Kinetics Database Resources
Choi, Y.M.; Park, J.; Lin, M.C.
Title: Experimental and Computational Studies of the Kinetics and Mechanisms for C6H5 Reactions with Acetone -h6 and -d6
Journal: J. Phys. Chem. A
Page(s): 7755 - 7761
Reference type: Journal article
(CD3)2CO + Phenyl → ·CD2C(O)CD3 + Benzene-d
DFT quantum calculations B3LYP/aug-cc-pvTZ energies. Rate expressions calculated using Truhlars Polyrate program. Tunneling correction CVT/SCT employed.
Quantum calculations found abstraction barrier of about 3.9 kcal/mol, C addition channel with barrier of about 9.4 kcal/mol, and O addition channel with barrier of about 12.4 kcal/mol. Thus, abstraction dominates. C addition channel can lead to beta scission of CH3 and formation of methyl phenyl ketone with calculated barrier of about 8.1 kcal/mol
Used transition states from quantum calculations to get functional form of rate expression in order to provide expression over a range of temperatures (298-1200 K). Adjusted calculated barrier of 3.9 kcal/mol to 3.3 kcal/mol to get rate expression to agree with experimental rate constants.
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Rate constant values calculated from the Arrhenius expression: