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The Decomposition of 2,2,3,3-Tetramethylbutane in KCl- and B2O3-coated Vessels in the Presence of Oxygen

DOI: 10.1039/f19827801165

Source and publish data:

Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 1165 - 1176 (1982)

Update date:2022-08-28

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Authors:

Baldwin, Roy R.Baldwin, Roy R.

Hisham, Mohamed W. M.Hisham, Mohamed W. M.

Keen, AlanKeen, Alan

Walker, Raymond W.Walker, Raymond W.

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Article abstract of DOI:10.1039/f19827801165

The decomposition of 2,2,3,3-tetramethylbutane (TMB) in the presence of oxygen has been studied in both KCl-coated and aged boric-acid-coated vessels.The values for k1 obtained with the two types of vessel surface are in close agreement, and combination of the values over the range 400-542 deg C gives A1 = 1.04 E17 s-1, E1 = 294.7 +/- 3 kJ mol-1, effectively identical with previous values using KCl-coated vessels, and thus confirming the thermochemistry suggested for the t-butyl radical: (CH3)3C-C(CH3)3 --> 2(CH3)3C. (1) The observed rate constant, kobs, defined by the equation -d/dt = kobs increases with increasing TMB concentration with both types of vessel surface and this variation has been used to evaluate the ratio k4/k70.5.The results with both types of vessel surface are in agreement, giving A4/A70.5 = 4.4 E5 (dm3 mol-1 s-1)0.5, E4 - 0.5 E7 = 81.7 +/- 8 kJ mol-1 over the range 400-520 deg C: HO2 + (CH3)3C-C(CH3)3 --> H2O2 + (CH3)3C --> C(CH3)2CH2 (4) HO2 + HO2 --> H2O2 + O2. (7)

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