CO2 absorption into aqueous solutions of two tertiary alkanolamines, namely, MDEA and DMEA with and without carbonic anhydrase (CA) was investigated with the use of the stopped-flow technique at temperatures in the range of 293-313 K, CA concentration varying from 0 to 100 g/m(3) in aqueous MDEA solution with the amine concentration ranging from 0.1 to 0.5 kmol/m(3), and CA concentration varying from 0 to 40 g/m(3) in aqueous DMEA solution with the amine concentration ranging from 0.05 to 0.25 kmol/m(3). The results show that the pseudofirst-order reaction rate (k(0, amine); s(-1)) is significantly enhanced in the presence of CA as compared with that without CA. The enhanced values of the kinetic constant in the presence of CA has been calculated and a new kinetics model for reaction of CO2 absorption into aqueous tertiary alkanolamine solutions catalyzed by CA has been established and used to make comparisons of experimental and calculated pseudo first-order reaction rate constant (k(0, with CA)) in CO2-MDEA-H2O and CO2-DMEA-H2O solutions. The AADs were 15.21 and 15.17%, respectively. The effect of pKa on the CA activities has also been studied by comparison of CA activities in different tertiary amine solutions, namely, TEA, MDEA, DMEA, and DEEA. The pKa trend for amines were: DEEA>DMEA>MDEA>TEA. In contrast, the catalyst enhancement in amines was in the order: TEA> MDEA> DMEA> DEEA. Therefore, it can be seen that the catalyst enhancement in the amines decreased with their increasing pKa values. (C) 2017 American Institute of Chemical Engineers.