Abstract
Low faradaic yields of Pb were found when electrolysing melts containing PbSO4 in solvents of either LiCl-KCl eutectic or Li2SO4-K2SO4-Na4SO4 eutectic and employing low current densities.
For all current densities employed, the decrease in current efficiency became greater as the lead sulphate concentration was increased but the influence of other sulphates was less pronounced.
From studies of the reaction of lead with the melt and a chronopotentiometric study of cathodic processes, we have found the following two reactions occur:
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(a)
Cathodic deposition of lead by the reversible reaction Pb2+ +2e⇌Pb
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(b)
Secondary non-electrochemical reaction of the electrodeposit 4Pb+5PbSO4→PbS+4PbO.PbSO4
The rate of the latter reaction is sufficient to account for the lowering in current efficiencies. No evidence could be found to support direct reduction of the sulphate anion.
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References
G. C. Bratt and R. W. Pickering,Met. Trans.,1 (1970) 2141.
C. H. Liu,J. Phys. Chem.,66 (1962) 164.
K. E. Johnson and H. A. Laitinen,J. Electrochem. Soc.,110 (1963) 314.
D. M. Wrench and D. Inman,Electrochem. Acta,12 (1967) 1601.
S. Senderoff, E. M. Klopp and M. L. Kronenberg. Eighth and Ninth Quarterly Technical Prog. Reports Contract NORD 18240 (1960).
B. Woodall quoted by H. Laitinen,Talanta,12 (1965) 1237.
B. W. Burrows and G. J. Hills,Electrochim. Acta,15 (1970) 445.
I. T. Gul'din and A. V. Buzhinskaya,Soviet Electrochemistry,1 (1965) 634.
F. I. L'vovich, S. A. Zaretskii and A. G. Morachevskii,Zhur. Phys. Khim.,40 (1967) 828.
A. A. Roudnitzki and I. P. Tverdovsky,Zhur. Phys. Khim.,9 (1936) 26.
P. L. King and B. J. Welch. Submitted for publication. P. L. King Ph.D. thesis, University of New South Wales, 1971.
B. J. Welch, P. L. King and R. A. Jenkins,Scand. J. Metallurgy,1 (1972) 49.
A. G. Bergman, Yu. J. Andryischenko and R. K. Bineeva,J. Inorg. Chem., U.S.S.R.,8 (1963) 880.
H. H. Kellogg,Trans. Met. Soc. A.I.M.E.,230 (1964) 1622.
W. H. Reinmuth,Anal. Chem.,33 (1961) 322.
M. Paunovic,J. Electroanal. Chem.,14 (1967) 447.
D. Inman, R. S. Sethi and R. Spencer,J. Electroanal. Chem.,29 (1971) 137.
D. Inman and J O'M Bockris,J. Electroanal. Chem.,3 (1962) 126.
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Hoa, T.K., Welch, B.J. Electrolysis of molten salt solutions containing PbSO4 . J Appl Electrochem 3, 45–52 (1973). https://doi.org/10.1007/BF01119466
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DOI: https://doi.org/10.1007/BF01119466