The protolysis of magnesium sesquicarbide, Mg2C3, with inorganic acids provides an interesting alternative to the more common hydrolysis of ionic carbides for obtaining their respective hydrocarbons. In particular, protolysis reactions with ammonium halides as precursors for hydrogen halides were investigated using in situ methods such as TGA/sDTA/MS and high-temperature XRPD. The protolysis reactions with NH4F and NH4Cl revealed two different reaction mechanisms yielding C3H4 and the respective magnesium halides as expected products. In the case of NH4Cl, intermediate phases that have not been previously observed, specificly (NH4)(2)MgCl4 (14/mmm) and two modifications of NH4MgCl3 (P6(3)/mmc), were structurally characterized.