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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:   299 - 451 K
Pressure:  2.67E-2 - 1.00E-1 bar
Rate expression:   6.97x10-13 [±6.64x10-14 cm3/molecule s] e-7940 [±249 J/mole]/RT
Bath gas:   Ar
Category:  Experiment
Data type:   Absolute value measured directly
Pressure dependence:   Rate constant is pressure independent
Experimental procedure:   Static or low flow - Data taken vs time
Excitation technique:   Flash photolysis (laser or conventional)
Time resolution:   In real time
Analytical technique:   Other (Vis-UV)
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

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Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm3/molecule s]
299 2.86E-14
300 2.89E-14
325 3.69E-14
350 4.56E-14
375 5.46E-14
400 6.41E-14
425 7.37E-14
450 8.35E-14
451 8.39E-14