Abstract
The Interest in understanding chemical phenomena in aqueous solutions at elevated temperatures and pressures has grown significantly during the last decade[1–9] Practical applications include hydrothermal oxidation of organic wastes, hydrothermal growth of crystals, spraying of ceramics, and hydrothermal synthesis reactions, e.g., the commercial hydrolysis of chlorobenzene to produce phenol and dibenzofuran. Because water at high temperatures is highly compressible, small changes in temperature and pressure lead to large changes in the density and the dielectric constant which produce large variations in ion solvation and acid-base equilibria. Fundamental chemical properties, which are well-known in aqueous chemistry at 298 K, are much less available for supercritical water (SCW) (T c = 647.13 K, p c = 0.322 g/cm3, P c = 220.55 bar) solutions. Examples of such properties include ion solvation and acid-base equilibria, which play a central role in solvent effects on chemical reaction rate and equilibrium constants, phase equilibria, and corrosion. In this article these properties are discussed on the basis of in-situ spectroscopic measurement and computer simulation of ion solvation and chemical equilibria. The structure of water about ions is also discussed elsewhere in this book [10].
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References
Shaw, R. W., Brill, T. B., Clifford, A. A., Eckert, C. A. and Franck, E. U. (1991) Supercritical Water: A Medium for Chemistry, Chenu and Eng. News 69, 26.
Tester, J. W., Holgate, H. R., Annellini, F. J., Webley, P. A., Killilea, W. R., Hong, G. T. and Bamer, H. E. (1993) in Emerging Technologies in Hazardous Waste Management III, eds. D. W. Tedder and F. G. Pohlaed, Am. Chem. Soc, Washington, pp. 35–76.
Gloyna, E. F. and Li, L. (1993) Supercritical Water Oxidation: An Engineering Update, Waste Management 13, 379–394.
Balbuena, P. B., Flanagie, L. W., Johnston, K. P. and Rossky, P. J. (1995) in Physical Chemistry of Aqueous Systems: Meeting the Needs of Industry, eds. H. J. White, J. V. Sengers, D. B. Neumann and J. C. Bellows, Begell House, New York, pp. 595–601.
Johnston, K. P., Balbuena, P. B., Xiang, T. and Rossky, P. J. (1995) Simulation and Spectroscopy of Solvation in Water from Ambient to Supercritical Conditions, Am. Chem. Soc. Symp. Series 608, 77–92.
Savage, P. E., Gopalan, S., Mizan, T. I., Martino, C. J. and Brock, E. E. (1995) Reactions at Supercritical Conditions: Applications and Fundamentals, AIChE J. 41, 1723.
Levelt-Sengers, J. M. H. (1999) in Supercritical Fluids- Fundamentals and Applications, ed. E. Kiran, Kluwer, Dordrecht.
Shaw, R. W. and Dahmen, N. (1999) in Supercritical Fluids- Fundamentals and Applications, ed. E. Kiran, Kluwer, Dordrecht.
Savage, P. E. (1999) Organic Chemical Reactions in Supercritical Water, Chemical Reviews 99, 603–622.
Chialvo, A. A., Cummings, P. T. and Cummings, P. (1999) in Supercritical Fluids-Fundamentals and Applications, Kluwer, Dordrecht.
Chen, X., Izatt, R. M. and Oscarson, J. L. (1994) Thermodynamic Data for Ligand Interaction with Proton and Metal Ions in Aqueous Solutions at High Temperatures, Chem. Rev. 94, 467–517.
Xiang, T. and Johnston, K. P. (1994) Acid-Base Behavior of Organic Compounds in Supercritical Water, J. Phys. Chem. 98, 7915.
Wofford, W. T., Gloyna, E. F. and Johnston, K. P. (1998) Boric Acid Equilibria in Near-Critical and Supercritical Water, Ind. Eng. Chem. Res. 37, 2045–51.
Soper, A. K. (1996) Bridge over troubled water: the apparent discrepancy between simulated and experimental non-ambient water structure, J. Phys.: Condens. Matter 8, 9263–67.
Jedlovszky, P., Brodholt, J. P., Bruni, F., Ricci, M. A., Soper, A. K. and Vallauri, R. (1998) Analysis of the hydrogen-bonded structure of water from ambient to supercritical conditions, J. Chem. Phys. 108, 8528–40.
Bellissent-Funel, M.-C., Tassaing, T., Zhao, H., Beysens, D., Guillot, B. and Guissani, Y. (1997) The structure of supercritical heavy water as studied by neutron diffraction, J. Chem. Phys. 107, 2942–49.
de Jong, P. H. K., Neilson, G. W. and Bellissent-Funel, M.-C. (1996) Hydration of Ni2+ and Cl- in a concentrated nickel chloride solution at 100° C and 300° C, J. Chem. Phys. 105, 5155–59.
Ohtaki, H., Radnai, T. and Yamaguchi, T. (1997) Structure of water under subcritical and supercritical conditions studied by solution x-ray diffraction, Chem. Soc. Rev. 26, 41–51.
