Abstract
The acid–base behavior of \(\mathrm{Fe}(\mathrm{CN})_{6}^{4-}\) was investigated by measuring the formal potentials of the \(\mathrm{Fe}(\mathrm{CN})_{6}^{3-}\)/\(\mathrm{Fe}(\mathrm{CN})_{6}^{4-}\) couple over a wide range of acidic and neutral solution compositions. The experimental data were fitted to a model taking into account the protonated forms of \(\mathrm{Fe}(\mathrm{CN})_{6}^{4-}\) and using values of the activities of species in solution, calculated with a simple solution model and a series of binary data available in the literature. The fitting needed to take account of the protonated species \(\mathrm{HFe}(\mathrm{CN})_{6}^{3-}\) and \(\mathrm{H}_{2}\mathrm{Fe}(\mathrm{CN})_{6}^{2-}\), already described in the literature, but also the species \(\mathrm{H}_{3}\mathrm{Fe}(\mathrm{CN})_{6}^{-}\) (associated with the acid–base equilibrium \(\mathrm{H}_{3}\mathrm{Fe}(\mathrm{CN})_{6}^{-}\rightleftharpoons \mathrm{H}_{2}\mathrm{Fe}(\mathrm{CN})_{6}^{2-} + \mathrm{H}^{+}\)). The acidic dissociation constants of \(\mathrm{HFe}(\mathrm{CN})_{6}^{3-}\), \(\mathrm{H}_{2}\mathrm{Fe}(\mathrm{CN})_{6}^{2-}\) and \(\mathrm{H}_{3}\mathrm{Fe}(\mathrm{CN})_{6}^{-}\) were found to be \(\mathrm{p}K^{\mathrm{II}}_{1}= 3.9\pm0.1\), \(\mathrm{p}K^{\mathrm{II}}_{2} = 2.0\pm0.1\), and \(\mathrm{p}K^{\mathrm{II}}_{3} = 0.0\pm0.1\), respectively. These constants were determined by taking into account that the activities of the species are independent of the ionic strength.
Similar content being viewed by others
References
Loos-Neskovic, C., Fédoroff, M.: Fixation mechanisms of cesium on nickel and zinc ferrocyanides. Solvent Extr. Ion Exch. 7, 131–158 (1989)
Loos-Neskovic, C., Fédoroff, M., Garnier, E., Jones, D.J.: Recovery of radioactive cesium with insoluble hexacyanoferrates: problems and perspectives. In: Yucomat 97: Materials Science Forum, vols. 282–283, pp. 171–181 (1998)
Loos-Neskovic, C., Fédoroff, M., Mecherri, M.O.: Ion fixation kinetics and column performance of nickel and zinc hexacyanoferrates(II). Analyst 115, 981–987 (1990)
Rock, P.A.: The standard oxidation potential of the ferrocyanide–ferricyanide electrode at 25 °C and the entropy of ferrocyanide ion. J. Phys. Chem. 70, 576–580 (1966)
Kolthoff, I.M., Tomsicek, W.J.: The oxidation potential of the system potassium ferrocyanide–potassium ferricyanide at various ionic strengths. J. Phys. Chem. 39, 945–954 (1935)
Hanania, I.H., Irvine, D.H., Eaton, W.A., George, P.: Thermodynamic aspects of the potassium hexacyanoferrate(III)–(II) system. II. Reduction potential. J. Phys. Chem. 71, 2022–2030 (1967)
Jordan, J., Ewing, G.J.: The protonation of hexacyanoferrates. Inorg. Chem. 1, 587–591 (1962)
Eaton, W.A., George, P., Hanania, I.H.: Thermodynamic aspects of the potassium hexacyanoferrate(III)–(II) system. I. Ion association. J. Phys. Chem. 71, 2016–2021 (1967)
Cohen, S.R., Plane, R.A.: The association of ferrocyanide ions with various cations. J. Phys. Chem. 61, 1096–1100 (1957)
Debye, P., Hückel, E.: Zur Theorie der Elektrolyte. I. Gefrierpunktserniedrigung und verwandte Erscheinungen. Z. Phys. 24, 185–206 (1923)
Davies, C.W.: Ion Association. Butterworth, London (1962)
Grenthe, I., Puigdomenech, I.: Modelling in Aquatic Chemistry, OECD—Nuclear Energy Agency (1997)
Brönsted, J.N.: Studies on solubility. IV. The principle of the specific interaction of ions. J. Am. Chem. Soc. 44, 877–898 (1922)
Brönsted, J.N.: Calculations of the osmotic and activity functions in solutions of uni-univalent salts. J. Am. Chem. Soc. 44, 938–948 (1922)
