The ultraviolet absorption spectrum of tert-butyl radicals and the rate constant for their recombination

Add time:07/13/2019    Source:sciencedirect.com

Using the technique of molecular modulation spectrometry, an ultraviolet absorption spectrum which we assign to t-butyl radicals has been obtained during the photolysis of azoisobutane and nitrogen mixtures and di-tert-butyl peroxide and isobutane mixtures. The spectrum is a broad absorption band about 20 nm wide centered at 230 nm lying on top of a weaker continuum that extends to 270 nm. At the peak (λ ≈ 229 nm) the cross section is 5 × 10−18 cm2. From the rate constant of their mutual reaction and the recombination/disproportionation ratio measured in separate experiments, the rate of the reaction 2(CH3)3C → (CH3)3CC(CH3)3 has been measured as (2.0 ± 0.3) × 10−12 cm3 molecule−1 s−1 at 25°C (1.2 × 109 g mol−1 s−1). This result is compared with other recent gas- and liquid-phase determinations.

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