Abstract
Equilibrium constants for the reaction of β-naphthoic acid and ammonia,K BHA, were measured with UV-vis spectroscopy in water from 25°C to 400°C. At high densityK BHA decreases with temperature, the normal behavior for an exothermic reaction of a stronger acid and base to a weaker acid and base. At low density, the reaction becomes endothermic as the solvation of the ionic products becomes weaker. These data were combined with literature results for the dissociation of water and ammonia to determine equilibrium constants for the dissociation of β-naphthoic acid and the reaction of β-naphthoic acid and OH−. Whereas the density (and dielectric constant) of water have only a modest effect on the isocoulombic reaction of β-naphthoic acid and OH−, they have a large effect on all of the other reactions which are ionogenic.
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R. W. Shaw, T. B. Brill, A. A. Clifford, C. A. Eckert, and E. U. Franck,Chem. Eng. News 69, 26 (1991).
L. J. Sealock, D. C. Elliott, E. G. Baker, and R. S. Butner,Ind. Eng. Chem. Res. 32, 1535 (1993).
J. F. Connolly,J. Chem. Eng. Data 11, 13 (1966).
J. W. Tester, inEmerging Technologies in Hazardous Waste Management III D. W. Tedder, F. G. Pohland, eds. vol. 518, (American Chemical Society, Washington, DC, 1993), pp. 35–76.
S. Green, T. Xiang, K. P. Johnston, and M. A. Fox,J. Phys. Chem. 99, 13787 (1995).
R. E. Mesmer and H. F. Holmes,J. Solution Chem. 21, 725 (1992).
D. D. Macdonald, S. Hettiarachchi, H. Song, K. Makela, R. Emerson, and M. Ben-Haim,J. Solution Chem. 21, 849 (1992).
R. E. Mesmer, W. L. Marshall, D. A. Palmer, J. M. Simonson, and H. F. Holmes,J. Solution Chem. 17, 699 (1988).
R. E. Mesmer, D. A. Palmer, and J. M. Simonson, inActivity Coefficients in Electrolyte Solutions, 2nd edn., K. S. Pitzer, ed. (CRC Publishers, Boca Raton, 1991), pp. 491.
G. C. Ulmer, H. L. Barnes,Hydrothermal Experimental Techniques (Wiley-Interscience, New York, 1987).
L. B. Kriksunov and D. D. Macdonald, inPhysical Chemistry of Aqueous Systems: Meeting the Needs of Industry J. H. J. White, J. V. Sengers, D. B. Neumamm, J. C. Bellows, eds. (Begell House, New York, 1994), pp. 432–440.
X. Chen, S. E. Gillespie, J. L. Oscarson, and R. M. Izatt,J. Solution Chem. 21, 803 (1992).
X. Chen, S. E. Gillespie, J. L. Oscarson, and R. M. Izatt,J. Solution Chem.,21, 825 (1992).
S. E. Gillespie, J. L. Oscarson, X. Chen, R. M. Izatt, and C. Pando,J. Solution Chem. 21, 761 (1992).
J. L. Oscarson, S. E. Gillespie, R. M. Izatt, X. Chen, and C. Pando,J. Solution Chem. 21, 789 (1992).
J. L. Oscarson,J. Solution Chem. 17, 841 (1988).
J. L. Oscarson, S. E. Gillespie, J. J. Christensen, R. M. Izatt, and P. R. Brown,J. Solution Chem. 17, 865 (1988).
J. R. Ruaya and T. M. Seward,Geochim. CosActa 51, 121 (1987).
H. F. Holmes, et al.,J. Chem. Thermodyn. 19, 863 (1987).
P. R. Tremaine, K. Sway, and J. A. Barbero.J. Solution Chem. 15, 1 (1987).
J. D. Frantz and W. L. Marshall,Am. J. Sci. 284, 651 (1984).
R. E. Mesmer and C. F. Baes,J. Solution Chem. 3, 307 (1974).
J. W. Larson, K. G. Zeeb, and L. G. Hepler,Can. J. Chem. 60, 2141 (1982).
R. E. Mesmer, C. F. Baes, and F. H. Sweeton,Inorg. Chem. 11, 537 (1972).
R. H. Busey and R. E. Mesmer,Inorg. Chem. 16, 2444 (1977).
X. Chen and R. M. Izatt, J. L. Oscarson,Chem. Rev. 94, 467 (1994).
H. D. Cochran and E. Johnson,J. Supercritical Fluids 3, 157 (1990).
H. D. Cochran, P. T. Cummings, and S. Karaborni,Fluid Phase Equilibria 71, 1 (1992).
P. B. Balbuena, K. P. Johnston, and P. J. Rossky,J. Phys. Chem. 100, 2706 (1996).
P. B. Balbuena, K. P. Johnston, and P. J. Rossky,J. Phys. Chem. 100, 2716 (1996).
T. Xiang and K. P. Johnston,J. Phys. Chem. 98, 7915 (1994).
H.-H. Perkampus,UV-VIS Spectroscopy and Its Applications (Springer-Verlag, New York, 1992).
N. J. Rose and R. S. Drago,J. Am. Chem. Soc. 81, 6138 (1959).
T. M. Seward,Geochim. Cosmochim. Acta 48, 121 (1984).
C. A. Heinrich and T. M. Seward,Geochim. Cosmochim. Acta 54, 2207 (1990).
A. G. Briggs, P. Tickle, and J. M. Wilson,Spectrochimica Acta 26A, 1399 (1970).
M. Uematsu and E. U. Franck,J. Phys. Chem. Data 9, 1291 (1980).
L. Haar, J. S. Gallagher, and G. S. Kell,NBS/NRC Steam Tables (Hemisphere, Washington, DC, 1984).
R. B. Gupta, University of Texas at Austin (1993).
E. T. Ryan, T. Xiang, K. P. Johnston, and M. A. Fox,J. Phys. Chem. 100, 9395 (1996).
K. P. Johnston, P. B. Balbuena, T. Xiang, and P. J. Rossky,ACS Symposium Series 608, 77 (1995).
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Xiang, T., Johnston, K.P. Acid-base behavior in supercritical water: β-naphthoic acid-ammonia equilibrium. J Solution Chem 26, 13–30 (1997). https://doi.org/10.1007/BF02439441
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DOI: https://doi.org/10.1007/BF02439441