Spectroscopic measurement of the acid dissociation constant of 2-naphthol and the second dissociation constant of carbonic acid at elevated temperatures

Abstract

2-Naphthol can be used to measure the pH of aqueous solutions if the acid dissociation constant for 2-naphthol is known at a given temperature. The temperature dependence of the acid dissociation constant for 2-naphthol was spectroscopically determined in borate buffer solutions under vapor-saturated pressure up to 200°C. The result was

where T is in Kelvin. The pH of carbonate buffer solutions was measured by obtaining the UV–visible spectra of 2-naphthol and utilized to determine the second dissociation constant of carbonic acid up to 175°C under vapor-saturated pressure. The result was
where T is in Kelvin. By using the temperature dependence of the dissociation constant, the isocoulombic reaction was studied. The plot of -log K_isoc against 1/T was approximately linear in the temperature range studied. The linearity can be used to predict the dissociation constant by the extrapolation of -log K_isoc to higher temperatures.

References

1. P. Boudreau and D. E. Canfield, Geochim. Cosmochim. Acta, 1993, 57, 317.
2. P. V. Cappellen, L. Charlet, W. Stumn and P. Wersin, Geochim. Cosmochim. Acta, 1993, 57, 3505.
3. D. W. Morrow, B. L. Gorham and J. N. Y. Wang, Geochim. Cosmochim. Acta, 1994, 58, 169.
4. L. N. Plummer and E. Busenberg, Geochim. Cosmochim. Acta, 1982, 46, 1011.
5. J. C. Peiper and K. S. Pitzer, J. Chem. Thermodyn., 1982, 14, 613.
6. B. N. Ryzhenko, Geochemistry, 1963, 2, 151.
7. J. Read, J. Solution Chem., 1975, 4, 53.
8. C. S. Patterson, G. H. Slocum, R. H. Busey and R. E. Mesmer, Geochim. Cosmochim. Acta, 1982, 46, 1653.
9. C. S. Patterson, R. H. Busey and R. E. Mesmer, J. Solution Chem., 1984, 13, 647.
10. P. C. Ho and D. A. Palmer, Geochim. Cosmochim. Acta, 1997, 61, 3027.
11. R. N. Roy, J. J. Gibbons, R. Williams, L. Godwin, G. Baker, J. M. Simonson and K. S. Pitzer, J. Chem. Thermodyn., 1984, 16, 303.
12. J. Ellis, Am. J. Sci., 1959, 257, 217.
13. Y. S. Huh, J. G. Lee, D. C. McPhail and K. Kim, J. Solution Chem., 1993, 22, 615.
14. I. J. Lee, G. S. Jung and K. Kim, J. Solution Chem., 1994, 23, 1283.
15. T. W. Shin, K. Kim and I. J. Lee, J. Solution Chem., 1997, 26, 379.
16. M. H. Kim, C. S. Kim, H. W. Lee and K. Kim, J. Chem. Soc., Faraday Trans., 1996, 92, 4951.
17. R. Boyer, G. Deckey, C. Marzzacco, M. Mulvaney, C. Schwab and A. M. Halpern, J. Chem. Educ., 1985, 62, 630.
18. J. P. Soumillion, P. Vandereecken, V. D. Auweraer, F. C. De Schryver and A. Schanck, J. Am. Chem. Soc, 1989, 111, 2217.
19. S. Green, T. Xiang, K. P. Johnston and M. A. Fox, J. Phys. Chem., 1995, 99, 13787.
20. S. N. Park, C. S. Kim, M. H. Kim, I. J. Lee and K. Kim, J. Chem. Soc., Faraday Trans., 1998, 94, 1421.
21. D. G. Hafeman, K. L. Crawford and L. J. Bousse, J. Phys. Chem., 1993, 97, 3058.
22. L. F. Silvester and K. S. Pitzer, J. Phys. Chem., 1977, 81, 1822.
23. K. S. Pitzer and G. Mayorga, J. Solution Chem., 1974, 3, 539.
24. D. J. Bradley and K. S. Pitzer, J. Phys. Chem., 1979, 83, 1599.
25. R. E. Mesmer, C. F. Baes, Jr. and F. H. Sweeton, Inorg. Chem., 1972, 11, 537.
26. W. L. Marshall and E. U. Franck, J. Phys. Chem. Ref. Data, 1981, 10, 295.
27. H. R. Corti and R. J. Fernandez-Prini, High-Temperature Aqueous Solutions: Thermodynamic Properties, CRC Press, Boca Raton, FL, 1992.
28. F. M. M. Morel and J. G. Hering, Principles and Applications of Aquatic Chemistry, Wiley, New York, 1993, p. 61.