Thermodynamic properties of three-ring aza-aromatics. 1. Experimental results for phenazine and acridine,and mutual validation of experiments and computational methods

Measurements leading to the calculation of thermodynamic properties for phenazine (Chemical Abstracts registry number [92-82-0]) in the ideal-gas state are reported. Experimental methods included adiabatic heat-capacity calorimetry, inclined-piston manometry, and combustion calorimetry. Thermodynamic properties for acridine (Chemical Abstracts registry number [260-94-6]) were reported previously and included those measured with adiabatic heat-capacity calorimetry, comparative ebulliometry, inclined-piston manometry, and combustion calorimetry. New measurement results for acridine reported here are densities determined with a vibrating-tube densimeter and heat capacities for the liquid phase at saturation pressure determined with a differential-scanning calorimeter (d.s.c.). All critical properties were estimated. Molar entropies for the ideal-gas state were derived for both compounds at selected temperatures. Independent calculations of entropies for the ideal-gas state were performed at the B3LYP/6-31+G(d, p) model chemistry for phenazine and acridine. These are shown to be in excellent accord with the calorimetric results. All results are compared with experimental property values reported in the literature.