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Fuel supercriticality has recently received significant attention due to the elevated pressures and temperatures that directly-injected (DI) fuel sprays encounter in modern internal combustion (IC) engines. This paper presents a theoretical examination of conventional and alternative DI fuels at conditions relevant to the operation of compression ignition (CI) engines. The focus is to identify the conditions under which the injected liquid fuel can bypass the atomization process and directly transition to a diffusional mixing regime with the chamber gas. Evaluating the microscopic length-scales of the phase boundary associated with the injection of liquid nitrogen into its own vapor, it is found that the conventional threshold based on the interfacial Knudsen number (i.e. Kn = 0.1) does not adequately quantify the direct transition between sub- and supercriticality. Instead, a threshold that is an order of magnitude smaller is more appropriate for this purpose.