Physicochemical processes important to the application of thermal emission mass spectrometry were identified and clarified. Effects of filament carbon concentration and temperature on plutonium ion emissions from a carburized rhenium filament were determined. Filament carbon concentration profoundly affected the appearance and duration of an ion signal. A useful ion signal was produced only when the carbon saturation temperature of the filament was exceeded, at which point first-order kinetics were either achieved or closely approached. This paper explains observed ion emission behavior in terms of pausible carbothermic reduction reactions and carbon diffusion processes that direct the course of those reactions. 31 references, 5 figures.