Abstract
The protonation constants of phthalate were determined in aqueous NaCl (0.1 ≤ I ≤ 5,mol⋅L−1) and in aqueous Me4NCl (0.1 mol⋅L−1 ≤ I ≤ 3,mol⋅L−1) at t = 25,∘C. Experimental data were employed in conjunction with literature data from studies in different ionic media (Et4NI: 0 ≤ I ≤ 1,mol⋅L−1; NaClO4: 0.05 mol⋅L−1 ≤ I ≤ 2,mol⋅L−1)to study the dependence on ionic strength using different models, such as the SIT and Pitzer equations, and an Extended Debye-Hückel type equation. Experimental calorimetric data in NaCl and protonation constants at different temperatures in Et4NI (5 ≤ t ≤ 45∘C) and in NaClO4 (15 ≤ t ≤ 35 ∘C) were also used to study their dependence on temperature. Recommended equilibrium data are reported together with a short discussion of a prospective protocol for drawing these data.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Martell, A.E., Smith, R.M., Motekaitis, R.J.: National Institute of Standard and Technology, NIST. Critically Selected Stability Constants of Metal Complexes. PC-based Database, Gaithersburg, MD 20899 (2004).
Pettit, L., Powell, K.J.: The IUPAC Stability Constants Database, Academic Software (2001).
May, P.M., Murray, K.: Database of chemical reactions designed to achieve thermodynamic consistency automatically. J. Chem. Eng. Data 46, 1035–1040 (2001).
Daniele, P.G., De Stefano, C., Foti, C., Sammartano, S.: The effect of ionic strength and ionic medium on the thermodynamic parameters of protonation and complex formation. Curr. Top. Solution Chem. 2, 253–274 (1997).
Brönsted, J.N.: Studies on solubility IV. Principle of the specific interaction of ions. J. Am. Chem. Soc. 44, 877–898 (1922).
Scatchard, G.: Concentrated solutions of strong electrolytes. Chem. Rev. 19, 309–327 (1936).
Guggenheim, E.A., Turgeon, J.C.: Specific interaction of ions. Trans. Faraday Soc. 51, 747–761 (1955).
Ciavatta, L.: The specific interaction theory in the evaluating ionic equilibria. Ann. Chim. (Rome) 70, 551–562 (1980).
Ciavatta, L.: The specific interaction theory in equilibrium analysia. Some empirical rules for estimatine interaction coefficients of metal ion complexes. Ann. Chim. (Rome) 80, 255–263 (1990).
Pitzer, K.S.: Thermodynamics of electrolytes. I. Theoretical basis and general equations. J. Phys. Chem. 77, 268–277 (1973).
Pitzer, K.S.: Activity Coefficients in Electrolyte Solutions, 2nd Edition, CRC Press, Boca Raton, Florida (1991).
Bretti, C., Foti, C., Sammartano, S.: Calculation of SIT parameters. Part I. A new approach in the use of SIT in determining the dependence on ionic strength of activity coefficients. Application to some chloride salts of interest in the speciation of natural fluids. Chem. Spec. Bioavail. 16, 105–110 (2004).
de Mendonça, A.J.G., Juusola, P.M.: Activity coefficients of dipotassium phthalate and potassium hydrogen phthalate in water at 298.15 K. Fluid Phase Equil 231, 114–124 (2005).
De Stefano, C., Princi, P., Rigano, C., Sammartano, S.: Computer analysis of equilibrium data in solution. ESAB2M: An improved version of the ESAB program. Ann. Chim. (Rome) 77, 643–675 (1987).
De Robertis, A., De Stefano C., Rigano, C.: Computer analysis of equilibrium data in solution. ES5CM fortran and basic programs for computing formation enthalpies from calorimetric measurements. Thermochim. Acta 138, 141–146 (1986).
De Stefano, C., Sammartano, S., Mineo, P., Rigano, C.: Computer Tools for the Speciation of Natural Fluids. In: Gianguzza, A., Pellizzetti, E., Sammartano, S. (eds.) Marine Chemistry–An Environmental Analytical Chemistry Approach, pp. 71–83. Kluwer Academic Publishers, Amsterdam (1997).
Clarke, E.C.W., Glew, D.N.: Evaluation of thermodynamic functions from equilibrium constants. Trans. Faraday Soc. 539–547 (1965).
Hamer, W.J., Pinching, G.D., Acree, S.F.: First dissociation constant of o-phthalic acid and related pH values of phthalate buffers from 0∘ to 60∘. J. Res. Nat. Bur. Standards 35, 539–564 (1945).
