The processes model in a flame during the n-alkanes air mixture combustion initiation is proposed, taking into account the supramolecular structures formation possibility in the peroxide clusters form. This approach is justified by the n-alkanes melting temperatures correlation with their autoignition temperatures and anti-knock indexes. The condensation possibility is provided for such high molecular structures. Boiling temperatures values at flame front pressures characteristic were evaluated. To predict the peroxide clusters melting temperatures, a formula developed earlier for the hydrocarbons condensed state was used, which takes into account the length and molecular weight of modeled clusters. Expected peroxide clusters melting temperatures were predicted for conditions of dimeric and tetrameric structures. A linear dependence was used to recalculation the obtained values in boiling temperatures. It is shown that the calculated clusters phase transitions characteristic temperatures can be realized in the flame front preparatory zone. Based on the condensation theory, the flame front thickness and the minimum non-extinguishing sphere radius during ignition were estimated: the obtained data closely coincide with these parameters known values.