Thermal decomposition of hexamethylethane in a flow system

Hexamethylethane has been decomposed in a flow system in the temperature range of 700–900 K. The mechanism involves carbon–carbon bond cleavage at the most highly substituted position and rapid formation of isobutene from the t‐butyl radical. The rate expression is and is completely consistent with deductions from radical buffer, shock‐tube, and direct recombination studies. Of special importance is experimental evidence for large decreases of the A factor with increasing temperature and a high heat of formation for the t‐butyl radical, ΔHf(tC4H9·)300 = 52.7 ± 6 kJ.