The vaporization enthalpies of a series of heterocyclic compounds some suspected of showing evidence of a higher degree of self association in comparison to many other nitrogen heterocycles, have been measured both by correlation gas chromatography (CGC) and for comparison by transpiration. The compounds share some structural similarities. They include 2- and 4-(N,N-dimethylamino)pyridine, 1,5-diazabicydo[4.3.0]non-5-ene, 1,8-diazabicydo[5.4.0]undec-7-ene, 1,2,4-triazolo[1,5-a]pyrimidine and imidazo[1,2-a]pyridine. The vaporization enthalpies of the first three of the compounds are well reproduced by a standard series of reference compounds, mainly pyridine derivatives. The latter two compounds and 4-(N,N-dimethylamino)pyridine exhibit vaporization enthalpies approximately 7 kJ.mol(-1) larger. Their values are reproduced by using standards previously shown to exhibit stronger but similar self-association properties. The crystal structure of 1,2,4-triazolo [1,5-a]pyrimidine has been determined in an effort to understand the nature of the self-association. The molecule crystallizes in planar stacks slightly offset with a stacking distance of 3.24 angstrom.