This work presents a theoretical study of the time-relaxation of both the electron energy distribution function and the populations of the different species of interest in the nitrogen afterglow of a ω/2π = 433 MHz discharge at p = 3.3 Torr, in a tube with radius R = 1.9 cm. It is shown that collisions of highly excited N2(X 1Σg+, v≳35) molecules with N(4S) atoms may be in the origin of the observed pronounced maxima for the concentrations of various species, including electrons, occurring downstream from the discharge after a dark zone. Slow electrons remain for very long times in the post-discharge (at least up to t∼10−3–10−2 s), and the strong coupling between the electron and metastable kinetics is clearly pointed out.