Absolute rate constants for hydrocarbon autoxidation. 29. Rate constants for abstraction of primary aliphatic hydrogens from 2,2-dimethylbutane by the tert-butylperoxy radical

Abstract

Rate constants for abstraction of primary and secondary hydrogens from 2,2-dimethylbutane by the tert-butylperoxy radical at temperatures from 323 to 353 K have been determined from autoxidations and co-autoxidations in the presence of tert-butyl hydroperoxide. At 333 K the rate constant for abstraction of a secondary hydrogen is ~1.5 × 10−3 M−1 s−1 and the rate constants for abstraction of a primary hydrogen from the tert-butyl and methyl groups of 2,2-dimethylbutane are ~4 × 10−5 and ~6 × 10−5 M−5 s−1 respectively.