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Extra info for Absolute Intensities in the Hydrogen-Chloride Rotation Spectrum
Any general mechanism should explain the data shown. Reactions (42)-(44) all show positive temperature coefficients and all are sufficiently fast to be important in atmospheric chemistry. The rate expression given for reaction (42) in Table 16 reflects a complex variation of k , which decreases in value by about 1 5 % between 298 and 474 Κ and then increases by a factor of 2 up t o 684 K. Grotheer et al  interpreted this behaviour as a change in mechanism, with mainly an association reaction C H O H + O2 - » O2CH2OH at l o w temperatures being replaced by an abstraction process at high temperatures.
Presumably, the C H 0 * would have t o undergo a concerted reaction t o form C H and H0 . 2 2 5 2 2 4 2 (hi) Walker and M c A d a m  have suggested that 0 h a s particular characteristics as an abstracting species. It is suggested that as 0 attacks an Η a t o m on the C H group in the C H radical, the high density of unpaired electrons on the remote Ο a t o m may lead t o bonding between this a t o m and the carbon a t o m with the localised free electron. A s the resulting ring would be relatively unstrained, the intermediate may have a degree of stability so that the competition between reverse decomposition and forward formation of C H could give rise t o a negative temperature coefficient.
Tertiary; Ο , secondary; χ , primary • , pentenyl; # , allyl C-H. One example, which has been examined in detail by Baldwin and Walker  and more recently by Pilling , is the chemistry associated with the formation and removal of neopentylperoxy radicals leading t o the formation of i-butene, acetone and 3,3dimethyloxetane ( D M O ) 40 (a) (CH ) CCH + 0 I 3 3 2 (CH ) CCH 0 3 3 2 *• 2 3 2 2 3 C H 2 2 CH OOH 2 / (CH ) OCH , (CH ) Q (b) z ^ ^ 2 + CH (°) (d) (CH ) CO + 2 H C H 0 + OH 3 3 2 (CH ) C-CH 3 2 2 CH O (DMO) 2 Baldwin and Walker confirmed the following t w o relative initial rates of product formation from studies of the addition of neopentane t o mixtures of H + 0 between 673 and 773K 2 d([DMO] + [ C H C O C H ] ) 3 3 k b K ^ [Oj] = d[i-C H ] 4 k 8 and < J [ C H C O C H 3 3 3 2 ( x y i i ) e = d[DMO] k c and were able t o determine kinetic data for a number of the elementary reactions involved.