Kinetics and mechanism of the thermal decomposition reaction of acetone cyclic diperoxide in the gas phase

1994 ◽  
Vol 26 (5) ◽  
pp. 503-509 ◽  
Author(s):  
L�zaro F. R. Cafferata ◽  
Jos� D. Lombardo
Keyword(s):  
Thermal Decomposition ◽  
Gas Phase ◽  
Decomposition Reaction ◽  
Kinetics And Mechanism

Theoretical Study of the Kinetics and Mechanism of the Thermal Decomposition of 3-Oxetanone in the Gas Phase

2017 ◽  
Vol 42 (1) ◽  
pp. 36-43 ◽  
Author(s):  
Mohammad Khavani ◽  
Javad Karimi
Keyword(s):  
Thermal Decomposition ◽  
Carbon Monoxide ◽  
Ethylene Oxide ◽  
Gas Phase ◽  
Transition States ◽  
Decomposition Reaction ◽  
Kinetics And Mechanism ◽  
Methyl Radical ◽  
Decomposition Products ◽  
Concerted Mechanism

The kinetics and mechanism of the thermal decomposition reaction of 3-oxetanone in the gas phase were studied using quantum chemical calculations. The major products of this reaction are formaldehyde, ketene, carbon monoxide, ethylene oxide, ethylene and methyl radical. Formaldehyde, ketene, carbon monoxide and ethylene oxide are the initial decomposition products and other species are the products of ethylene oxide decomposition. The results of B3LYP and QCISD(T) calculations reveal that thermal decomposition of 3-oxetanone to ethylene oxide and carbon monoxide is more probable than to formaldehyde and ketene from an energy viewpoint. Moreover, quantum theory of atoms in molecules and natural bond orbital analysis indicate that 3-oxetanone decomposition to formaldehyde, ketene, carbon monoxide and ethylene occurs via a concerted mechanism and bonds that are involved in the transition states have a covalent character. Moreover, the calculated changes in bond lengths in the transition states reveal that bond breaking and new bond formation occur asynchronously in a concerted mechanism.

Kinetics and mechanism of the thermal decomposition reaction of 3,3-Bis(azidomethyl)oxetane/tetrahydrofuran copolymer

2010 ◽  
Vol 22 (11) ◽  
pp. 1219-1224 ◽  
Author(s):  
Yang Luo ◽  
Pei Chen ◽  
Feng-Qi Zhao ◽  
Rong-Zu Hu ◽  
Shang-Wen Li ◽  
...  
Keyword(s):  
Thermal Decomposition ◽  
Decomposition Reaction ◽  
Kinetics And Mechanism

DFT Investigation of the Kinetics and Mechanism of the Thermal Decomposition of Oxalic Acid

2017 ◽  
Vol 42 (1) ◽  
pp. 44-51 ◽  
Author(s):  
Mohammad Khavani ◽  
Mohammad Izadyar ◽  
Azam Jamsaz
Keyword(s):  
Thermal Decomposition ◽  
Energy Density ◽  
Oxalic Acid ◽  
Gas Phase ◽  
Density Functional ◽  
Lone Pair ◽  
Theoretical Data ◽  
Density Functional Theory Calculations ◽  
Kinetics And Mechanism ◽  
Kinetic Energy Density

Density functional theory calculations with different functionals have been performed to investigate the kinetics and mechanism of the thermal decomposition of oxalic acid in the gas phase and in solution in aniline, N-methylaniline, quinoline and DMSO. Five major possible mechanisms for this reaction have been proposed. Comparison between the theoretical data and experimental results shows that in the most probable path of this reaction CO, CO2 and H2O are produced. Moreover, this reaction is a little faster in the gas phase than in solvents. Quantum theory of atoms in molecules analysis indicates that C–C and O–H bond formations in the transition states have a covalent nature, because the ratios of kinetic energy density to potential energy density at the corresponding bond critical points are smaller than 0.5. Based on natural bond orbital analysis, during transition state formation, the interaction energy between the lone pair of electrons of the oxygen atom and the π* molecular orbital of the critical C–O bond is reduced and solvents affect the charge transfer process.

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