The electrochemical behavior of ferrocene (Fc) and ferriceniurn (Fc(+)) was investigated by cyclic voltammetry with convolutional and semi-differential electroanalyses in the temperature range 298-373 K in the hydrophobic room temperature ionic liquid systems consisting of bis(trifluoromethanesulfone)imide anion with quaternary ammonium cation. The experimental results indicated that the redox reaction of Fc/Fc(+) was reversible in this ionic liquid and the charge-transfer rate constant (k(o)) has been obtained. Mass transport towards the electrode is a simple diffusion process and the diffusion coefficient (D) for Fc/Fc(+) has been also calculated. These results indicated that the k(o) and D increased with increasing temperature in ionic liquids. The validity of the Arrhenius law was verified by investigating the temperature dependences of k(o) and D. (C) 2005 Elsevier Ltd. All rights reserved.