Piperazine (PZ) is widely recognized as a promising solvent for postcombustion capture (PCC) of carbon dioxide (CO2). In view of the highly conflicting data describing the kinetic reactions of CO2(aq) in piperazine solutions, the present study focuses on the identification of the chemical mechanism, specifically the kinetic pathways for CO2(aq) in piperazine solutions that form the mono- and dicarbamates, using the analysis of stopped-flow spectrophotometric kinetic measurements and H-1 NMR spectroscopic data at 25.0 degrees C. The complete set of rate and equilibrium constants for the kinetic pathways, including estimations for the protonation constants of the suite of piperazine carbamates/carbamic acids, is reported here using an extended kinetic model which incorporates all possible reactions for CO2(aq) in piperazine solutions. From the kinetic data determined in the present study, the reaction of CO2(aq) with free PZ was found to be the dominant reactive pathway. The superior reactivity of piperazine is confirmed in the kinetic rate constant determined for the formation of piperazine monocarbamic acid (k(7) = 2.43(3) x 10(4) M-1 s(-1)), which is within the wide range of published values, making it one of the faster reacting amines. The corresponding equilibrium constant for the formation of the monocarbamic acid, K-7, markedly exceeds that of other monoamines. Kinetic and equilibrium constants for the remaining pathways indicate a minor contribution to the overall kinetics at high pH; however, these pathways may become more significant at higher CO2 loadings and lower pH values where the concentrations of the reactive species are correspondingly higher.