Abstract
The use of yttria-stabilized zirconia (YSZ) electrodes of the type Hg/HgO/ZrO2(Y2O3)/H+, for measuring pH in aqueous solutions at high subcritical (150<T<374°C) and supercritical temperatures (T>374°C) is reviewed. The construction and operation of the YSZ and reference electrodes employed in these studies are described and their application in measuring the pH of a variety of technologically-important aqueous system is discussed. We show that the YSZ electrode is thermodynamically viable at temperatures into the supercritical region, and that it is a primary pH sensor in that calibration is not necessary, provided that the activity of water is known. However, highly accurate pH measurements at high subcritical and supercritical temperatures will require the development of more accurate reference electrodes.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
R. G. Bates,Determination of pH, Theory and Practice (Wiley-Interscience, New York, 1973).
R. E. Mesmer,Geochim. et Cosmochim. Acta 55, 1171 (1991).
D. D. Macdonald, S. Hettiarchchi, and S. J. Lenhart,J. Solution Chem. 17, 719 (1988).
L. W. Niedrach,J. Electrochem. Soc. 127, 2122 (1980).
T. Tsuruta and D. D. Macdonald,J. Electrochem. Soc. 129, 1221 (1982).
S. hettiarachchi and D. D. Macdonald,J. Electrochem. Soc. 131, 2206 (1984).
S. Hettiarachchi, P. Kedzierzawski, and D. D. Macdonald,J. Electrochem. Soc. 132, 1866 (1985).
M. J. Danielson and O. H. Koski,J. Electrochem. Soc. 132, 296 (1985);132, 2037 (1985).
C.-T. Liu and W. T. Lindsay,J. Solution Chem. 1, 45 (1972).
D. J. G. Ives and G. J. Janz,Reference Electrodes (Academic Press, New York, 1961).
D. D. Macdonald,Corrosion 34, 75 (1978).
D. D. Macdonald, A. C. Scott, and P. R. Wentrcek,J. Electrochem. Soc. 126, 908 (1978).
K. Makela, S. Hettiarachchi, R. Emerson, and D. D. Macdonald, unpublished data.
W. Bogaerts and A. A. Van Haute,Proc. Int. Congr. Met. Corros. 4, 169 (1984) [published by Nat. Res. Council Canada].
D. D. Macdonald, A. C. Scott, and P. R. Wentrcek,J. Electrochem. Soc. 126, 1618, (1979).
P. Henderson,Z. Physik. Chem. 59, 118 (1907);63, 325 (1908).
C. F. Baes and R. E. Mesmer,Hydrolysis of Cations (Wiley-Interscience, New York, 1976).
J. Pang and D. D. Macdonald, to be published.
R. S. Greeley, W. T. Smith, R. W. Stoughton, and M. H. Lietzke,J. Phys. Chem. 64, 652, 1445, 1861 (1960).
D. D. Macdonald, inModern Aspects of Electrochemistry, Vol. 11, B. E. Conway and J. O'M. Bockris, eds., (Plenum Press, New York, (1975) p. 141.
G. B. Naumov, B. N. Ryzhenko, and I. L. Khodakovsky,Handbook of Thermodynamic Data, USGS-WRD-74-001 (1974).
R. E. Mesmer, C. F. Baes, and F. H. Sweeton,Inorg. Chem. 11, 537 (1972).
J. P. Paine and P. Millett, private communications.
H. Song, D. D. Macdonald, C. Shoemaker, and J. P. Paine, inProc. Fourth Int. Symp. Environ. Degrad. Mat. Nucl. Power Systs.-Water Reactors, D. Cubicciotti, ed., (NACE, Texas, 1990), p. 12.
R. Garnsey,Nucl. Energy 18, 2 (1979).
J. R. Park and D. D. Macdonald,Corrosion 45, 563 (1988).
M. Ben-Haim and D. D. Macdonald, to be published (1991).
W. L. Marshall and E. V. Jones,J. Inorg. Nucl. Chem. 36, 2313 (1974).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Macdonald, D.D., Hettiarachchi, S., Song, H. et al. Measurement of pH in subcritical and supercritical aqueous systems. J Solution Chem 21, 849–881 (1992). https://doi.org/10.1007/BF00651512
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00651512