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Author(s):   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
Volume:   107
Page(s):   7755 - 7761
Year:   2003
Reference type:   Journal article
Squib:   2003CHO/PAR7755-7761

Reaction:   Acetone + PhenylBenzene + CH3C(O)CH2(·)
Reaction order:   2
Temperature:   298 - 1200 K
Pressure:  2.67E-2 - 1.00E-1 bar
Rate expression:   6.96x10-15 [±2.46x10-15 cm3/molecule s] (T/298 K)(4.20±0.10) e3875 [±216 J/mole]/RT
Bath gas:   Ar
Category:  Theory
Data type:   Transition state theory
Comments:   Combined experimental and quantum study. C6H5 produced by 248 nm KrF excimer laser photolysis of C6H5NO. C6H5 detected using cavity ring down spectroscopy at 504.8 nm versus time. Typical acetone 0-0.35 torr in 20-75 torr Argon. Used both acetone and deuterated acetone (d6).

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.

View full bibliographic record.

Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm3/molecule s]
298 3.32E-14
300 3.38E-14
350 5.18E-14
400 7.68E-14
450 1.11E-13
500 1.55E-13
550 2.13E-13
600 2.86E-13
650 3.77E-13
700 4.89E-13
750 6.25E-13
800 7.88E-13
850 9.83E-13
900 1.21E-12
950 1.48E-12
1000 1.79E-12
1050 2.15E-12
1100 2.56E-12
1150 3.03E-12
1200 3.56E-12