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Mechanistic and kinetic aspects of the reduction of nitryl chloride in aprotic media
Author(s) -
Boughriet A.,
Coumare A.,
Fischer J. C.,
Wartel M.
Publication year - 1988
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550201003
Subject(s) - chemistry , kinetic energy , electrochemistry , reaction rate constant , sulfolane , chloride , atmospheric temperature range , kinetics , thermodynamics , electrode , organic chemistry , physics , quantum mechanics , solvent
In order to bring more information on the thermodynamic and kinetic behavior of nitryl chloride in aprotic media, we have surveyed exhaustively the first NO 2 Cl‐reduction step in sulfolane (at the platinum electrode), taking into account our preliminary results about the electrochemical properties of NO 2 Cl in aprotic solvents. We have excluded the intervention of the weak ionic dissociation of NO 2 Cl (NO 2 Cl ⇆ NO 2 ++ Cl − [I]) and its slow molecular decomposition as: 2NO 2 Cl ⇄ Cl 2 + 2NO 2 •(⇄ N 2 O 4 ) [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 NO 2 Cl 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.