Thermodynamic properties of Ba-Bi alloys, including the activity, partial molar entropy and enthalpy, were determined using the electromotive force (emf) technique for fourteen compositions, x(Ba) = 0.05-0.80. Emf measurements were performed at ambient pressure using a Ba(s)vertical bar CaF2-BaF2 vertical bar Ba(in Bi) or Ba-Bi (x(Ba) = 0.05)vertical bar CaF2-BaF2 vertical bar Ba(in Bi) electrochemical cells at 723-1073 K. At 773 K, activity values of Ba were as low as 6.6 x 10(-16) at mole fraction x(Ba) = 0.05 and approached unity for mole fractions x(Ba) >= 0.80. Stable emf values were observed at mole fractions x(Ba) = 0.05-0.25, exhibiting less than a 5 mV difference between the heating and cooling cycles. Mole fractions x(Ba) >= 0.30 exhibited increased hysteresis or had an unexpected emf profile due to the formation of metastable phases such as Bi and Ba5Bi3, confirmed by Xray diffraction. The Ba-Bi alloys were further characterized using differential scanning calorimetry over the entire composition range. Based on these data, a revised Ba-Bi binary phase diagram is proposed. (C) 2016 Elsevier Ltd. All rights reserved.