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Single fuel droplet vaporization, with special attention to the case of ethanol, is considered in this study. First, we showed, using an order-of-magnitude analysis and detailed unsteady simulations, that the commonly used quasi-steady assumption is not suitable for an accurate description of the liquid phase during the evaporation process. Second, we demonstrated that an increase in the relative importance of radiation explains the departures of the evaporation rate from the d2-law observed experimentally when sufficiently large droplets – initial radius above 0.25 mm – evaporated in ambient temperatures around 800 K. The multicomponent formulation included here, in which the physical properties of both liquid and gas phases depend on the concentration of the different species involved, was validated by comparing our numerical results with experimental data of ethanol, n-heptane, ethanol–water and n-dodecane–n-hexadecane droplets available in the literature. Because of its technological relevance, we dedicated special attention to the effect of the droplet water content and ambient humidity on the evaporation time of ethanol droplets. Our computations showed higher vaporization rates with increasing ambient humidity as a consequence of the extra heat generated during the condensation of moisture on the droplet surface.