Activation parameters and conformational stabilities characterizing the internal rotation about the peptide bond in a series of N,N-asymmetric dialkylformamides (HCONR1R2 : R-1 = CH3, R-2 = propyl, butyl, and isopropyl) and N,N-asymmetric dialkyltrifluoroacetamides (F3CCONR1R2 : R-1 = CH3, R-2 = propyl, butyl, and isopropyl) are determined from temperature-dependent gas-phase H-1 NMR spectra. Conformer free energy differences, Delta G(298)(0)(syn-anti), in cal mol(-1), and activation free energies, Delta G(298)(double dagger), in kcal mol(-1), for the formamides are -83(14)/19.4(0.1) for R-2 = Propyl, -80(14)/19.3(0.1) for R-2 = butyl, and -91(13)/19.1(0.1) for R-2 = isopropyl and for the trifluoroacetamides 178(24)/16.8(0.1) for R-2 = propyl, 191(53)/16.6(0.1) for R-2 = butyl, and 218(29)/16.3(0.1) for R-2 = isopropyl. The preferred conformer in both the gas and Liquid phases has the N-methyl group syn to the carbonyl oxygen in the formamide systems and the N-methyl group anti to the carbonyl oxygen in the trifluoroacetamides. The gas-phase results are compared to liquid-phase values.