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In the present study emission spectroscopy is used to investigate gas composition effect on macro and microscopic parameters radiative spectral distribution, translational and rotational temperatures, electronically – vibrationally – rotational energy level distribution functions in the electronic excited states of the nitrogen and hydrogen molecules, and as well as atomic hydrogen of DC glow discharge (pressure of 4 Torr, discharge current of 70 mA) and the strongly inhomogeneous microwave discharge generated near the end of the electrode antenna (frequency of 2.45 GHz, pressure 4 Torr, incident microwave power of 100 W) in mixtures of hydrogen with nitrogen (percentages of N2 98.2% 85.8% and H2 1.8% 14.2%). A new approach is developed for modeling and processing of the nonequilibrium plasma emission spectra. It allows for evaluating population densities of atomic hydrogen, nitrogen ion and nitrogen molecules in the excited states at their significant deviation from Boltzmann’s distribution in the case of spectral overlapping of the atomic lines and molecular bands.