Matubayasi, N., Wakai, C. and Nakahara, M. (1997) NMR study of water structure in super-and subcritical conditions, Phys. Rev. Letters 78, 2573–76.
Tucker, S. C. and G. Goodyear (1999) in Supercritical Fluids- Fundamentals and Applications, ed. E. Kiran, Kluwer, Dordrecht.
Allen, M. P. and Tildesley, D. J. (1987) Computer Simulation of Liquids, Oxford University Press, New York.
Buback, M. and Crerar, D. (1987) in Hydrothermal Experimental Techniques, eds. U. G. and H. Barnes, Wiley, New York.
Matubayasi, N., Wakai, C. and Nakahara, M. (1997) Structural study of supercritical water. I. Nuclear magnetic resonance spectroscopy, J. Chem. Phys. 107, 9133–40.
Gorbaty, Y. E. and Kalinichev, A. G. (1995) Hydrogen Bonding in Supercritical Water. 1. Experimental Results, J. Phys. Chem. 99, 5336–40.
Gupta, R. B., Panayiotou, C. G., Sanchez, I. C. and Johnston, K. P. (1992) Theory of Hydrogen Bonding in Supercritical Fluids, AIChE J. 38, 1243.
Wallen, S. L., Palmer, B. J. and Fulton, J. L. (1998) The ion pairing and hydration structure of Ni2+ in supercritical water at 425°C determined by x-ray absorption fine structure and molecular dynamics studies, J. Chem. Phys. 108, 4039–4046.
Niemeyer, E. D. and Bright, F. (1997) On the Local Environment Surrounding Pyrene in Near and Supercritical Water, Appl. Spectrosc. 51, 1547–1553.
Ikushima, Y., Hatakeda, K., Saito, N. and Arais M. (1998) An in situ Raman spectroscopy study of subcritical and supercritical water: The peculiarity of hydrogen bonding near the critical point, J. Chem. Phys. 108, 5855–5860.
Spohn, P. D. and Brill, T. B. (1989) Raman Spectroscopy of the Species in Concentrated Aqueous Solutions of Zn(NO3)2, Ca(NO3)2, Cd(NO3)2, LiNO3, and NaNO3 up to 450°C and 30 MPa, J. Phys. Chem. 93, 6224–6231.
Schoppelrei, J. W. and Brill, T. B. (1997) Spectroscopy of Hydrothermal Reactions. 7. Kinetics of Aqueous [NH3OH]NO3 at 463–523 K and 27.5 MPa by Infrared Spectroscopy, J. Phys. Chem, A. 101, 8593–8596.
Rice, S. F., Steeper, R. R. and Aiken, J. D. (1998) Water Density Effects on Homogeneous Water-Gas Shift Reaction Kinetics, J. Phys. Chem. A 102, 2673–2678.
Ryan, E. T., Xiang, T., Johnston, K. P. and Fox, M. A. (1996) Excited-State Proton Transfer Reactions in Subcritical and Supercritical Water, J. Phys. Chem. 100, 9395–9402.
Schoppelrei, J. W., Kieke, M. L. and Brill, T. B. (1996) Spectroscopy of Hydrothermal Reactions. 2. Reactions and Kinetic Parameters of [NH3OH]NO3 and Equilibria of (NH4)2 CO3 Determined with a Flow Cell and FT Raman Spectroscopy, J. Phys. Chem. 100, 7463–70.
Seward, T. M. (1984) The formation of lead(II) chloride complexes to 300°C: a spectrophotometric study, Geochim. Cosmochim. Acta 48, 121.
Heinrich, C. A. and Seward, T. M. (1990) A spectrophotometric study of aqueous iron(II) chloride complexing from 25 to 200°C, Geochim. Cosmochim. Acta 54, 2207.
Bennett, G. E. and Johnston, K. P. (1994) UV-visible Absorbance Spectroscopy of organic Probes in Supercritical Water, J. Phys. Chem. 98, 441.
Chlistunoff, J. B. and Johnston, K. P. (1998) UV-Vis Spectroscopic Determination of the Dissociation Constant of Bichromate from 160°C to 400°C, J. Phys. Chem. B. 102, 3933.
Mesmer, R. E., Palmer, D. A. and Simonson, J. M. (1991) in Activity Coefficients in Electrolyte Solutions,2nd Edition, ed. K. S. Pitzer, CRC Press, Boca Raton, pp. 491.
Mesmer, R. E., Marshall, W. L., Palmer, D. A., Simoeson, J. M. and Holmes, H. F. (1988) Thermodynamics of Aqueous Association and lonization Reactions at High Temperatures and Pressure, J. Solution Chem. 17, 699–718.
Balbuena, P. B., Johnston, K. P. and Rossky, P. J. (1996) Molecular Dynamics Simulation of Electrolyte Solutions in Ambient and Supercritical Water: II. Relative Acidity of HCl, J. Phys. Chem. 100, 2716–2722.
