doi: 10.12461/PKU.DXHX202410046
17. [17]
  Chonghang Sun , Xingfang Zheng , Lin Li , Xiaolei Jiang , Fangdong Hu . 类比法在有机化学机理教学中的应用——以羰基化合物及羧酸衍生物为例. University Chemistry, 2026, 41(9): 382-391. doi: 10.12461/PKU.DXHX202508095
18. [18]
  Bolin Sun , Jie Chen , Ling Zhou . 乙烯型卤代烃的亲核取代反应. University Chemistry, 2025, 40(8): 152-157. doi: 10.12461/PKU.DXHX202410032
19. [19]
  Hongting Yan , Aili Feng , Rongxiu Zhu , Lei Liu , Dongju Zhang . Reexamination of the Iodine-Catalyzed Chlorination Reaction of Chlorobenzene Using Computational Chemistry Methods. University Chemistry, 2025, 40(3): 16-22. doi: 10.12461/PKU.DXHX202403010
20. [20]
  Guowen Xing , Guangjian Liu , Le Chang . Five Types of Reactions of Carbonyl Oxonium Intermediates in University Organic Chemistry Teaching. University Chemistry, 2025, 40(4): 282-290. doi: 10.12461/PKU.DXHX202407058

Get Citation

PDF

XML

Metrics

PDF Downloads(15)
Abstract views(1473)
HTML views(170)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Study on the Atmospheric Reaction of NO2 with HSO:Mechanism and Kinetics

Metrics

通讯作者: 陈斌, bchen63@163.com

Study on the Atmospheric Reaction of NO₂ with HSO:Mechanism and Kinetics