The electrochemical behavior of several kinds of carbon have been studied in various molten fluorides. The temperature range of the electrolyte employed in this experiment is related to the melting point of each melt, e.g., 50°–120°C for
NH4F·2HF
, 80°–150°C for
KF·2HF
, 260°C for
KF·HF
, and 470°–600°C for
normalLiF‐normalNaF‐KF
. The values of the peak current density
false(inormalpfalse)
at ca. 6V vs. Pt and the minimum current density
false(inormala−false)
at the potentials over 6V vs. Pt were measured from the anodic polarization curves obtained by cyclic voltammetry with a sweep rate of 200 mV · s−1, and then they were interpreted kinetically. The value of
inormala
was theoretically proved to be proportional to the rate of decomposition of
false(CF)n
film formed on the surface of carbon anode. From the plots of
loginormala
against the reciprocal of absolute temperature (1/T), the activation energy of the disproportionation of
false(CF)n
film obtained in the molten
normalLiF‐normalNaF‐KF
system was 22.0–25.9 kcal · mol−1. In contrast, that in each case of the molten
KF·HF
,
KF·2HF
, and
NH4F·2HF
was only 5.5–9.4 kcal · mol−1. However, the carbon anode was often broken in the presence of
HF
. The disproportionation of the
false(CF)n
film is catalyzed by
HF
and the physical etching of the carbon anode could be explained in terms of the formation of an intercalation compound containing
HF
.
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