This work presents the electrochemical study of Yb(III) ions in molten alkali metal chlorides in the temperature range 723-1073 K. Transient electrochemical techniques such as linear sweep, cyclic and square wave voltammetry, and potentiometry at zero current have been used to investigate the reduction mechanism, transport parameters and thermodynamic properties of the reaction YbCl2 + 1/2Cl(2) = YbCl3 The results obtained show that the reduction reaction Yb(III) + e(-) double left right arrow Yb(II) is reversible being controlled by the rate of the mass transfer. The diffusion coefficient of [YbCl6](3-) complex ions has been determined at different temperatures in the fused eutectic LiCl-KCl, the equimolar NaCl-KCl and the CsCl media. The apparent standard potential of the soluble-soluble redox system Yb(III)/Yb(II) has been obtained by cyclic voltammetry. The influence of the nature of the solvent on the electrochemical and thermodynamic properties of ytterbium compounds is discussed. (c) 2008 Elsevier Ltd. All rights reserved.