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Author(s):   Shestov, A.A.; Popov, K.V.; Knyazev, V.D.
Title:   Kinetics of the CH2Cl+CH3 and CHCl2+CH3 radical-radical reactions
Journal:   J. Phys. Chem. A
Volume:   109
Page(s):   6249 - 6254
Year:   2005
Reference type:   Journal article
Squib:   2005SHE/POP6249-6254

Reaction:   ·CH3 + ·CH2Cl → Products
Reaction order:   2
Temperature:   301 - 800 K
Pressure:  6.00E11 - 1.20E12 bar
Rate expression:   3.93x10-11 [cm3/molecule s] e757 [J/mole]/RT
Category:  Experiment
Data type:   Absolute value measured directly
Pressure dependence:   None reported
Experimental procedure:   Static or low flow - Data taken vs time
Excitation technique:   Flash photolysis (laser or conventional)
Time resolution:   In real time
Analytical technique:   Mass spectrometry
Comments:   Methyl radicals were produced by photolysis of acetone at 193 nm. Chloromethyl and dichloromethyl radicals were produced by 193 nm photolysis of dichloromethane or trichloromethane, respectively. Decays of both CH2Cl and CH3 were followed in real time with photoionization mass spectrometry.

The primary detected reaction product was C2H4 resulting from chemically activated elimination of HCl from the initial adduct.

View full bibliographic record.

Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm3/molecule s]
301 5.32E-11
325 5.20E-11
350 5.10E-11
375 5.01E-11
400 4.93E-11
425 4.87E-11
450 4.81E-11
475 4.76E-11
500 4.71E-11
525 4.67E-11
550 4.64E-11
575 4.60E-11
600 4.57E-11
625 4.55E-11
650 4.52E-11
675 4.50E-11
700 4.48E-11
725 4.46E-11
750 4.44E-11
775 4.42E-11
800 4.40E-11