Abstract:
The oxidation of 2,2,3,3-tetramethylbutane in KCl-coated vessels has been studied between 440 and 54O°C, and over the pressure range 60-500 Torr. The results are consistent with a simple mechanism comprising reactions (l)-(3)
(CH3)3C— C(CH3)3 -> 2t-C4H9 t-C4H9 + O2 —> i-C4H8 + HO2 surface
HO2-> tH2O+iO2.
(1)
(2)
(3)
After allowance for a small (<20 %) contribution from a chain process, accurate Arrhenius parameters Ai = 6.0x 1016 s-1, Ei = 290.4 kJ mol-1 have been obtained by combination with Tsang’s results. From the thermochemistry of reaction (1) and literature values for k-i, values of AfJ7298 (t-Bu) = 44.0 + 4.0 kJ mob* and 5298(t-Bu) = 304.2±4.0 J K-1 mol-1 are recommended.
Analysis of the products shows that ~1 % of the t-butyl radicals give isobutene oxide and over the temperature range 470-542°C, Az/Au = 13.8 and £13 — E2 = 13.0 kJ mol-1 where reaction (13) is the overall process,
t-C4H9 + O2 — C4H8O+OH. (13)
Reaction (13) is discussed in terms of the peroxy radical isomerisation and decomposition theory and Arrhenius parameters are suggested for the (1, 4/>) H atom transfer reaction (17) in t-butylperoxy radicals
(CH3)3CO2 -> (CH3)2C(OOH)CH2.
(17)
