Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 24, Issue 3, Pages 1510-1519Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1cp03911c
Keywords
-
Ask authors/readers for more resources
This study investigated the rate coefficients of CH2OH reacting with O3 and found that the presence of a water molecule affects the product distribution. The calculated rate coefficients were consistent with experimental values and revealed the impact of a water molecule on the reaction mechanism.
The hydroxymethyl (CH2OH) radical is an important intermediate species in both atmosphere and combustion reaction systems. The rate coefficients for CH2OH + O-3(2) and (CH2OH + O-3(2) (+H2O)) reactions were calculated using the Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation (ME) simulation and canonical variational transition state theory (CVT) between the temperature range of 200 to 1500 K based on the potential energy surface constructed using CCSD(T)//omega B97XD/6-311++G(3df,3pd). The results show that CH2OH + O-3(2) leads to the formation of CH2O and HO2 at temperatures below 800 K, and goes back to reactants at high temperature (>1000 K). When a water molecule is added to the reaction, the formation of CH2O and HO2 is favored at all temperatures. The calculated rate coefficient for the CH2OH + O-3(2) (2.8 x 10(-11) cm(3) molecule(-1) s(-1) at 298 K) is in good agreement with the previous experimental values (similar to 1 x 10(-11) cm(3) molecule(-1) s(-1) at 298 K). The rate coefficients for the water-assisted reaction (2.4 x 10(-16) cm(3) molecule(-1) s(-1) at 1000 K) is at least 3-4 orders of magnitude smaller than the water-free reaction (6.2 x 10(-12) cm(3) molecule(-1) s(-1) at 1000 K). This result is consistent with the similar types of reaction system. Our calculations also predict that the effect of a single water molecule favors the formation of CH2O in the combustion condition. However, the water-free reaction favors the formation of CH2O in the atmospheric condition. The current study helps to understand how a single water molecule changes the reaction mechanism and chemical kinetic behaviour under atmospheric and combustion conditions.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available