Although enols have been identified in alcohol and other flames and in interstellar space and have been implicated in the formation of carboxylic acids in the urban troposphere in the past few years, the reactions that give rise to them are virtually unknown. To address this data deficit, particularly with regard to biobutanol combustion, we have carried out a number of ab initio calculations with the multilevel methods CBS-QB3 and CBS-APNO to determine the activation enthalpies for methyl addition to the CH2 group of CH2=CHX where X = H, OH, and CH3. These average at 26.3 +/- 1.0 kJ mol(-1) and are not influenced by the nature of X; addition to the CHX end is energetically costlier and does show the influence of group X = OH and CH3. Replacing the attacking methyl radical by ethyl makes very little difference to addition at CH2 and follows the same trend of a higher barrier for addition to the CH(OH) end. In the case of H-addition it is more problematic to draw general conclusions since the DFT-based methodology, CBS-QB3, struggles to locate transition states for some reactions. However, the increase in barrier heights in reaction at the CHX end in comparison to addition at the methylene end is evident, For hydrogen atom reaction with the carbonyl group in the compounds methanal, ethanal, propanal, and butanal we see that for addition at the O-center the barrier heights of ca. 38 kJ mol(-1) are not influenced by the nature of the alkyl group whereas addition at the C-center is different on going from H -> alkyl but seems to be invariant at 20 kJ mol(-1) once alkylated. Rate constants for H-atom elimination from 1-hydroxyethyl, 1-hydroxypropyl, and 1-hydroxybutyl radicals, valid over the range 800-2000 K, are reported. These demonstrate that enols are more prevalent than previously suspected and that 1-buten-1-ol should be almost as abundant as its isomeric aldehyde 1-butanal during the combustion of 1-butanol and that this will also be the case for other alcohols provided that the appropriate structural features are present. Since the toxicity of enols is not known experiments and further theoretical studies are clearly desirable before the large-scale usage of alcohol biofuels commences. An enthalpy of formation for butanal of Delta H-f(298.15 K) = -204.4 +/- 1.4 kJ mol(-1) [Buckley, E.; Cox, J. D. Trans. Faraday Soc. 1967, 63, 895-901] is recommended, the uncertainty surrounding that for the 2-hydroxypropyl radical has been markedly reduced, and new values for 1-buten-1-ol, 1-propen-1-ol, and 2-propen-2-ol of -171.8 +/-1.6, -151.8 1 +/- 1.7, and -169.9 +/- 1.5 kJ mol(-1), respectively, are proposed.