Abstract
The relative mean activity coefficients of the M3[Fe(CN)6]2 salts, M=Mg, Ca, Sr, Ba, are measured down to about 5×10−6 mol-kg−1 using the liquid membrane cell method. In the dilute region these salts display negative instead of positive deviations from the limiting law, contrary to Debye-Hückel's theory predictions. An indirect method based on auxiliary emf measurements in MCl2, K3Fe(CN)6 and KCl, rather than a theory-assisted direct extrapolation to zero of the relative activity coefficients, is used to identify the actual values of the activity coefficients. The data are compared with Mayer's theory, ion-pair theory and numerical integration of the Poisson-Boltzmann equation. Best-fit coefficients of Pitzer's equation which meet the activity coefficients of the M3[Fe(CN)6]2 salts to be reproduced, are reported.
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Malatesta, F., Giacomelli, A. & Zamboni, R. Activity coefficients from the emf of liquid membrane cells V. alkaline earth hexacyanoferrates (III) in aqueous solutions at 25°C. J Solution Chem 25, 61–73 (1996). https://doi.org/10.1007/BF00972759
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DOI: https://doi.org/10.1007/BF00972759