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Focusing on the most important NaAl(OH)4-NaOH-H2O system in the industry of alumina production, the theory into NaAl(OH)4-NaOH-H2O system are involved and the values of parameters are determined. Then the applicability applicable to the establishment of calculation model of activity coefficients in NaAl(OH)4-NaOH-H2O system and the value of aNaAl(OH)4 is estimated as 0.3595 nm.