We present new observations of the (6,6) and (9,9) inversion transitions of the hydronium ion toward Sagittarius B2(N) and W31C. Sensitive observations toward Sagittarius B2(N) show that the high, ~ 500 K, rotational temperatures characterizing the population of the highly-excited metastable H3O+ rotational levels are present over a wide range of velocities corresponding to the Sagittarius B2 envelope, as well as the foreground gas clouds between the Sun and the source. Observations of the same lines toward W31C, a line of sight that does not intersect the Central Molecular Zone, but instead traces quiescent gas in the Galactic disk, also imply a high rotational temperature of ~ 380 K, well in excess of the kinetic temperature of the diffuse Galactic interstellar medium. While it is plausible that some fraction of the molecular gas may be heated to such high temperatures in the active environment of the Galactic center, characterized by high X-ray and cosmic ray fluxes, shocks and high degree of turbulence, this is unlikely in the largely quiescent environment of the Galactic disk clouds. We suggest instead that the highly-excited states of the hydronium ion are populated mainly by exoergic chemical formation processes and temperature describing the rotational level population does not represent the physical temperature of the medium. The same arguments may be applicable to other symmetric top rotors, such as ammonia. This offers a simple explanation to the long-standing puzzle of the presence of a pervasive, hot molecular gas component in the central region of the Milky Way. Moreover, our observations suggest that this is a universal process, not limited to the active environments associated with galactic nuclei.