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The NPG–TRIS binary system (NPG = (CH3)2C(CH2OH)2 = 2,2-dimetyl-1,3-propanodiol; TRIS = NH2C(CH2OH)3 = 2-Amino-2-(hydroxymethyl)-1,3-propanediol) was intensively investigated as a thermal energy storage system, due to the reversibility of its phase transitions and their associated energy. An adapted methodology was applied to precisely quantify its sublimation tendency. Relevant thermochemical data were revisited and evaluated using some specific experimental procedures. We also determined that the widely accepted requirement of working in an inert atmosphere to avoid deviations due to hygroscopicity is not necessary. Nevertheless, to take advantage of the energetic properties of the NPG–TRIS system, closed containers will be required to avoid NPG losses, due to its quantitatively determined high sublimation tendency.