Theoretical study of the oxidation reactions of sulfurous acid/sulfite with ozone to produce sulfuric acid/sulfate with atmospheric implications

被引：13

作者：

Fang Sheng ^{[1
]}

Liu Jingjing ^{[2
]}

Chen Yu ^{[1
]}

Tao Fu-Ming ^{[3
]}

Duan Xuemei ^{[1
]}

Liu Jing-yao ^{[1
]}

机构：

[1] Jilin Univ, Inst Theoret Chem, Lab Theoret & Computat Chem, Changchun 130023, Jilin, Peoples R China

[2] Tsinghua Univ, Minist Educ, Dept Chem, Key Lab Organ Optoelect & Mol Engn, Beijing 100084, Peoples R China

[3] Calif State Univ Fullerton, Dept Chem & Biochem, Fullerton, CA 92834 USA

来源：

RSC ADVANCES | 2018年 / 8卷 / 15期

基金：

中国国家自然科学基金;

关键词：

UBER DIE KONSTITUTION; SAUREN SULFITE; ABSTRACTION REACTIONS; ORGANIC-COMPOUNDS; AB-INITIO; SO2; ACID; KINETICS; DIOXIDE; GAS;

D O I：

10.1039/c8ra00411k

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Herein, theoretical studies were performed on the atmospheric oxidation of sulfurous acid (H2SO3) and sulfite ions (HSO3-) by ozone (O-3) to produce sulfuric acid and hydrosulfate ions. The most favorable path for the H2SO3 + O-3 reaction has been found to be initiated from concerted H-abstraction and oxygen addition, with an overall energy barrier of 18.3 kcal mol(-1). On the other hand, the most favorable path for the HSO3- + O-3 reaction is initiated from oxygen addition, with an overall energy barrier of only 0.3 kcal mol(-1). Kinetic simulations were performed to estimate the significance of these reactions in the formation of atmospheric sulfate and destruction of the ozone layer. The results provide new insight into the missing source of atmospheric sulfate and particulate matter.

引用

页码：7988 / 7996

页数：9

共 66 条

[1] Reduced HOMO-LUMO gap as an index of kinetic stability for polycyclic aromatic hydrocarbons [J].

Aihara, J .

JOURNAL OF PHYSICAL CHEMISTRY A, 1999, 103 (37) :7487-7495

[2]

Akimoto H, 2016, SPRINGER ATMOS SCI, P1, DOI 10.1007/978-4-431-55870-5

[3] Atmospheric Significance of Water Clusters and Ozone-Water Complexes [J].

Anglada, Josep M. ;

Hoffman, Gerald J. ;

Slipchenko, Lyudmila V. ;

Costa, Marilia M. ;

Ruiz-Lopez, Manuel F. ;

Francisco, Joseph S. .

JOURNAL OF PHYSICAL CHEMISTRY A, 2013, 117 (40) :10381-10396

[4] A LONG-RANGE TRANSPORT MODEL FOR AMMONIA AND AMMONIUM FOR EUROPE [J].

ASMAN, WAH ;

JANSSEN, AJ .

ATMOSPHERIC ENVIRONMENT, 1987, 21 (10) :2099-2119

[5] KINETICS AND MECHANISMS OF THE GAS-PHASE REACTIONS OF OZONE WITH ORGANIC-COMPOUNDS UNDER ATMOSPHERIC CONDITIONS [J].

ATKINSON, R ;

CARTER, WPL .

CHEMICAL REVIEWS, 1984, 84 (05) :437-470

[6] Mechanism and kinetics study on the ozonolysis reaction of 2,3,7,8-TCDD in the atmosphere [J].

Bai, Jing ;

Sun, Xiaomin ;

Zhang, Chenxi ;

Gong, Chen ;

Hu, Jingtian ;

Zhang, Jianghua .

JOURNAL OF ENVIRONMENTAL SCIENCES, 2014, 26 (01) :181-188

[7] Theoretical studies on atmospheric chemistry of CHF2CF2CH2OH: Reaction with OH radicals, lifetime and global warming potentials [J].

Baidya, Bidisha ;

Lily, Makroni ;

Chandra, Asit K. .

COMPUTATIONAL AND THEORETICAL CHEMISTRY, 2017, 1119 :1-9

[8] Dimethyl sulfide and dimethyl sulfoxide and their oxidation in the atmosphere [J].

Barnes, I ;

Hjorth, J ;

Mihalopoulos, N .

CHEMICAL REVIEWS, 2006, 106 (03) :940-975

[9] H2SO4 formation from the gas-phase reaction of stabilized Criegee Intermediates with SO2: Influence of water vapour content and temperature [J].

Berndt, Torsten ;

Jokinen, Tuija ;

Sipila, Mikko ;

Mauldin, Roy L., III ;

Herrmann, Hartmut ;

Stratmann, Frank ;

Junninen, Heikki ;

Kulmala, Markku .

ATMOSPHERIC ENVIRONMENT, 2014, 89 :603-612

[10] TRANSITION-METAL-CATALYZED OXIDATION OF SULFUR(IV) OXIDES - ATMOSPHERIC-RELEVANT PROCESSES AND MECHANISMS [J].

BRANDT, C ;

VANELDIK, R .

CHEMICAL REVIEWS, 1995, 95 (01) :119-190

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