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The prediction of the fire hazard of a tank during burning of leaking contents is significant during the emergency response to tank fire accidents. A detailed investigation was conducted in small-scale tank fire experiments with different filling levels and tray sizes. The liquid (n-heptane) leaked from the tank and burned in the containment structure (the tray) below, heating the tank and emitting radiative heat flux to the surroundings. The temperature of the leaking contents increased as the heating progressed and eventually reached its boiling point. When the leaking contents boiled and burned, the fire hazard was the greatest because the internal pressure increased rapidly, and the mass burning rate and thermal radiation reached a maximum. Modifying the previous models, this paper proposed a virtual tray modeling approach for predicting the mass burning rate and thermal radiation during the burning of boiling leaking contents. The maximum relative error between measurement and prediction was approximately 20%, indicating the availability of the modified models. A three-dimensional transient simulation was set up using the computational fluid dynamics (CFD) technique to predict the temperature response of the leaking contents, and thus, the elapsed time before boiling and burning of the contents was well predicted. These results can provide scientific support for emergency response teams to control similar tank fire accidents. [ABSTRACT FROM AUTHOR]