Spectroscopic measurement is conducted using a free-piston double-diaphragm shock tube to investigate the nonequilibrium phenomena in the shock layer. The shock velocity and spectrum position correlated to the shock front are determined using a double-laser schlieren measurement system for precise localization. Emission spectra of N
2(1+), N
2(2+) and N
2+(1−) band systems are obtained by means of time-frozen imaging spectroscopy. A spectrum fitting method is used to determine the rotational and vibrational temperatures from the measured spectra, and temperature distribution correlated to the shock front is finally obtained. The measured rotational temperatures are in high nonequilibrium with the translational temperature expected from the numerical prediction of the two-temperature model. The measured rotational temperature for N
2(2+) is lower than those for N
2(1+) and N
2+(1−) immediately behind a shock wave. Hence, rotational relaxation for the N
2C state looks slower than those for the N
2B and N
2+ B states. On the contrary, the measured vibrational temperatures for N
2(1+), N
2(2+) and N
2+(1−) are close to each other, and agree well with the numerical prediction of the two-temperature model. The experiment and numerical analysis suggest that the electronic excitation temperature is in nonequilibrium with the vibrational temperature.
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