A variant of microfluidic setup design for the study of extraction kinetics has been proposed. Mass transfer constants for Am(III) and Eu(III) and observed rate constants were obtained for N-,O-donor ligands featuring phenanthroline and bipyridyl cores. The possibility of determining rate constants for cations independently of each other makes it possible to observe the kinetic effect of separation. The extraction rate was found to be lower for the bipyridyl ligand, compared to phenanthroline. The values of the rotation barriers for the ligands were calculated using the DFT method. The values correlate with the obtained low extraction rate for the bipyridyl ligand. Also, crystallographic data showing anti-conformation for the bipyridyl ligand align with the kinetic data. Surface tension was also determined for the systems with the studied ligands. It is shown that at equal ligand concentrations, the value of surface tension agrees with the extraction rate. Furthermore, it is shown that for the bipyridyl ligand, prior contact of the organic phase with nitric acid significantly affects the surface tension.