The amine carbamate related equilibrium (RNHCOO- + H2O reversible arrow RNH2 + HCO3-) has been investigated with C-13 NMR (Nuclear Magnetic Resonance) spectroscopy for a series of linear primary alkanolamines, and the apparent carbamate decomposition equilibrium constants have been estimated. A quantitative NMR method for the calculation of the concentration of the species formed in solution has been provided, including the assessment of each of the fast exchanging proton species (whose nuclei resonate at the same chemical shifts in the NMR spectra). For this purpose, NMR-based calibration curves were utilized and an alternative method was applied for validation. The overall results showed that the amount of carbamate found at the equilibrium decreased as the length of the carbon chain increased, while the corresponding apparent carbamate decomposition equilibrium constants featured the same order of magnitude (10(-2)).