Activity Coefficients of Acids, Bases, and

ACTIVITY COEFFICIENTS OF ACIDS, BASES, AND SALTS (continued)... 

Standard KCl Solutions for Calibrating Conductivity Cells Molar Conductivity of Aqueous HF, HCl, HBr, and HI Equivalent Conductivity of Electrolytes in Aqueous Solution Ionic Conductivity and Diffusion at Infinite Dilution Activity Coefficients of Acids, Bases, and Salts... 

M.K. Chantooni, Jr. and I.M. Kolthoff, Acid-base equilibria in methanol, acetonitrile, and dimethyl sulfoxide in acids and salts of oxalic acid and homologs, fumaric and o-phthalic acids. Transfer activity coefficients of acids and ions, J. Phys. Chem. 79 (1975), pp. 1176-1182. 

The activity coefficients of sulfuric acid have been deterrnined independentiy by measuring three types of physical phenomena cell potentials, vapor pressure, and freeting point. A consistent set of activity coefficients has been reported from 0.1 to 8 at 25°C (14), from 0.1 to 4 and 5 to 55°C (18), and from 0.001 to 0.02 m at 25°C (19). These values are all based on cell potential measurements. The activity coefficients based on vapor pressure measurements (20) agree with those from potential measurements when they are corrected to the same reference activity coefficient. 

For this calculation it is assumed that both the acid and the base are completely dissociated and the activity coefficients of the ions are unity in order to obtain the pH values during the course of the neutralisation of the strong acid and the strong base, or vice versa, at the laboratory temperature. For simplicity of calculation consider the titration of 100 mL of 1M hydrochloric acid with 1M sodium hydroxide solution. The pH of 1M hydrochloric acid is 0. When 50 mL of the 1M base have been added, 50 mL of unneutralised 1M acid will be present in a total volume of 150 mL. 

For symmetric electrolytes i=l for 1 2 electrolytes (e.g., Na2S04), 1 3 electrolytes (AICI3), and 2 3 electrolytes ([Al2(S04)3], the corresponding valnes of A, are 1.587, 2.280, and 2.551. Mean ionic activity coefficients of many salts, acids, and bases in binary aqneons solutions are reported for wide concentration ranges in special handbooks. 

Although these effects are often collectively referred to as salt effects, lUPAC regards that term as too restrictive. If the effect observed is due solely to the influence of ionic strength on the activity coefficients of reactants and transition states, then the effect is referred to as a primary kinetic electrolyte effect or a primary salt effect. If the observed effect arises from the influence of ionic strength on pre-equilibrium concentrations of ionic species prior to any rate-determining step, then the effect is termed a secondary kinetic electrolyte effect or a secondary salt effect. An example of such a phenomenon would be the influence of ionic strength on the dissociation of weak acids and bases. See Ionic Strength... 

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