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Thermodynamic phase equilibria in synthetic slags (Al₂O₃–CaO–FeO–SiO₂–V₂O₃) were investigated with 0–27 wt.% vanadium oxide corresponding to industrial coal–petroleum coke (petcoke) feedstock blends in a simulated gasifier environment. Samples encompassing coal–petcoke mixed slag compositions were equilibrated at 1500 °C in a 64 vol.% CO/36 vol.% CO₂ atmosphere (Po₂ ≈ 10^–8 atm at 1500 °C) for 72 h, followed by rapid water quench, then analyzed by inductively coupled plasma optical emission spectrometry, X-ray diffractometry, and scanning electron microscopy with wavelength dispersive spectroscopy. With increasing CaO content, FeO content, or both; the slag homogeneity region expanded and a composition range exhibiting crystals wasmore » reduced. The mullite (Al₆Si₂O₁₃) crystalline phase was not present in the slags above 9 wt.% FeO while the karelianite (V₂O₃) crystalline phase was always present in compositions studied if a sufficient amount of vanadium existed in the slag. Furthermore, based on the present experimental equilibrium evaluation, a set of isothermal phase diagrams showing effects of CaO and FeO on thermodynamic phase stabilities in the vanadium-bearing slags is proposed. Some uses of the diagrams for potential industrial practice are discussed.« less