[en] On γ-irradiation of dilute solutions of propiolic acid in CFCl3 at 77 K, no e.s.r. spectrum assignable to the parent cation was detected. Instead, a triplet was observed with a coupling of 5.8 G, which we assign to the dimer cation (HC≡CCO2H)2 sup(+.). On similar treatment, the esters MeC≡CCO2Me and HC≡CCO2Me gave only the rearranged cations: RC≡CC(=OH)OCH2. (author)