P. Nikitas, SURFACE PHASE-TRANSITIONS AT CHARGED INTERFACES PROBLEMS IN THEIR EXPERIMENTAL AND THEORETICAL INVESTIGATION, Electrochimica acta, 39(13), 1994, pp. 2055-2059
The possibility of a phase transition to proceed reversibility within
an electrified interface is examined. It is shown that the inhomogenei
ty of a real interface and in particular the existence of a diffuse la
yer is likely to put serious obstacles for a phase transition to take
place reversibly, especially when the controlled electrical variable i
s the electrode potential. However, their occurrence cannot be ruled o
ut. Reversible phase transitions may be more easily observed if the el
ectrode charge density is used as the independent electrical variable.
Irreversible transitions are also expected under charge density contr
olled conditions. In this case negative capacities might be observed.
Finally, the various problems about the clarification of the nature of
a phase transition experimentally and the implications to their theor
etical description are also discussed.