The inertness of molecular nitrogen and the reactivity of acetylene suggest there are significant variations in the nature of triple bonds. To understand these differences, we performed generalized valence bond as well as more accurate electronic structure calculations on three molecules with putative triple bonds: N-2, HCN, and HC2H. The calculations predict that the triple bond in HC2H is quite different from the triple bond in N-2 with HCN being an intermediate case but closer to N-2 than HC2H. The triple bond in N-2 is a traditional triple bond with the spins of the electrons in the bonding orbital pairs predominantly singlet coupled in the GVB wave function (92%). In HC2H, however, there is a substantial amount of residual CH(a(4)Sigma(-)) fragment coupling in the triple bond at its equilibrium geometry with the contribution of the perfect pairing spin function dropping to 82% (77% in a full valence GVB calculation). This difference in the nature of the triple bond in N-2 and HC2H may well be responsible for the differences in the reactivities of N-2 and HC2H.