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The Liquid Junction Potential in Potentiometric Titrations. X. The Calculation of Potentials Across Liquid Junctions of the Type AY|AY+HY+BYz(B)+AyL for Emf Cells Where Strong or Weak Complexes are Formed at Constant Ionic Strength and −log10[H+]≤7

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Abstract

Equations are derived for the calculation of the total potential anomalies in Emf cells with liquid junctions (ΔE J ) in mV and at 25.0 °C, defined as

$$\Delta E_J=({+ {\rm or} -})(59.16/z_j)\log _{10} f_{{\it JTS2}}+E_D+E_{Df}$$

wherez j = the charge number of the potential determining ion, J, and TS2 = terminal solution 2 ≡ test solution. This definition includes the activity factor (f J ) contributions to the measuring electrode, the ideal diffusion potential (E D ) and the contribution of the activity factors to E D , denoted by E Df . The cell assumed to contain an equilibrium solution which exists in the system, HY – BY z(B)–A y L in the ionic medium (A+, Y−) with the experimental condition I (ionic strength) = CM, constant, in the mixed solutions. Here, L y − denotes the ligand and B z (B)+ the metal ions.

The reasons for the dependence of the equilibrium constants on the ionic medium are given. The change of the equilibrium constants with the experimental conditions in a given ionic medium is also explained.

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  1. Erzsébet Néher-Neumann

    Present address: , Smedsbacksgatan 7, 3 tr., 115 39, Stockholm, Sweden

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  1. Department of Chemistry, Inorganic Chemistry Royal Institute of Technology (KTH), S-100 44, Stockholm, Sweden

    Erzsébet Néher-Neumann

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Néher-Neumann, E. The Liquid Junction Potential in Potentiometric Titrations. X. The Calculation of Potentials Across Liquid Junctions of the Type AY|AY+HY+BYz(B)+AyL for Emf Cells Where Strong or Weak Complexes are Formed at Constant Ionic Strength and −log10[H+]≤7. J Solution Chem 35, 1085–1107 (2006). https://doi.org/10.1007/s10953-006-9051-z

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