Flash point information is crucial for evaluating the fire and explosion (FE thus, their results are inapplicable to commercial mixtures of several liquids. In this study, two ternary mixtures, namely 1-butanol − acetic acid − ethylbenzene and 2-pentanol − acetic acid − ethylbenzene, were investigated. These mixtures comprise two binary constituents with minimum flash point behavior (MinFPB) and one binary constituent with maximum flash point behavior (MaxFPB). The ternary constituents do not exhibit MinFPB or MaxFPB; therefore, the aforementioned ternary mixtures can be considered the first known members of the fp 3.3.0−1b class ( Da Cunha et al., 2018 ). A model developed for ternary miscible mixtures was used to predict the flash point behaviors of the mixtures. The nonrandom two-liquid (NRTL), Wilson, original universal quasi-chemical functional-group activity coefficients (UNIFAC) and UNIFAC-Dortmund models were used to predict the activity coefficients of the binary and ternary constituents. The mixture of 1-butanol or 2-pentanol with acetic acid exhibited MaxFPB, indicating that acetic acid can substantially reduce the F&E risks of these alcohols. The findings can be applied in hazard identification, F&E hazard reduction, process safety design, fuel design, and the risk management of ignitable waste liquids.