This paper (part 1) and the following one (part 2) aim to assess the viability of some tropospheric oxidation channels for two symmetrical alkynes, ethyne (acetylene) and but-2-yne. Paper I defines the features of the DFT(B3LYP)/6-311G(3df,2p) energy hypersurface and qualitatively considers the practicability of different pathways through the estimate of free energy barriers. Paper 2 will assess this in more detail by way of master equation simulations. Oxidized in the presence of HO and O, (with the possible intervention of NO), ethyne and but-2-yne are known to produce mainly glyoxal or dimethylglyoxal and, to a lesser extent, formic or acetic acid. The initial attack by HO gives an adduct, from which several pathways (la-c, 2a-e) originate. Pathway la passes through the 2-oxoethyl (vinoxyl) radical, or the analogous dimethyl-substituted intermediate, which could in principle undergo 0, addition (and subsequently, but through a demanding step, give the dialdehydes). However, in paper 2 it is assessed that the vinoxyl, as a nonthermalized intermediate, will preferentially follow unimolecular pathways to ketene or acetyl. Pathway 2a is the most important pathway: a very steep free energy cascade, started by O-2 addition to the initial HO adduct with a concerted barrierless 1,5 H shift, gives a hydroperoxyalkenyloxyl radical intermediate. Peroxy bond cleavage finally produces the dialdehydes and regenerates HO. Pathways 2b and 2c originate from O-2 addition to the initial HO adduct and produce, via different ring closures, either dioxetanyl or alkyl dioxiranyl radicals, respectively. Two subsequent fragmentations occur in both cases and give the carboxylic acids and a carbonyl radical, which can indirectly generate hydroxyl. Two further pathways (1c and 2e) see NO intervention onto the peroxyl radicals formed along pathways 1 and 2. Both could enhance dialdehyde production, while simultaneously depressing the carboxylic acid yield.