Scatchard, G.: Concentrated solutions of strong electrolytes. Chem. Rev. 19, 309–327 (1936)
Pitzer, K.S.: Ion interaction approach: theory and data correlation. In: Pitzer, K.S. (ed.) Activity Coefficients in Electrolyte Solutions, 2nd edn., pp. 75–153. CRC Press, Boca Raton (1991)
Stokes, R.H., Robinson, R.A.: Interactions in aqueous nonelectrolyte solutions. I. Solute–solvent equilibria. J. Phys. Chem. 70, 2126–2130 (1966)
Lobo, V.M.M.: Handbook of Electrolyte Solutions. Elsevier, Amsterdam (1989)
Ly, J., Poitrenaud, C.: Détermination des constantes de formation des complexes nitrate de cadmium(II) en solutions aqueuses concentrées en sels. Analusis 14, 192–199 (1986)
Camacho Frias, E., Pitsch, H., Ly, J., Poitrenaud, C.: Palladium complexes in concentrated nitrate and acid solutions. Talanta 42, 1675–1683 (1995)
Mokili, B., Poitrenaud, C.: Modelling of the extraction of neodymium and praesodymium nitrates from aqueous solutions containing a salting-out agent or nitric acid by tri-n-butylphosphate. Solvent Extr. Ion Exch. 14, 635–651 (1996)
Mokili, B., Poitrenaud, C.: Modelling of nitric acid and water extraction from aqueous solutions containing a salting-out agent by tri-n-butylphosphate. Solvent Extr. Ion Exch. 13, 755–769 (1995)
Mokili, B., Poitrenaud, C.: Medium effect on the separation factor in liquid–liquid extraction. Application to the separation of trivalent lanthanide nitrates by tri-n-butylphosphate. Solvent Extr. Ion Exch. 15, 455–481 (1997)
Charrin, N., Moisy, Ph., Blanc, P.: Contribution of the concept of simple solutions to calculation of the density of ternary and quaternary solutions of thorium(IV) or plutonium(IV) nitrate: An(NO3)4/UO2(NO3)2/HNO3/H2O. Radiochim. Acta 88, 445–451 (2000)
Kappenstein-Grégoire, A.C., Moisy, Ph., Cote, G., Blanc, P.: Determination of binary data for neptunium(V) nitrate. Radiochim. Acta 91, 371–378 (2003)
Kappenstein-Grégoire, A.C., Moisy, Ph., Cote, G., Blanc, P.: Dimerization of Np(V) and media effects in concentrated solutions. Radiochim. Acta 91, 665–672 (2003)
Hamer, W.J., Wu, Y.-C.: Osmotic coefficients and mean activity coefficients of uni-univalent electrolytes in water at 25 °C. J. Phys. Chem. Ref. Data 1, 1047–1099 (1972)
Charrin, N., Moisy, Ph., Garcia-Argote, S., Blanc, P.: Thermodynamic study of the ternary system Th(NO3)4/HNO3/H2O. Radiochim. Acta 86, 143–149 (1999)
Al-Niaimi, N.S., Wain, A.G., McKay, H.A.C.: Stability constants of the chloride and nitrate complexes of neptunium(V) and neptunium(VI). J. Inorg. Nucl. Chem. 32, 977–986 (1970)
Hu, Y.-F.: The thermodynamics of nonelectrolyte systems at constant activities of any number of components. J. Phys. Chem. B 107, 13168–13177 (2003)
Mikulin, G.I.: Voprossy Fizicheskoi Khimii Rastvorov Electrolitov (Problems in Physical Chemistry of Electrolyte Solutions). Izd. Khimiya, Leningrad (1968)
Sella, C., Bauer, D.: Determination of the hydrogen ion and chloride ion activities in hydrochloric acid. Hydrometallurgy 23, 353–364 (1990)
Acknowledgements
This research was supported by GNR PARIS, ANR AMPLI (ANR-07-BLAN-0295) and Areva NC.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Crozes, X., Blanc, P., Cote, G. et al. Acid–Base Properties of the \(\mathrm{Fe}(\mathrm{CN})_{6}^{3-}\)/\(\mathrm{Fe}(\mathrm{CN})_{6}^{4-}\) Redox Couple in the Presence of Various Background Mineral Acids and Salts. J Solution Chem 41, 503–515 (2012). https://doi.org/10.1007/s10953-012-9805-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10953-012-9805-8