The role of nitrogen in the oxidation of Ti-2W, Ti-10Al-2W (at.%) and Ti6242S was investigated using experiments in air and in Ar-20%O2, and two-stage experiments where the reaction gas was switched from one mixture to the other. When switching from Ar-20%O2 to air, the oxidation rates first increased during a short period, then decreased. This surge of mass gain following the introduction of air was attributed to N pickup, forming a nitride layer and a N-enriched zone in the alloy, below the oxide layer. The subsequent decrease of oxidation rate was attributed to the formation of nitride and/or N-rich zone, which both act as diffusion barriers for oxygen. Switching from air to Ar-20%O2 caused an increase in the oxidation rate of the W-containing alloys, which was attributed to the consumption of this barrier. The gas change had no significant effect on the oxidation rate of Ti6242S, which formed a much thinner nitride layer in air. The faster the nitride layer grows, the faster it is consumed when removing N from the reaction gas, probably because of a higher diffusion rate of N in W-doped TiO2 compared to TiO2 formed on Ti6242S.