In this thesis, the electrochemical promotion of lr and Rh based catalysts was studied for the complete combustion of ethylene and propylene. The study was performed by using two types of electrocatalytical cells: a classical, pellet type cell and a tubular cell. This work has two major goals. The first one is the optimization of the employed electrocatalytical systems from electrochemical point of view. The second one concerns the study of the mechanism of the electrochemical promotion. The major part of this work concerns the electrochemical characterization of two cell types: a pellet type cell and a tubular cell. On the basis of the obtained results the modélisation of the potential and current distribution was performed, providing key parameters for the development of more efficient cell configurations. On one hand, these configurations ensure an uniform current distribution on the working electrode and enable correct catalyst potential measurement. On the other hand, it minimizes the current bypass in the bipolar tubular cell. The aim of the investigation in a two-compartment reactor was to evaluate and to compare the Au and Ir electrodes used in this work. Under 400°C, gold was found to be much worse material than lrÛ2 both as reference and counter electrode. Its potential was affected by oxygen and propylene adsorption and no equilibrium of electrochemical reaction was obtained at such low temperature. On the base of this knowledge, several materials better adapted to electrochemical promotion conditions have been proposed. Using the two-compartment reactor potential measurements under steady state conditions allowed to verify the mechanism of the propylene combustion on Rh and that of ethylene combustion on lr based catalysts proposed in the literature. Ameliorations of the existent kinetic models were proposed. The kinetic measurements were then analyzed with the additional help of ex situ XPS analysis. This study allowed to link the oxidation state of the catalyst surface with the extent of electrochemical promotion of the catalysts. It also allowed the ex situ observation of the appearance of new oxygen (oxide) species on the gas exposed surface of Ir catalyst. This new type of oxygen was different from the oxygen of Ir02 oxide, and it can represent the promoting species, according to backspiïïover theory. The same oxygen species was observed on well oxidized Ir02 catalyst surface, even before the polarization of this catalyst. Its presence was associated to the catalyst-support effect. It explains the high activity of Ir02 catalyst by comparison with the catalytic activity of lr metal. XPS analysis of Rh based catalysts indicated the possibly formation of an inferior Rh oxide (close to RhO) due to polarization. This may be a possible explanation of the observed permanent electrochemical promotion. Voltammetric charge measurements in very narrow potential window were performed while changing the catalyst thickness. The charge was demonstrated to be proportional to the catalyst thickness, suggesting the presence of the charged species on the gas exposed catalyst surface. The analogy between this situation and that of the emerged electrodes in liquid state electrochemistry was emphasized. The voltammograms obtained in this study were interpreted in the quite new, original way, which allowed to calculate the capacity of the different catalyst interfaces, the gas/catalyst interface, and the triple phase boundary, in good agreement with reference values from impedance spectroscopy measurements. Finally, the reaction rate transients during galvanostatic polarization of lr based catalyst have been moralized. The model fits well the experimental results.