Xiang, T. and Johnston, K. P. (1997) Acid-Base Behavior in Supercritical Water: β-Naphthoic Acid-Ammonia Equilibrium, J. Solution Chemistry 26, 13–30.
Ramayya, S. and Antal, M. J., Jr (1990) Influence of pressure on the acid-catalysed rate constant for 1-propanol dehydration in supercritical water, J. Am. Chem. Soc. 112, 1927–1931.
Ulmer, G. C. and Barnes, H. L. (1987) Hydrothermal Experimental Techniques, Wiley-Interscience, New York.
Dell’Orco, P. C., Foy, B. R., Le, L., Ely, J., Patterson, K. and Buelow, S. J. (1995) Hydrothermal Oxidation of Organic Compounds by Nitrate and Nitrite, ACS Symp. Ser. 608, 179.
Palmer, D. A., Wesolowski, D. and Mesmer, R. E. (1987) A Potentiometric investigation of the hydrolysis of chromate(VI) ion in NaCl Media to 175°C, J. Solution Chem. 16, 443–463.
Straatsma, T. P. and McCammon, J. A. (1992) Computational Alchemy, Ann. Rev. Phys. Chem. 43, 407–35.
Flanagin, L. W., Balbuena, P. B., Johnston, K. P. and Rossky, P. J. (1995) Temperature and Density Effects on an SN2 Reaction in Supercritical Water, J. Phys. Chem 99, 5196.
Bennett, G. E., Rossky, P. J. and Johnston, K. P. (1995) Continuum Electrostatics Model for an SN2 Reaction in Supercritical Water, J. Phys. Chem. 99, 16136–16143.
Balbuena, P. B., Johnston, K. P. and Rossky, P. J. (1996) Molecular Dynamics Simulation of Electrolyte Solutions in Ambient and Supercritical Water: I. Ion Solvation, J. Phys. Chem. 100, 2706–2715.
Johnston, K. P., Bennett, G. E., Balbuena, P. B. and Rossky, P. J. (1996) Continuum Electrostatic Model for Ion Solvation and Relative Acidity of HCl in Supercritical Water, J. Am. Chem. Soc. 118, 6746–6752.
Flanagin, L. W., Balbuena, P. B., Johnston, K. P. and Rossky, P. J. (1997) Ion Solvation in Supercritical Water Based on an Adsorption Analogy, J. Phys. Chem. 101, 7798–8005.
Berendsen, H. J. C., Grigera, J. R. and Straatsma, T. P. (1987) The missing term in effective pair potentials, J. Phys. Chem. 91, 6269–71.
Dang, L. X. (1998) Importance of Polarization Effects in Modeling the Hydrogen Bond in Water Using Classical Molecular Dynamics Techniques, J. Phys. Chem. B. 102, 620–24.
de Pablo, J. J., Prausnitz, J. M., Strauch, H. J. and Cummiogs, P. T. (1990) Molecular simulation of water along the liquid-vapor coexistence curve from 25°C to the critical point, J. Chem. Phys. 93, 7355–7359.
Guissani, Y. and Guillot, B. (1993) A computer simulation study of the liquid-vapor coexistence curve of water, J. Chem. Phys. 98, 8221–8235.
Guillot, B. and Guissani, Y. (1993) A computer simulation study of the temperature dependence of the hydrophobic hydration, J. Chem. Phys. 99, 8075.
Del Buono, G. S., Rossky, P. J. and Schnitker, J. (1991) Model dependence of quantum isotope effects in liquid water, J. Chem. Phys. 95, 3728–37.
Gilson, M. K. and Sharp, K. A. (1987) Calculating the Electrostatic Potential of Molecules in Solution: Method and Error Assesment, J. Comput. Chem. 9, 327–335.
Davis, M. E. and McCammon, J. A. (1990) Electrostatics in biomolecular structure and dynamics, Chem. Rev. 90, 509–21.
Luo, H. and Tucker, S. C. (1995) Compressible Continuum Solvation Model for Molecular Solutes, J. Am. Chem. Soc. 117, 11359–11360.
Luo, H. and Tucker, S. C. (1997) A Compressible Continuum Model Study of the Chloride plus Methyl Chloride Reaction in Supercritical Water, J. Phys. Chem. B, 1063–71.
Kajimoto, O., Futakami, M, Kobayashi, T. and Yamasaki, K. (1988) Charge-Transfer-State Formation in Supercritical Fluid: (N, N-Dimethylamino) benzonitrile in CF3H., 92, 1347.
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Johnston, K.P., Rossky, P.J. (2000). Solution Chemistry in Supercritical Water: Spectroscopy and Simulation. In: Kiran, E., Debenedetti, P.G., Peters, C.J. (eds) Supercritical Fluids. NATO Science Series, vol 366. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-3929-8_14
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DOI: https://doi.org/10.1007/978-94-011-3929-8_14
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