In this work we study the formation of NH3, N2O and H-2 side products during operation of three-way catalytic converters (TWC) in a simulated engine exhaust. We used a commercial Pd-only TWC and supported Pd model catalysts in light-off and during constant temperature tests under rich conditions. N2O is observed primarily during light-off and its low temperature formation (110-320 degrees C) proceeds via reduction of NO by CO when O-2 is present, or by H-2 in its absence. We detected also N2O formation at 500 degrees C that has not been reported previously, proceeding via reduction with CO. NH3 is formed in the 200-600 degrees C range via reduction of NO by H-2. The H-2 required to produce NH3 is generated via steam reforming and water gas-shift reactions over the catalysts. On a molar basis, the H-2 emission is about five-fold higher than that of NH3 during cold start of TWC. We determined the effect of SO2 level during constant temperature experiments at 500 degrees C, extending the work of Gandhi and Shelef [1]. In CeO2-containing catalysts the interaction with SO2 favors the production of N2O, but lowers that of NH3, apparently by suppressing selectively the reaction path leading to H-2 needed for the reaction. Our study suggests that the use of low and ultra-low sulfur gasoline by cars equipped with TWC lowers the emission of N2O to the atmosphere during high temperature operation but enhances the production of NH3 and H-2. This is a matter of concern because NH3 is involved in the formation of nano, fine and ultra fine inorganic particles in the atmosphere. (C) 2012 Elsevier B.V. All rights reserved.