scholarly journals Quamtum Mechanical Approach to Gas Phase Reaction of Isopropanol with Sulfanyl Radical  

2021 ◽  
Vol 31 (3) ◽  
pp. 37-42
Keyword(s):  
Transition State Theory ◽  
Energy Surface ◽  
Reaction Pathway ◽  
State Theory ◽  
Tunnel Effect ◽  
Phase Reaction ◽  
Reaction Products ◽  
Substitution Reactions ◽  
Total Product ◽  
Mechanical Approach

i-C3H7OH (IPA) is one of the potential fuel additives. The reaction mechanism of isopropanol with sulfanyl radical was investigated at the CCSD(T)//B3LYP/6-311+G(3df,2p) level of theory. Ten possible reaction pathways giving PR1-PR10 including three H-abstraction reactions and seven substitution reactions were considered. Based on the determined potential energy surface and molecular parameters, the rate constants and branching ratios of each reaction pathway were calculated at the temperature range of 298K - 2000K by using the transition state theory considering the Eckart tunnel effect. The kinetics results showed that at 298K, the reaction products were mainly PR2 ((CH3)2COH + H2S) (~ 100%). However, at 2000K, the contribution of PR2 decreased to 77.8% of the total product, while, PR3 (CH3CH(CH2)OH + H2S) and PR1 ((CH3)2CHO + H2S) accounted for 16.7% and 5.5% of the total product, respectively.

scholarly journals Theoretical study of the addition and hydrogen abstraction reactions of the methyl radical with formaldehyde and hydroxymethylene

2018 ◽  
Vol 83 (10) ◽  
pp. 1113-1122
Author(s):  
Huu Nguyen ◽  
Xuan Nguyen
Keyword(s):  
Transition State Theory ◽  
Energy Surface ◽  
Theoretical Study ◽  
Hydrogen Abstraction ◽  
Single Point ◽  
State Theory ◽  
Hydrogen Atom Abstraction ◽  
Methyl Radical ◽  
Variational Transition State Theory ◽  
Kinetics Of

The mechanism, thermochemistry and kinetics of the addition and hydrogen-atom abstraction reactions of the methyl radical with formaldehyde and hydroxymethylene were investigated by ab initio calculations. The potential energy surface (PES) of the reactions were calculated by single point calculations at the CCSD(T)/6-311++G(3df,2p) level based on geometries at the B3LYP/6-311++G(3df,2p) level. The rate constants of various product channels were estimated by the variational transition state theory (VTST) and are discussed for the seven reactions in the temperature range of 300?2000 K and at 101325 Pa pressure. The calculated results showed that all the hydrogen abstraction reactions are more favorable than the addition ones.

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