Desai, I.R. Nair, V.S.K.: Metal complexes in solution. I. Phthalates of some transition metals. J. Chem. Soc. 2360–2366 (1962).
Nair, V.S.: Metal complexes in solution. II. Zinc malonate and phthalate. J. Chem. Soc. 1450–1455 (1965).
De Robertis, A., De Stefano, C., Rigano, C., Sammartano, S.: Thermodynamic parameters for the protonation of carboxylic acids in aqueous tetraethylammonium iodide solutions. J. Solution Chem. 19, 569–587 (1990).
Rey-Castro, C., Castro-Varela, R., Herrero, R., Sastre de Vicente, M.E.: Acid–base equilibria of phthalic acid in saline media: ion association from Pitzer equations. Talanta 60, 93–101 (2003).
Lumme, P., Kari, E.: Phthalic acid as a reagent in inorganic qualitative analysis of metal ions. Part III. Thermodynamics of the protonation of phthalate ion in aqueous sodium perchlorate solutions. Acta Chem. Scand. A29, 117–124 (1975).
Tomat, G., Magon, L., Portanova, R., Cassol, A.: Complexes of thorium(IV) with dicarboxylate ligands in aqueous solution. Z. Anorg. Allg. Chem. 393, 184–192 (1972).
Napoli, A., Magri, A.: Oxovanadium(IV) and dioxouranium(VI) complexes with some pyrazinecarboxylic acids. Ann. Chim. (Rome) 79, 93–96 (1989).
Goncalves, M., Mota, A.: Complexes of vanadyl and uranyl ions with the chelating groups of humic matter. Talanta 34, 839–847 (1987).
Napoli, A., Magri, A.: Oxovanadium(IV) complexes with α-pyridinedicarboxylic acids. Ann. Chim. (Rome) 77, 783–788 (1987).
Olin, A., Svanstrom, P.: The complex formation of hydrogen(+), cadmium(2+) and lead(2+) ions with benzoate, phthalate and isophthalate ions. Acta Chem. Scand. A32, 435–438 (1978).
Napoli, A. Liberti, A.: Potentiometric study of complexes between aluminum ion and phthalic and benzoic acids. Gazz. Chim. Ital. 100, 906–915 (1970).
De Bruin, H., Kaitis, D., Temple, R.: The extraction of anionic beryllium complexes by tri-iso-octylamine. Aust J. Chem. 15, 457–466 (1962).
Khanolkar, V., Jahagirdar, D., Khanolkar, D.: Mixed ligand chelates of uranyl ion. J. Inorg. Nucl. Chem. 35, 931–940 (1973).
Bretti, C., Crea, F., Foti, C., Sammartano, S.: Solubility and activity coefficients of o-phthalic acid and cystine in NaCl aq , (CH3)4NCl aq and (C2H5)4NI aq at different ionic strengths, at t = 25 ∘C. J. Chem. Eng. Data 50, 1761–1767 (2005).
Sammartano, S.: unpublished data.
Rivett, A.C.D., Rosemblum, E.I.: The influence of a second solute on the solubility of ortho-phthalic acid. Trans. Faraday Soc. 9, 297–309 (1914).
Braibanti, A., Ostacoli, G., Paoletti, P., Pettit, L.D., Sammartano, S.: Potentiometric apparatus and technique for the pH-metric measurement of metal-complex equilibrium constants. Pure Appl. Chem. 59, 1721–1728 (1987).
Tuck, D.G.: A proposal for the use of a standard format for the publication of stability constant measurements. Pure Appl. Chem. 61, 1161 (1989).
McIntyre, F.: Concentration scales: A plea for physico-chemical data. Mar. Chem. 4, 205 (1976).
Hepler, L.G.: Correct calculation of Δ H ∘, Δ C p ∘, and Δ V ∘ from temperature and pressure dependences of equilibrium constants: The importance of thermal expansion and compressibility of the solvent. Thermochimica Acta 50, 69–72 (1981).
Östhols, E., Wanner, H.: The NEA Thermochemical Data Base Project, Le Seine-St. Germain, France (2000).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Bretti, C., De Stefano, C., Foti, C. et al. Critical Evaluation of Protonation Constants. Literature Analysis and Experimental Potentiometric and Calorimetric Data for the Thermodynamics of Phthalate Protonation in Different Ionic Media. J Solution Chem 35, 1227–1244 (2006). https://doi.org/10.1007/s10953-006-9057-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10953-006-9057-6