An electrochemical study of the molecular and ionic dissociation of NO2Cl in aprotic media

In order to bring more information on the thermodynamic and kinetic behavior of nitryl chloride in aprotic media, we have surveyed exhaustively the first NO2C1-reduction step in sulfolane (at the platinum electrode), taking into account our preliminary results about the electrochemical properties of NOzCl in aprotic solvents. We have excluded the intervention of the weak ionic dissociation of NOzCl (NOZC1 NOz' + C1- [I]) and its slow molecular decomposition as: 2N02C1 ClZ + 2NO; (e N204) [I13 in this process. We have admitted the occurrence of a rapid chemical reaction which controls kinetically the electrochemical system studied: NO + NOzCl 4 NOCl + NO; [III].By analyzing the kinetic currents resulting from the 1st cathodic wave of NOzCl 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.

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Electron‐transfer kinetics and activation barriers for the reductions of nitrosonium and nitronium ions in aprotic solvents

Wartel¹

1993

Int J of Chemical Kinetics

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Using the cyclic voltammetry (CV), the electron-transfer kinetics for the reductions of NO+ and NOz' cations have been studied at the Pt electrode in nitromethane, sulfolane, and propylene carbonate. The heterogeneous rate constants have been determined by two independent procedures from the transfer coefficient a, the diffusion coefficient D, from a detailed examination of the CV-peak separations, and from an inspection of the values of the cathodic peak potentials at different scan rates. The results have been compared to those reported in the literature, and discussed. In the classical model, outer-sphere electron-transfer reactions are considered subject to an activation energy arising from solvent reorganization and bond reorganization processes. The solvent and molecular reorganizational barriers for these electroreductions have been assessed in aprotic media. The Marcus-Hush theory has been applied to the self-exchange reactions of the NOz+/NOz and NO+/NO couples in an attempt to predict the rate of electron transfer. The findings indicate some improvement between theory and experiment. However, it should be noted that the experimental values of k, found for the NOz+ reduction in the solvents used are still too high in comparison with those determined theoretically. In view of the fairly strong coordination of the solvent molecule(s) as ligandb) to NOz+ and NO+ cations, we believe that such discrepancies should stem, to some extent, from the involvement of an inner-sphere pathway by generation of an activated complex on the surface of the Pt electrode. 0

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An electrochemical study of the molecular and ionic dissociation of NO2Cl in aprotic media

Cited by 7 publications

References 17 publications

ChemInform Abstract: Electrochemical Study of the Molecular and Ionic Dissociation of NO₂Cl in Aprotic Media.

ChemInform Abstract: Electrochemical Study of the Molecular and Ionic Dissociation of NO₂Cl in Aprotic Media.

Mechanistic and kinetic aspects of the reduction of nitryl chloride in aprotic media

Electron‐transfer kinetics and activation barriers for the reductions of nitrosonium and nitronium ions in aprotic solvents

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An electrochemical study of the molecular and ionic dissociation of NO2Cl in aprotic media

Cited by 7 publications

References 17 publications

ChemInform Abstract: Electrochemical Study of the Molecular and Ionic Dissociation of NO2Cl in Aprotic Media.

ChemInform Abstract: Electrochemical Study of the Molecular and Ionic Dissociation of NO2Cl in Aprotic Media.

Mechanistic and kinetic aspects of the reduction of nitryl chloride in aprotic media

Electron‐transfer kinetics and activation barriers for the reductions of nitrosonium and nitronium ions in aprotic solvents

Contact Info

Product

Resources

About

ChemInform Abstract: Electrochemical Study of the Molecular and Ionic Dissociation of NO₂Cl in Aprotic Media.

ChemInform Abstract: Electrochemical Study of the Molecular and Ionic Dissociation of NO₂Cl in Aprotic Media.