An absolute measurement of the rate constant for t‐butyl radical combination

The rate constant for tert‐butyl radical recombination has been measured near 700°K by the very‐low‐pressure pyrolysis (VLPP) technique and was found to be 108.8±0.3 M−1·sec−1 with neglibible temperature dependence. The thermochemical parameters for tertbutyl radicals were varied within reasonable limits to bring into agreement the data for the decomposition of 2,2,3,3‐tetramethyl butane and the recombination of tert‐butyl radicals. The revised thermochemistry also makes the gas‐phase results and liquid‐phase results compatible.