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Absract: The potential-pH diagram is a useful tool to discuss the redox reaction in hydrometallurgical processes.However, as for many chromium compounds, most of their thermodynamic data were seldom reported and not available.The potential-pH diagrams of the Cr-H2O system at temperatures of 298.15K, 323.15K, 373.15K and 423.15K were established through thermodynamic calculation with coupling of experimental results.