Understanding the catalytic role of oxalic acid in SO&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt; hydration to form H&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;SO&amp;lt;sub&amp;gt;4&amp;lt;/sub&amp;gt; in the atmosphere

Lv, Guochun; Sun, Xiaomin; Zhang, Chenxi; Li, Mei

doi:10.5194/acp-19-2833-2019

Cited by 29 publications

(22 citation statements)

References 64 publications

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“…charge and H2, H4 atom gains the charge by 0.04 and 0.01 a.u., respectively with respect to I1. The redistribution of electronic charge on the reactive species shows that the mechanism proposed in this study takes place through hydrogen atom transfer reaction, which is in accordance with previous study on hydrogen atom transfer reaction for closed shell system . In the transition state, TS1‐di, the oxygen atom O2 of second water molecule starts to bind with S atom of HNSO 2 with S‐O2 distance of 1.8 Å.…”

Section: Resultssupporting

confidence: 90%

Hydrolysis of HNSO₂: A potential route for atmospheric production of H₂SO₄ and NH₃

Manonmani

Sandhiya

Senthilkumar

2020

Int J of Quantum Chemistry

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The hydrolysis of sulfonylamine (HNSO 2 ) results in the formation of sulfuric acid along with ammonia, and is of significant interest due to their negative impact on environment and life on Earth. The formation of H 2 SO 4 through the reaction of HNSO 2 with (H 2 O) [2][3][4] has been studied using high level electronic structure calculations. This hydrolysis reaction is a step-wise process, in the first step a H-atom from H 2 O is transferred to the N-atom of HNSO 2 which results in the formation of NH 2 , and in the next step, H 2 SO 4 , NH 3 and water molecule(s) are formed. The results show that the energy barrier associated with the formation of intermediates and product complexes is reduced by 7 to 10 kcal/mol when the number of water molecules is increased from 2 to 4. The rate constant was calculated using canonical variational transition state theory with small curvature tunneling correction over the temperature range of 200 to 1000 K. At 298 K, the calculated rate constant for the formation of intermediate in the first step is 2.24 × 10 −16 , 1.03 × 10 −12 , and 2.10 × 10 −11 cm 3 mol −1 s −1 , respectively, for the reaction with water dimer, trimer and tetramer. The calculated enthalpy and free energy show that the reaction corresponding to the formation of H 2 SO 4 is highly exothermic and exoergic in nature. K E Y W O R D Skinetics, sulfonylamine, sulfuric acid, water dimer, water tetramer, water trimer, aereosol, atmospheric reaction

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Section: Resultssupporting

confidence: 90%

Hydrolysis of HNSO₂: A potential route for atmospheric production of H₂SO₄ and NH₃

Manonmani

Sandhiya

Senthilkumar

2020

Int J of Quantum Chemistry

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“…The structures of the reactant (RC), product (PC), intermediate (IM), and transition states (TS) are optimized using M06-2X density functional method with the 6-311++G (d, p) basis set [37]. This is relatively accurate and time-efficient when used to study the reaction mechanism and has been employed successfully in our previous studies [38,39]. The vibrational frequencies have been obtained to verify that the reactant complexes, intermediates, and product complexes have all positive frequencies and that the transition state (TS) geometries have only one imaginary frequency at the same level.…”

Section: Methodsmentioning

confidence: 99%

Synergistic Reaction of SO2 with NO2 in Presence of H2O and NH3: A Potential Source of Sulfate Aerosol

