Journal of the Chemical Society - Faraday Transactions p. 1303 - 1312 (1995)
Update date:2022-08-25
Topics:
Seres, Laszlo
Fischer, Ronald
Scherzer, Klaus
Goergenyl, Miklos
The azoisopropane-initiated thermal reaction of (E)-CH3CH=CHCH3 has been studied in the temperature range 489.5-542.0 K.For the reactions (CH3)2CHN=NCH(CH3)2 --> 2 2-C3H7(.) + N2 (1) 2-C3H7(.) + (E)-CH3CH=CHCH3 --> C3H8 + (E)-C4H7(.) (4) --> (CH3)2CHCH(CH3)CH(CH3)(.) (5) 2 2-C3H7(.) --> (CH3)2CHCH(CH3)2 (2) the following Arrhenius parameters were determined: log(k1/s-1) = (16.42 +/- 0.30) - (201.9 +/- 3.0) kJ mol-1/θ log<(k4/k21/2)/dm3/2 mol-1/2 s-1/2> = (3.64 +/- 0.40) - (46.9 +/- 2.1) kJ mol-1/θ log<(k5/k21/2)/dm3/2 mol-1/2 s-1/2> = (2.53 +/- 0.60) - (39.5 +/- 2.4) kJ mol-1/θ where θ = RT in 10.For the croos-combination ratios of the radicals 2-C3H7(.) and (Z)-C4H7(.), Φ<2-C3H7(.), (Z)-C4H7(.)>t = 2.12 +/- 0.10 was obtained, where the subscript t refers to the terminal combination.Formation of certain characteristic products was observed in various addition/isomerization/dissociation processes. 2-C3H7(.) addition to (E)-CH3CH=CHCH3 is suggested as the rate-determining step, followed by 1,4- and 1,5-H-atom shifts.
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