Abstract: This paper deals with,from the point of view of thermodynamics,the possibility of NaCl addition to chloridizing Volatilization of Ga during Sodiumination roasting of V-slag,in a temperature range 600~1200K.Conclusions are drawn that the magnitude of Cl₂-O₂ ratio is considerably related to the formation of aqueous sodium vana-date and reaches its maximum value,when NaCl and Na₂O·V₂O₅ are at equilibrium state;and GaCl₃ comes from Ga by chloridization and then volatilizes.Also.the thermo-dynamic calculation shows that the formation pressure of GaCl₃ is quite high,therefore the attempt is worthy to be made.