Abstract: | In order to bring more information on the thermodynamic and kinetic behavior of nitryl chloride in aprotic media, we have surveyed exhaustively the first NO2Cl-reduction step in sulfolane (at the platinum electrode), taking into account our preliminary results about the electrochemical properties of NO2Cl in aprotic solvents. We have excluded the intervention of the weak ionic dissociation of NO2Cl (NO2Cl ? NO + Cl? I]) and its slow molecular decomposition as: 2NO2Cl ? Cl2 + 2NO (? N2O4) II] in this process. We have admitted the occurrence of a rapid chemical reaction which controls kinetically the electrochemical system studied: \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm NO} + {\rm NO}_{\rm 2} {\rm Cl}\buildrel {k^*} \over \longrightarrow {\rm NOCl} + {\rm NO}_{\rm 2}^ \cdot {\rm}{\rm III]} $\end{document}. By analyzing the kinetic currents resulting from the 1 st cathodic wave of NO2Cl at the temperature range 303–323 K, the rate constant, k*, and the activation energy, E*, of reaction III] have been determined. These results and those previously found in the gas phase are discussed. |