Experimental mutual diffusion coefficients of potassium chloride, magnesium nitrate, cobalt chloride and beryllium sulphate in aqueous solutions have been compared with those estimated by the Onsager-Fuoss. From the observed deviations, we are proposing a model that allows to estimate the percentages of H 3O + (aq) resulting of hydrolysis of some ions (i.e, beryllium, cobalt, potassium and magnesium ions), contributing in this way to a better knowledge of the structure of these systems. The diffusion of beryllium sulphate is clearly the most affected by the beryllium ion hydrolysis.
diffusion coefficients, aqueous solutions, electrolytes, hydration, коэффициенты диффузии, водные растворы, электролиты, гидратация
1. R.A. Robinson, R.H. Stokes, Electrolyte Solutions, second ed., Butterworths, London, 1959.
2. H.S. Harned, B.B. Owen, The Physical Chemistry of Electrolytic Solutions, third ed., Reinhold Pub. Corp., New York, 1964.
3. H.J.V. Tyrrell, K.R. Harris, Diffusion in Liquids: a Theoretical and Experimental Study, Butterworths, London, 1984.
4. V.M.M. Lobo, Handbook of Electrolyte Solutions, Elsevier, Amsterdam, 1990.
5. J.N. Agar, and V.M.M. Lobo (Measurement of diffusion coefficients of electrolytes by a modified Open-Ended Capillary Method), J. Chem. Soc., Faraday Trans. I 71, 1659-1666 (1975).
6. R. Callendar and D.G. Leaist (Diffusion coefficients for binary, ternary, and polydisperse solutions from peak-width analysis of Taylor dispersion profiles), J. Sol. Chem. 35, 353-379 (2006).
7. J. Barthel, F. Feuerlein, R. Neuder and R. Wachter (Calibration of conductance cells at various temperatures), J. Sol. Chem. 9, 209-212 (1980).
8. L. Onsager and R.M. Fuoss (Irreversible processes in electrolytes. Diffusion. conductance and viscous flow in arbitrary mixtures of strong electrolytes), J. Phys. Chem.36, 2689-2778 (1932).
9. V.M.M. Lobo, A.C.F. Ribeiro and L.M.P. Verissimo (Diffusion coefficients in aqueous solutions of potassium chloride at high and low concentrations), J. Mol. Liq. 94, 61-66 (2001).
10. V.M.M. Lobo, A.C.F. Ribeiro and L.M.P. Veríssimo (Diffusion coefficients in aqueous solutions of magnesium nitrate), Ber. Bunsen Gesells. Phys. Chem. Chem. PhYS. 98, 205-208 (1994).
11. A.C.F. Ribeiro, V.M.M. Lobo and J.J.S. Natividade (Diffusion coefficients in aqueous solutions of cobalt chloride at 298.15 K), J. Chem. Eng. Data 47, 539-541 (2002).
12. V.M.M. Lobo, A.C.F. Ribeiro and L.M.P. Veríssimo (Diffusion coefficients in aqueous solutions of beryllium sulphate at 298 K), J. Chem. Eng. Data 39, 726-728 (1994).
13. A.J.M. Valente, A.C.F. Ribeiro, V.M.M. Lobo and A. Jiménez (Diffusion coefficients of lead(II) nitrate in nitric acid aqueous solutions at 298.15 K), J. Mol. Liq. 111, 33-38 (2004).
14. C.F. Baes, R.E. Mesmer, The Hydrolysis of Cations, John Wiley & Sons, New York, 1976.
15. J. Burgess, Metal Ions in Solution, John Wiley & Sons, Chichester, Sussex, England, 1978.
16. A.C.F. Ribeiro, V.M.M. Lobo, L.R.C. Oliveira, H.D. Burrows, E.F.G. Azevedo, S. I.G. Fangaia, P.M.G. Nicolau and Fernando A.D.R.A. Guerra (Diffusion coefficients of chromium chloride in aqueous solutions at 298.15 and 303.15 K), J. Chem. Eng. Data 50, 1014-1017 (2005).
17. A.C.F. Ribeiro, M.A. Esteso, V.M.M. Lobo, A.J.M. Valente, A.J.F.N. Sobral and H.D. Burrows (Diffusion coefficients of aluminium chloride in aqueous solutions at 298.15 K, 303.15 K and 310.15 K), Electrochim. Acta.52, 6450-6455 (2007).
18. A L.M.P. Veríssimo, A.C.F. Ribeiro, V.M.M. Lobo and M.A. Esteso (Effect of hydrolysis on diffusion of ferric sulphate in aqueous solutions), J. Chem. Thermodyn. 55, 56-59 (2012).
19. A A.C.F. Ribeiro, J.C.S. Gomes, L.M.P. Veríssimo, C.Romero L.H. Blanco, M.A. Esteso (Diffusion of cadmium chloride in aqueous solutions at physiological temperature 310.15 K), J. Chem. Thermodyn. 57, 404-407 (2013).