This work examines the inherent features in the low temperature oxidation of cycloalkanes which distinguish cyclic alkanes from open-chain alkanes. The first part of the discussion is based on the recent motored-engine studies of cyclic hydrocarbons, [Yang and Boehman, Proc. Combust. Inst. 32, p.419; Yang and Boehman, Combust. Flame, 157, p. 495], and focuses on the formation of conjugate olefins in low temperature oxidation. While less reactive than linear alkanes of similar size, cyclic hydrocarbons produced significant amounts of conjugate olefins during low temperature oxidation, which is uncharacteristic of linear alkanes. Conformational analyses in this paper and in a companion paper reveal that the inhibited low temperature chain branching and the promoted olefin formation are due to the steric structures of the cyclic compounds limiting the number of hydrogens available to the (1,5) H-shift but alternatively enhancing the opportunity for the (1,4) H-shift during the isomerization of the fuel peroxy radicals, ROO center dot -> (center dot)QOOH. The second part of this work focuses on the role of methyl substitution in low temperature oxidation of cycloalkanes, which is drastically different from that of linear alkanes. Ab initio calculations are conducted on cyclohexane and methylcyclohexane to compute the activation energy of the (1,5) and (1,4) H-shift with full consideration of species conformation. The presence of the methyl group is found to enable low activation-energy channels in the (1,5) H-shift. Next, the impact of methyl substitution on the formation of conjugate olefins is discussed for methylcyclohexane and methylcyclopentane. Based on the experimentally determined yields of conjugate olefin isomers, estimations are made of the fraction of each fuel radical that is converted to conjugate olefins. For both compounds, more tertiary radicals are converted to conjugate olefins than secondary radicals, and primary radicals have the least fraction being converted. (C) 2010 The Combustion Institute. Published by Elsevier Inc. All rights reserved.