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To explicate the thermodynamics of the chromite ore lime-free roasting process, the thermodynamics of reactions involved in this process was calculated and the phrases of sinter with different roasting times were studied.The thermodynamics calculation shows that all the standard Gibbs free energy changes of the reactions to form Na2CrO4, Na2O·Fe2O3, Na2O·Al2O3 and Na2O·SiO2 via chromite ore and Na2CO3 are negative, and the standard Gibbs free energy changes of the reactions between MgO, Fe2O3 and SiO2 released from chromite spinel to form MgO·FezO3 and MgO·SiO2 are also negative at the oxidative roasting temperatures (1173-1473 K).The phrase analysis of the sinter in lime-free roasting process shows that Na2O·Fe2O3, Na2O·Al2O3 and NazO·SiO2 can be formed in the first 20 min, but they decrease in contents and finally disappear with the increase of roasting time.The final phase compositions of the sinter are Na2CrO4, MgO·Fe2O3, MgO·SiO2 and MgO.The results indicate that Na2CrO4 can be formed easily via the reaction of Na2CO3 with chromite ore.Na2O·Fe2O3, Na2O·Al2O3 and Na2O·SiO2 can be formed as intermediate compounds in the roasting process and they can further react with chromite ore to form Na2CrO4.MgO released from chromite ore may react with iron oxides and silicon oxide to form stable compounds of MgO·Fe2O3 and MgO·SiO2, respectively.