Experimental results obtained by combined in situ scanning probe micro
scopy (SPM) and electrochemical impedance spectroscopy (EIS) studies o
f underpotential deposition (UPD) of Pb on Ag(lll) and Ag(100) are cor
related and interpreted in terms of the kinetics of local electrode pr
ocesses. Exchange current densities at different underpotentials are r
elated to different low-dimensional (1D and 2D) Pb phases directly obs
erved by in situ SPM. First order phase transitions between expanded (
gas-like) and condensed (liquid- or solid-like) 2D Pb phases as well a
s surface alloy formation processes are taken into account for the int
erpretation of impedance data, Relatively simple conditions are obtain
ed on Ag(111) substrates where the formation of a condensed Pb monolay
er starting exclusively at monatomic steps is observed by in situ SPM
at low supersaturations with respect to the condensed 2D Pb phase. The
analysis of SPM and EIS data indicates that the lateral growth of the
condensed Pb monolayer preferentially occurs via a direct transfer of
Pb2+ from the electrolyte to the step edges. (C) 1998 Published by El
sevier Science Ltd. All rights reserved.