Equilibrium Constants Determination of the Species Formation in the Al(III)-H2O System by Integration of 27Al-NMR Signals and Fitting with Species Fractions
DOI:
https://doi.org/10.29356/jmcs.v52i1.1045Keywords:
27Al-NMR, hydrolysis of Al3 , formation constants, potentiometric titrations, conductometric titrationsAbstract
A quantitative methodology to determine formation constants that takes into consideration the 27Al-NMR signals of Al(III)- H2O systems has been analyzed, where area fractions beneath the peaks recorded were associated with the corresponding species fractions. The values of the formation constants were compared with the model obtained by potentiometric studies. In agreement with previous reports, the -log*β values obtained by NMR and potentiometry, at 0.020 M ≤ [Al(III)]total ≤ 0.500 M are 12.96 ± 0.02 for Al(OH)3, 13.50±0.02 for Al3(OH)45+, and 109.70±0.09 for Al13(OH)327+, by assuming that Al(OH)2+ has a value of 5.29. Additionally the equilibrium constant values obtained allowed fitting of the conductimetry titrations in the 6.00(10-3) M ≤ [Al(III)]total ≤ 0.120 M. The algorithm presented in this work gives a support to establish that the area fractions of NMR signals are proportional to the species concentration fractions.
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3. Kinrade, S. D.; Swaddle,T. H. Inorg. Chem. 1989, 28, 1952-1954.
4. Yokoyama, T.; Kinoshita, S.; Wakita, H.; Watanabe, T. Anal. Sci. 1991, 7. Suppl., 429-430.
5. Caravan, P.; Orvig, Ch. Inorg. Chem. 1997, 36, 236-248.
6. Djurdjevic, P.; Cvijovic, M.; Vesna, Z. Spectrosc. Lett. 2005, 38, 617-634.
7. Tossell, J. A. Geochim. Cosmochim. Ac. 2001, 87, 115-124.
8. Perry, C. C.; Shafran, K. L. J. Inorg. Biochem. 2001, 87, 115-124.
9. Djurdjevic, P.; Cvijovic, M.; Zakrzewska, J. J. Coord. Chem. 2005, 58, 1615-1629.
10. Ratomir, M. J.; Ljubinka, G. J.; Djurdjevic, P. T. J. Solution Chem. 2005, 34, 1235-1261.
11. Frink, C. R.; Peech, M. Inorganic Chemistry. 1963, 3, 473-478
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14. Öhman, L. O.; Sjöberg, S.; Ingri, N. Acta Chem. Scand. 1983, A37, 561-568
15. Letterman, R. D.; Asolekar, S. R. Wat. Res. 1990, 24, 931-939
16. Öhman, L. O.; Forsling, W. Acta Chem. Scand. 1981, A35, 795-802
17. Gans, P.; Sabatini, A.; Vacca., A.J. Chem. Soc. Dalton Trans. 1985, 1195-1200
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“OPIUM” is available (free of charge) on http://www.natur.cuni.cz/~kyvala/opium.html , accessed in January, 2008
19. Akitt, J.W.; Greenwood, N. N.; Khandelwal, B. L.; Lester, G. D. J. Chem. Soc. Dalton Trans. 1972, 604-610
20. Bottero, J. Y.; Cases, J. M.; Fiessinger, F.; Poirier, J. E. J. Phys. Chem. 1980, 84, 2933-2939
21. Marklund, E.; Öhman, L. O. Acta Chem. Scand. 1990, 44, 228-234
22. Botello, J. C.; Morales-Domínguez, E.; Domínguez, J. M.; Gutiérrez, A.; Rojas-Hernández, A.; Ramírez, M. T. Spectrochimica Acta Part A. 2003, 59, 1477-1486
23. Gómez-Zaleta, B.; Ramírez-Silva, M. T.; Gutiérrez, A.; González-Vergara, E.; Güizado-Rodríguez, M.; Rojas-Hernández, A. Spectrochimica Acta Part A. 2006, 64, 1002-1009
24. Rojas-Hernández, A.; Moya-Hernández, R.; Rueda-Jackson, J. C.; Ramírez-Silva, M. T.; in Emerging Fields in Sol-Gel Science and
Technology; López, T. M.; Avnir, D.; Aegerter, M. Eds. Kluwer, Boston, 2003, 354-380
25. Domínguez, J. M.; Botello-Pozos, J. C.; López-Ortega, A.; Ramírez, M. T.; Sandoval-Flores, G.; Rojas-Hernández, A. Catalysis Today. 1998, 43, 69-77
26. Nazarenko, V. A.; Biryuk, E. A. Zhur. Neorg. Khim. 1974, 19, 632-635
27. Bourcier, W. L.; Knauss, K. G.; Jackson, K. J. Geochim. Cosmochim. Ac. 1993, 57, 747-762
28. Akitt , J. W.; Elders, J. M. J. Chem. Soc. Dalton Trans. 1988, 1347-1355
29. Puigdomenech, I. MEDUSA (Making Equilibrium Diagramas Using Sophisticated Algorithms) http://www.kemi.kth.se/medusa/, accessed in January, 2008
30. Castellan, G. W. Physical Chemistry, Addison-Wesley, Reading, 1983, Chapter 31
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