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Author(s):   Caralp, F.; Forst, W.; Henon, E.; Bergeat, A.; Bohr, F.
Title:   Tunneling in the reaction of acetone with OH
Journal:   Phys. Chem. Chem. Phys.
Volume:   8
Page(s):   1072 - 1078
Year:   2006
Reference type:   Journal article
Squib:   2006CAR/FOR1072-1078

Reaction:   (CH3)2CO + ·OHCH3C(O)CH2(·) + H2O
Reaction order:   2
Temperature:   199 - 700 K
Rate expression:   1.36x10-14 [cm3/molecule s] (T/298 K)4.43 e-6577 [J/mole]/RT
Category:  Uncategorized
Comments:   Total Abstraction (two channels). No rate expressions given in paper, only rate constants. Rate expression given here is NIST fit to rate constants in tables in paper.

Studied reaction of CH3C(O)CH3 acetone + OH. Two possible product channels abstraction going to CH3COCH2 + H2O, and the other addition of OH followed by beta scission of CH3. Addition/beta scission channel is small compared to abstraction. Also studied isotope effect using CD3C(O)CD3.

Used ab initio potential surfaces from earlier work by the authors PCCP 5, 333 (2003) and JCP 119, 10600 (2003). Used RRKM theory to derive rate constants. Including tunneling correction zero curvature tunneling WKB approximation.

All reaction channels proceed through weakly bound adducts. The abstraction channel is the sum of two configurations with different hydrogen bonding arrangements. Tunneling correction is very important at low temperatures. The calculated rate constants agree well (20-30%) with experimental values including describing curvature in temperature dependence.

View full bibliographic record.


Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm3/molecule s]
199 4.27E-17
200 4.46E-17
250 2.64E-16
300 1.00E-15
350 2.90E-15
400 6.94E-15
450 1.46E-14
500 2.77E-14
550 4.88E-14
600 8.09E-14
650 1.28E-13
700 1.93E-13