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Samples with alumina rich compositions in the system MgO–Al2O3 were investigated with DTA up to 2473K. The peritectic reaction L+Al2O3→ Spinel predicted from calculations was confirmed in this study. A critical literature review was done focusing on the degree of inversion of stoichiometric spinel MgAl2O4. Experimental results and the most reliable literature data were used for re-optimisation of thermodynamic parameters of the quasi binary system.