Abstract
Molten bisulphates form an interesting class of low-temperature fused salts which quench to form glasses; some technical and theoretical applications of these systems are discussed. The NaHSO4KHSO-4 eutectic (46.5% KHSO4, m.p. 125°C,T g 25°C) is easy to study since at lower temperatures decomposition of the melt is retarded and supercooling readily occurs. The solvent properties of this eutectic towards both inorganic and organic solutes have been investigated. The oxidation states available to transition and post-transition metals were studied spectrophotometrically and voltametrically; the results show a very restricted pattern of redox chemistry. The (abbreviated) electrochemical series is V(V)/V(IV)>Mn(III)/Mn(II)>H(I)/H2(O)>Ag(I)/Ag(O)>Mo(VI)/Mo(V)> Hg(I)/Hg(O)>Cu(II)/Cu(O)>Zn(II)/Zn(O). The Hammett acidity function,H 0, was measured as in the range −1 to −2. Various factors influencing redox reactions in the melt are discussed.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
S. E. Rogers and A. R. Ubbelohde,Trans. Farad. Soc. 46, 1051 (1950).
S. Tajima, M. Soda, T. Mari, and N. Baba,Electrochim. Acta 1, 205 (1959).
A. M. Shams el Din,ibid. 7, 613 (1962).
A. J. Arvia and H. A. Videla,ibid. 10, 21 (1965).
A. J. Arvia and H. A. Videla,ibid. 10, 33 (1965).
A. J. Arvia and H. A. Videla,ibid. 11, 537 (1966).
A. J. Arvia, A. J. Calandra, and H. A. Videla,ibid. 13, 167 (1968).
A. J. Arvia, F. De Vega, and H. A. Videla,ibid. 13, 581 (1968).
A. J. Arvia, A. J. Calandra, and H. A. Videla,ibid. 14, 25 (1969).
L. Cambi and G. Bozza,Ann. Chim. Appl. 13, 221 (1923).
D. Tomkova, P. Jiru, and J. Rosicky,Coll. Czeck. Commun. 25, 957 (1960).
G. E. Walrafen, D. E. Irish, and J. F. Young,J. Chem. Phys. 37, 662 (1962).
T. Forland and W. A. Weyl,J. Am. Ceram. Soc. 33, 186 (1950).
J. A. Duffy, F. P. Glasser, and M. D. Ingram,J. Chem. Soc. A, 551 (1968).
C. A. Angell and C. T. Moynihan, in ‘Molten Salts, Characterization and Analysis’, p. 315. Ed. Gleb Mamantov, Marcel Dekker (1969).
R. Bose, R. Weiler, and P. B. Macedo,Phys. Chem. Glasses,11, 117 (1970).
J. A. Duffy and W. J. D. Macdonald,J. Chem. Soc.,A, 977 (1970).
J. A. Duffy and W. J. D. Macdonald,Phys. Chem. Glasses,11, 1 (1970).
J. A. Duffy and W. J. D. Macdonald,J. Chem. Soc.,A, 2066 (1970).
J. A. Duffy, and M. D. Ingram,Chem. Instrum. (to be submitted).
J. A. Duffy,Phys. Chem. Glasses 9, 190 (1968).
J. A. Duffy, S. M. Forbes, and M. D. Ingram,J. Chem. Soc. A, 452 (1970).
J. A. Duffy and M. D. Ingram,J. Chem. Phys. (in press).
R. P. Seward and J. P. Miller,J. Phys. Chem. 69, 3156 (1965).
A. Conte and S. Casadio,Ric. Sci. 36, 433 (1966).
P. A. H. Wyatt, ‘Annual Reports’,Chem. Soc. (1969), p. 93.
L. W. Hamilton and M. D. Ingram (unpublished work).
G. Tridot, G. Nowogroki, J. Nicole, M. Wozniak, and J. Canonne,C.R. Acad. Sci. Paris, Ser. C 270, 204 (1970).
D. M. Gruen and R. L. McBeth,Pure Appl. Chem. 6, 23 (1963).
J. A. Duffy and M. D. Ingram,J. Am. Ceram. Soc. 51, 544 (1968).
K. W. Fung and K. E. Johnson,Can. J. Chem. 47, 4999 (1969).
J. A. Duffy and M. D. Ingram,J. Chem. Soc. A, 2398 (1969).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Ingram, M.D., Duffy, J.A. & Forbes, S.M. Electrochemical behaviour and glass formation in molten bisulphates. J Appl Electrochem 1, 53–63 (1971). https://doi.org/10.1007/BF00615747
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00615747