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Title: Structure-reactivity relationship in ketones plus OH reactions: A quantum mechanical and TST approach
Journal: J. Phys. Chem. A
Volume: 108
Page(s): 2740 - 2749
Year: 2004
Reference type: Journal article
Squib: 2004ALV/CRU2740-2749
Reaction:
(CH3)2CO + ·OH → CH3C(O)CH2(·) + H2O
Reaction order:
2
Temperature:
280 - 440
K
Rate expression:
5.18x10-12 [cm3/molecule s] e-8201 [J/mole]/RT
Category: Theory
Data type:
Ab initio
Pressure dependence:
Rate constant is pressure independent
Comments:
The authors used CCSD(T)//BHandHLYP/6-311G(d,p) calculations to study the OH hydrogen abstraction reaction from acetone, 2-pentanone, and methyl butanone (3-methyl-2-butanone). The calulations appear to confirm the formation of a hydogen-bonded transition-state complex involving the carbonyl oxygen for some H abstractions, particularly those beta to the carbonyl, which result in a 6-center transition state. Good agreement between calculated and experimental k at 298 K has been obtained.
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Rate constant values calculated from the Arrhenius expression:
| T (K) | k(T) [cm3/molecule s] |
|---|---|
| 280 | 1.53E-13 |
| 300 | 1.93E-13 |
| 325 | 2.49E-13 |
| 350 | 3.09E-13 |
| 375 | 3.73E-13 |
| 400 | 4.40E-13 |
| 425 | 5.09E-13 |
| 440 | 5.51E-13 |