Abstract
Abstract : The integrated intensities as a function of temperature were measured for one NO2 and for four N2O4 combination bands in the spectral region from 1 to 5 microns. The temperature was varied from 50 to 100 C for the gas-phase studies and from 25 to 100 C for the liquid-phase experiment . In the spectral region from 5 to 15 microns, integrated intensities at 25 C were measured for one NO2 and for three N2O4 fundamental bands. Results from a series of absorption spectra were interpreted in accordance with the Wilson-Wells-Penner-Weber method. Measured intensities for N2O4 combination bands in the liquid and gas phases were compared and found to differ by less than 16% for 3 out of 4 combination bands studied; for the fourth band, the observed difference was about 50%. Results for all of the combination bands indicate that the integrated intensities vary approximately as 1/T in the temperature range under consideration. Absolute intensity data may be used for a spectroscopic determination of the heat of dissociation for gases in chemical equilibrium. For the reaction N2O4 yielding reversibly 2NO2, the heat of dissociation value, using the temperature dependence of the absorption bands, was 13.1 Kcal/(mole N2O4); this value is in fair agreement with the value of 13.7 Kcal/(mole N2O4) obtained by techniques utilizing density measurements.
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