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用自制的锂离子选择电极和经典Ag-AgCl电极,测定25℃时LiCl-Li_2SO_4-H_2O三元体系中离子强度0.01～6.0mol·kg~(-1)的LiCl的平均活度系数.由实验数据,用多元线性回归法求取Pitzer方程、Harned方程的离子作用参数和系数,并用上述方程计算LiCl在混合溶液中的平均活度系数,分别以In_(γ±LiCl)和log_(γ±LiCl)的形式与实验值进行比较,标准偏差均小于0.008.本工作测得的LiCl平均活度系数的自然对数与等压法测定的渗透系数拟合的Pitzer方程参数计算值比较,标准偏差为0.0097.同时计算了Li_2SO_4在该体系中的平均活度系数和混合溶液的渗透系数以及混合超额自由能.
The average activity coefficient of LiCl with ionic strength of 0.01-6.0 mol · kg ~ (-1) in LiCl-Li_2SO_4-H_2O ternary system at 25 ℃ was measured by a homemade Li-ion selective electrode and a classical Ag-AgCl electrode. Data, the Pitzer equation and the ion action parameters and coefficients of Harned equation were obtained by multivariate linear regression method. The average activity coefficients of LiCl in the mixed solution were calculated by the above equation. The average activity coefficients of LiCl in the mixed solution were calculated by In (γ ± LiCl) and log_ (γ ± LiCl ) With the experimental values were compared with the standard deviation of less than 0.008 The natural logarithm of the average activity coefficient of LiCl measured in this work is compared with the calculated Pitzer equation parameter of the permeability coefficient measured by the isobaric method with a standard deviation of 0.0097. At the same time, the average activity coefficient of Li_2SO_4 in the system, the permeability coefficient of mixed solution and the mixed excess free energy were calculated.