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Title: | Understanding the kinetics of thermal decomposition of 2,3-epoxy-2,3-dimethylbutane using RRKM theory | Authors: | SHIROUDI, Abolfazl Zahedi, Ehsan |
Issue Date: | 2016 | Source: | RSC advances, 6(94), p. 91882-91892 | Abstract: | The thermal decomposition kinetics of 2,3-epoxy-2,3-dimethylbutane have been studied computationally using density functional theory, along with various exchange–correlation functionals and an extremely large basis set. The calculated energy profiles have been supplemented with calculations of kinetic rate constants and branching ratios under atmospheric pressure and in the fall-off regime have been supplied, using transition state theory (TST) and statistical Rice–Ramsperger–Kassel–Marcus (RRKM)theory. Kinetic rate constants and branching ratios under atmospheric pressure and in the fall-off regime have been supplied, using transition state and RRKM theories. By comparison with experiment, all our calculations indicate that, from a kinetic viewpoint, the most favorable process is thermal decomposition of 2,3-epoxy-2,3-dimethylbutane into the 2,3-dimethylbut-3-en-2-ol, whereas under thermodynamic control of the reactions, the most abundant product derived from the 2,3-epoxy-2,3-dimethylbutane species will be the 3,3-dimethylbutan-2-one species. The regioselectivity of the decomposition decreases with increasing temperatures and decreasing pressures. In line with rather larger energy barriers, pressures larger than 10-6 bar are in general sufficient for ensuring a saturation of the computed unimolecular kinetic rate constants compared with the high-pressure limit (TST) of the RRKM unimolecular rate constants. The bonding evolution theory indicated that thermal decomposition of 2,3-epoxy-2,3-dimethylbutane into the 2,3-dimethylbut-3-en-2-ol takes place along three differentiated successive structural stability domains after passing the reactant from the associated transition state. | Notes: | Shiroudi, A (reprint author), Hasselt Univ, Ctr Mol & Mat Modelling, Agoralaan,Gebouw D, B-3590 Diepenbeek, Belgium. abolfazl.shiroudi@uhasselt.be | Keywords: | 2,3-epoxy-2,3-dimethylbutane; decomposition; energy barriers; rate constants; unimolecular reaction; reaction mechanisms | Document URI: | http://hdl.handle.net/1942/22518 | e-ISSN: | 2046-2069 | DOI: | 10.1039/C6RA21963B | ISI #: | 000385367300096 | Rights: | This journal is © The Royal Society of Chemistry 2016 | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2017 |
Appears in Collections: | Research publications |
Files in This Item:
File | Description | Size | Format | |
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c6ra21963b.pdf Restricted Access | Published version | 1.41 MB | Adobe PDF | View/Open Request a copy |
c6ra21963b1.pdf Restricted Access | Supplementary material | 181.21 kB | Adobe PDF | View/Open Request a copy |
Manuscript 2.pdf | Peer-reviewed author version | 753.47 kB | Adobe PDF | View/Open |
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