Wang

Zhang

et al. 2019

IJMS

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Effect of H2O and NH3 on the synergistic oxidation reaction of SO2 and NO2 is investigated by theoretical calculation using the molecule system SO2-2NO2-nH2O (n = 0, 1, 2, 3) and SO2-2NO2-nH2O-mNH3 (n = 0, 1, 2; m = 1, 2). Calculated results show that SO2 is oxidized to SO3 by N2O4 intermediate. The additional H2O in the systems can reduce the energy barrier of oxidation step. The increasing number of H2O molecules in the systems enhances the effect and promotes the production of HONO. When the proportion of H2O to NH3 is 1:1, with NH3 included in the system, the energy barrier is lower than two pure H2O molecules in the oxidation step. The present study indicates that the H2O and NH3 have thermodynamic effects on promoting the oxidation reaction of SO2 and NO2, and NH3 has a more significant role in stabilizing product complexes. In these hydrolysis reactions, nethermost barrier energy (0.29 kcal/mol) can be found in the system SO2-2NO2-H2O. It is obvious that the production of HONO is energetically favorable. A new reaction mechanism about SO2 oxidation in the atmosphere is proposed, which can provide guidance for the further study of aerosol surface reactions.

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“…Plentiful computational studies have also shown that DHAT reactions result in a catalytic effect. Examples include: (i) gas‐phase hydrolysis of HFCO is catalyzed by H 2 SO 4 ; (ii) decomposition of CF 3 OH is catalyzed by formic acid; (iii) SO 3 hydration is catalyzed by oxalic acid; (iv) SO 3 +NH 3 reaction is catalyzed by NH 3 , etc. Furthermore, double H‐atom exchange reactions of HO 2 +HX (X=F, Cl, Br, I) have also been predicted computationally …”

Section: Figurementioning

confidence: 99%

Reactions of Criegee Intermediates are Enhanced by Hydrogen‐Atom Relay Through Molecular Design

2020

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We report a type of highly efficient double hydrogen atom transfer (DHAT) reaction. The reactivities of 3‐aminopropanol and 2‐aminoethanol towards Criegee intermediates (syn‐ and anti‐CH3CHOO) were found to be much higher than those of n‐propanol and propylamine. Quantum chemistry calculation has confirmed that the main mechanism of these very rapid reactions is DHAT, in which the nucleophilic attack of the NH2 group is catalyzed by the OH group which acts as a bridge of HAT. Typical gas‐phase DHAT reactions are termolecular reactions involving two hydrogen bonding molecules; these reactions are typically slow due to the substantial entropy reduction of bringing three molecules together. Putting the reactive and catalytic groups in one molecule circumvents the problem of entropy reduction and allows us to observe the DHAT reactions even at low reactant concentrations. This idea can be applied to improve theoretical predictions for atmospherically relevant DHAT reactions.

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Understanding the catalytic role of oxalic acid in SO<sub>3</sub> hydration to form H<sub>2</sub>SO<sub>4</sub> in the atmosphere

Cited by 29 publications

References 64 publications

Hydrolysis of HNSO₂: A potential route for atmospheric production of H₂SO₄ and NH₃

Hydrolysis of HNSO₂: A potential route for atmospheric production of H₂SO₄ and NH₃

Synergistic Reaction of SO2 with NO2 in Presence of H2O and NH3: A Potential Source of Sulfate Aerosol

Reactions of Criegee Intermediates are Enhanced by Hydrogen‐Atom Relay Through Molecular Design

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Understanding the catalytic role of oxalic acid in SO&lt;sub&gt;3&lt;/sub&gt; hydration to form H&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; in the atmosphere

Cited by 29 publications

References 64 publications

Hydrolysis of HNSO2: A potential route for atmospheric production of H2SO4 and NH3

Hydrolysis of HNSO2: A potential route for atmospheric production of H2SO4 and NH3

Synergistic Reaction of SO2 with NO2 in Presence of H2O and NH3: A Potential Source of Sulfate Aerosol

Reactions of Criegee Intermediates are Enhanced by Hydrogen‐Atom Relay Through Molecular Design

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Understanding the catalytic role of oxalic acid in SO<sub>3</sub> hydration to form H<sub>2</sub>SO<sub>4</sub> in the atmosphere

Hydrolysis of HNSO₂: A potential route for atmospheric production of H₂SO₄ and NH₃

Hydrolysis of HNSO₂: A potential route for atmospheric production of H₂SO₄ and NH₃