NONSTOICHIOMETRIC DISSOLUTION OF LANTHANUM FLUORIDE (LAF3) AND ITS RELEVANCE TO A PROCESS OF ION-SELECTIVE CHARGE SEPARATION AT THE SOLID-SOLUTION INTERFACE
Y. Tani et al., NONSTOICHIOMETRIC DISSOLUTION OF LANTHANUM FLUORIDE (LAF3) AND ITS RELEVANCE TO A PROCESS OF ION-SELECTIVE CHARGE SEPARATION AT THE SOLID-SOLUTION INTERFACE, Journal of electroanalytical chemistry [1992], 378(1-2), 1994, pp. 205-213
The solubilities of lanthanum fluoride (LaF3) powder and single crysta
ls were measured in various aqueous electrolyte solutions. In contrast
with the classical assumption of the stoichiometric dissolution of La
F3, it was found that the dissolution of the component cation La3+ was
undetectable and the fluoride ion dissolved preferentially: c(F) - >
3c(La3+) where c is the ion concentration. X-ray photoelectron spectro
scopy (XPS) of the LaF3 surface treated with electrolyte solutions cor
roborated this observation. As a result of the preferential fluoride d
issolution, charge separation was expected to occur in such a way that
the LaF3 surface would have positively charged ''fluoride-vacancies''
. This was confirmed by changes in membrane potential as a function of
the fluoride dissolution and the adsorption of an anionic adsorption
marker (eosin Y) on the solid surface. It was also found that the pref
erential dissolution of fluoride ions was accompanied by simultaneous
adsorption of almost the same amount of electrolyte anions (e.g. NO3-)
onto the LaF3 surface. This was confirmed by both solution measuremen
ts and surface analysis by diffuse reflectance IR Fourier transform (D
RIFT) spectrometry. The result of this anion adsorption was explained
in terms of ion exchange to ensure electroneutrality in the bulk of th
e adjacent electrolyte solution, which would otherwise be violated by
the preferential fluoride dissolution. The anionic adsorption marker a
nd DRIFT measurements were used to characterize further the above-ment
ioned ion exchange and selective uptake of fluoride ions into the ''fl
uoride vacancies''. Release of the adsorbed eosin Y or electrolyte ani
ons, such as NO3-, from the LaF3 surface was found to be induced by F-
or OH- ions only. On the basis of this observation, the response mech
anism of the fluoride ion-selective electrodes was discussed.