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We study the electronic kinetics of metastable molecular nitrogen N2(A3Su+) in upper atmospheres of N2-rich planets. The simulation of N2(A3u+) vibrational populations at the altitudes of upper atmospheres of the planets is made. The mixtures of N2-O2 and N2-CH4-CO is considered for the atmospheres of Earth and Titan-Triton-Pluto, respectively. The role of molecular inelastic collisions in intermolecular electron energy transfer processes is investigated. The influence of metastable molecular nitrogen N2(A3Su+) on the electronic excitation of O2 and CO molecules in inelastic collisions is studied. It is shown that the increase in the density of upper atmospheres of the planets leads to more significant excitation of electronically excited O2 and CO by intermolecular electron energy transfers from N2(A3Su+).