The effects of thermal oxidation on the molecular and macromolecular structures of additive free PE were investigated between 100 °C and 140 °C in air in order to tentatively establish non‐empirical structure/property relationships. In the first part, the changes in POOH concentration were assessed by three different analytical methods: iodometry, modulated differential scanning calorimetry, and Fourier transform infrared (FTIR) spectrophotometry after SO2 treatment. All these methods provided very similar results until the end of the induction period, after which iodometry overestimated strongly POOH concentration because it titrates also other chemical species formed at high conversion ratios, namely double bonds. In parallel, the changes in carbonyl group concentration were determined by FTIR spectrophotometry after NH3 treatment. As the accumulation kinetics of ketones, aldehydes, and carboxylic acids were closely interrelated, the question of their actual formation mechanisms in the current thermal oxidation mechanistic scheme was raised. An alternative reaction pathway was proposed for the bimolecular decomposition of POOH. In the second part, the corresponding changes in weight and number average molecular masses were monitored by high temperature gel permeation chromatography equipped with a triple detection technology. As both quantities decreased dramatically from the beginning of exposure and their ratio Mw/Mn tends toward the asymptotic value of 2 and it was concluded that a “pure” chain scission process operated. Finally, as the number of chain scissions perfectly correlates, the concentration sum of aldehydes and their oxidation products (i.e., carboxylic acids), it was also concluded that these carbonyl groups result exclusively from the β scission of alkoxy radicals. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43287.

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