Chromium has a wide range of applications including metals and alloys manufacturing, pigments, corrosion resistance coatings and leather tanning. The production of chromium chemicals is based on the oxidative alkali roasting of chromite ores, which leads to the formation of water-soluble alkali chromates. Previous investigations reported that when chromite is roasted with soda-ash, a molten salt containing chromium, which is mainly composed of sodium carbonate and sodium chromate (Na 2 CO 3 -Na 2 CrO 4 binary mixture), forms under typical roasting conditions. The physical properties of the liquid phase, which are dependent on the temperature, charge and gangue compositions, play an important role on the oxidation reaction and may limit the chromate recovery by hindering the oxygen transport to the reaction interface. This investigation focuses on the alkali roasting of chromite ore at 1,000 o C using NaOH and KOH, followed by water leaching. The influence of the alkali ratio on the chromium extraction yield is analysed, and the results obtained with both hydroxides are compared. Sample characterisation and thermodynamic analysis, including phase diagrams, equilibrium calculations and computation of liquidus curves, are combined with the purpose of studying the formation of the molten salt phase under different roasting conditions and its effect on the final chromium recovery.