应用离子选择性电极进行溶液热力学研究(X)-RbCl在(H_2O～DMF)混合溶剂中热力学性质的测定(298.15～318.15K)

STUDY ON THE THERMODYNAMICS OF SOLUTION USING IONSELECTIVE ELECTRODE(Ⅹ)THERMODYNAMIC PROPERTIES OF RbCl IN MIXED SOLVENTS AT DIFFERENT TEMPERATURE

应用Ｃｏｒｎｉｎｇ一价阳离子选择电极（Ｍ＋～ＩＳＥ）和Ｏｒｉｏｎ氯离子选择性电极（Ｃｌ－～ＩＳＥ）组成可逆电池，即Ｃｌ－～ＩＳＥ／ＲｂＣｌ（ｍ），Ｈ２Ｏ（１－ｘ），ＤＭＦ（ｘ）／Ｍ＋～ＩＳＥ通过测定上述测量电池的标准电动势（Ｅ０ｍ／ｍＶ），根据溶液热力学原理，运用扩展的Ｄｅｂｙｅ～Ｈüｃｋｅｌ公式，计算求得了ＲｂＣｌ由Ｈ２Ｏ至（Ｈ２Ｏ～ＤＭＦ）混合溶剂的标准迁移自由能（ΔＧ０ｔ／ｋＪ·ｍｏｌ－１）和ＲｂＣｌ在（Ｈ２Ｏ～ＤＭＦ）混合溶剂中的活度系数（γ±），并对上述热力学性质随混合溶剂组成的变化规律进行了初步的讨论．

おhe reversible cells consists of the Corning monovalent cation selective electrode(M+ISE) and chloride selective (Cl-ISE)electrode,namely Cl-～ISE/RbCl(m),H2O(1-x),DMF(x)/M+～ISEThe standard Electromotive forces (E0m/mV) of the measured cells have been measured at four temperatures from 298.15K to 318.15K,then the standard free energies of transfer (ΔG0t/kJ·mol-1)of RbCl from H2O to (H2ODMF) mixtures and the activity coefficients (γ±) of RbCl in Water and the mixed solvents have been calculated.The behavior of change of standard free energies of transfer and activity coefficients of RbCl with molar fractions X of organic substances in the mixed solvents have been mainly discussed on the bases of salvation theory of electrolyte solution.