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Densities of LiB 5 O 6 (OH) 4 (aq) at molalities of 0.09859−0.89493 mol•kg −1 were measured at 5 K intervals from 283.15 to 363.15 K at 101.325 kPa using a precise Anton Paar Digital vibrating-tube densimeter. The apparent molar volumes (V ϕ ), thermal expansion coefficients (α), and partial molar volumes (V̅ B ) were obtained. On the basis of experimental data, diagrams of the thermodynamic parameters (α, V ϕ , and V̅ B ) against molality at different temperatures were plotted. According to the Pitzer model of apparent molar volume, the Pitzer parameters V̅ B , ß M,X (0)v , ß M,X (1)v , ß M,X (2)v , and C M,X v and the coefficients a i of the temperature-dependence formula f(i, p, T) = a 1 + a 2 ln(T/298.15) + a 3 (T − 298.15) + a 4 /(620 − T) + a 5 (T − 227) (where T is the temperature in Kelvin) for LiB 5 O 6 (OH) 4 were fitted by the least-squares method. The predictive apparent molar volumes agree well with the experimental values, and those results indicated that the single salt parameters and the temperature-dependence formula are reliable.