The response mechanisms of a thermionic detector with enhanced nitrogen selectivity operating in an inert gas environment were investigated. According to accepted theory, the analyte has to contain electronegative functional groups in order for negative ions to be formed by the extraction of electrons from the thermionic source. This leads to a selective detector response for compounds containing nitro groups or multiple halogens. However, in the tests described here, polycyclic aromatic nitrogen hydrocarbons (PANHs), acridines, and carbazoles were used as reference substances. These compounds contain no electronegative functional groups. None of the investigated acridines exhibited any response from the detector, but carbazoles generated a strong structure-related detector response. By examining partial charges for all hydrogens of all individual carbazoles and acridine, it was demonstrated that the acidic hydrogen atom attached to the nitrogen heteroatom of the carbazoles has a strong influence on the detector response. Ionization of carbazoles may occur by dissociation of the nitrogen-hydrogen bond during contact with the thermionic surface. Support for this theory was provided by the linear relationship between the relative detector response and the deprotonization energy of the carbazoles (coefficients of determination of 0.90 and 0.98 for linear and quadratic models, respectively, were obtained). Further, there appeared to be no linear relationship between the detector response and electron affinity of the carbazoles, (R2 value, 0.32). Thus, the mechanism involved in ionization of the carbazoles is probably not direct electron transfer from the thermionic surface to the carbazoles. Principal component analysis (PCA) showed that the thermal conductivity of chemically inert detector gases also has an influence on the detector response. The investigated gases were helium, neon, nitrogen, carbon dioxide, and argon. It was found that thermal conductivity can be used to rank the detector response for the carbazoles, and there was no discernible response when helium, which has the highest thermal conductivity, was used as the detector gas.