Electrochemical and thermodynamic behaviour of oxygenated nitrogen compounds and aromatic hydrocarbons in nitromethane, and the nitration process with NO+2 (solvation phenomena)

Coumare, A.; Wartel, M.

doi:10.1016/0013-4686(90)87017-v

Cited by 7 publications

(9 citation statements)

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“…The electrochemical oxidation of the oxygenated nitrogen compounds has been studied previously in various media, but the reported results are often inconsistent. − For example, the redox potential of the NO 2 /NO 2 + couple was reported to vary by more than 0.6 V in the same solvent. , This ambiguity was assigned to the problem of contamination by traces of water that can react with nitrogen oxides to generate new electroactive species . Due to lack of detailed mechanistic understanding of nitrite oxidation, there are significant contradictions and variations in the interpretation of the successive oxidation waves of the nitrite anion. ,,,,, …”

Section: Introductionmentioning

confidence: 99%

Predicting the Electrochemical Behavior of Lithium Nitrite in Acetonitrile with Quantum Chemical Methods

et al. 2014

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Electrolyte stability is an essential prerequisite for the successful development of a rechargeable organic electrolyte Li-O2 battery. Lithium nitrate (LiNO3) salt was employed in our previous work because it was capable of stabilizing a solid-electrolyte interphase on the Li anode. The byproduct of this process is lithium nitrite (LiNO2), the fate of which in a Li-O2 battery is unknown. In this work, we employ density functional theory and coupled-cluster calculations combined with an implicit solvation model for neutral molecules and a mixed cluster/continuum model for single ions to understand the chemical and electrochemical behavior of LiNO2 in acetonitrile (AN). The redox potentials of oxygenated nitrogen compounds predicted in this study are in excellent agreement with the experimental results (the average accuracy is 0.10 V). Theoretical calculations suggest that the reaction between the nitrite ion and its first oxidation product, nitrogen dioxide (NO2), in AN solution proceeds via the initial formation of a trans-ONO-NO2 dimer that is subject to autoionization and the subsequent reaction of produced nitrosyl ion (NO(+)) with NO2(-). Good agreement between experimental and simulated cyclic voltammograms for electrochemical oxidation of LiNO2 in AN provides support to the proposed mechanism of coupled electrochemical and chemical reactions. The results suggest a possible mechanism of regeneration of LiNO3 in electrolyte in the presence of oxygen, which is uniquely possible under charging conditions in a Li-O2 battery.

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Section: Introductionmentioning

confidence: 99%

Predicting the Electrochemical Behavior of Lithium Nitrite in Acetonitrile with Quantum Chemical Methods

et al. 2014

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“…The reported equilibrium constants (log K) for the autoionization of N 2 O 4 in nitromethane and sulpholane at 298 K are −9.2 and −7.2, respectively. 15 The strong solvating ability of DMA, a solvent with a comparatively high donor number, is expected to increase the ionic dissociation of N 2 O 4 compared with nitromethane and sulpholane. Furthermore, the ionic recombination of NO 2 − with NO + is expected to occur near the diffusion-controlled limit, which ultimately enables the conversion of NO 2 − into an equimolar mixture of NO 3 − and NO.…”

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confidence: 99%

“…The observation that NO 2 – is electrochemically oxidized within the charging potential range of the O 2 electrode in Li/O 2 cells led us to perform a mechanistic analysis of NO 2 – electrochemistry in DMA. A mechanism comprising electrochemical and chemical reactions has been previously conjectured to account for cyclic voltammetry (CV) data obtained in organic electrolytes under inert atmosphere comprising two successive oxidation waves: − NO 2 − → NO 2 + normale 2 NO 2 ⇌ normalN 2 normalO 4 NO 2 − + 1 2 normalN 2 normalO 4 → NO 3 − + NO NO → NO + + normale …”

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confidence: 99%

“…The only satisfactory fit with the experimental CV data was obtained when autoionization of N 2 O 4 was explicitly incorporated into the model by substituting reactions and for reaction : normalN 2 normalO 4 ⇌ NO + + NO 3 − NO 2 − + NO + → NO 2 + NO According to this mechanism, the first electron-transfer step (reaction ) is followed by a series of rapid chemical reactions starting with dimerization of the resulting NO 2 (reaction ), followed by autoionization of N 2 O 4 (reaction ) to form nitrosonium (NO + ) and NO 3 – ions and finally ionic recombination of NO 2 – with NO + (reaction ). The reported equilibrium constants (log K ) for the autoionization of N 2 O 4 in nitromethane and sulpholane at 298 K are −9.2 and −7.2, respectively . The strong solvating ability of DMA, a solvent with a comparatively high donor number, is expected to increase the ionic dissociation of N 2 O 4 compared with nitromethane and sulpholane.…”

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confidence: 99%

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Lithium Nitrate As Regenerable SEI Stabilizing Agent for Rechargeable Li/O₂ Batteries

Uddin

Bryantsev

Giordani

et al. 2013

J. Phys. Chem. Lett.

109

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A major unsolved problem with rechargeable Li/O2 batteries is the identification of electrolyte compositions that allow efficient and stable cycling of both Li metal and O2 electrodes simultaneously. Previously, lithium nitrate (LiNO3) was employed in a rechargeable Li/O2 battery to stabilize the solid–electrolyte interphase on Li metal in an electrolyte based on N,N-dimethylacetamide (DMA), a solvent with favorable properties vis-à-vis the O2 electrode. We show that LiNO3 is regenerated following reaction with Li metal in the presence of dissolved O2, which may account for the surprising long-term cycling previously demonstrated in DMA. According to this new concept, nitrate anions incorporated into the electrolyte react with Li metal to form soluble nitrite anions and a passivating layer of Li2O on the Li electrode surface. The soluble nitrite anions subsequently react with dissolved O2 through a combined electrochemical and chemical process that results in regeneration of nitrate. Discovery of this regenerative principle provides a strategy for using other solvents that have favorable characteristics in the O2 electrode but are highly unstable toward Li metal without the use of a ceramic Li-ion-conducting membrane.

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“…Prior to use, nitromethane was filtered through a dry-alumina column in a dry-box and under argon (residual water 5 dried by passing the resulting stream through two traps containing P4O10, and collected in a trap at ca. -95°C.…”

Section: Chemicalsmentioning

confidence: 99%

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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Electrochemical and thermodynamic behaviour of oxygenated nitrogen compounds and aromatic hydrocarbons in nitromethane, and the nitration process with NO+2 (solvation phenomena)

Cited by 7 publications

References 26 publications

Predicting the Electrochemical Behavior of Lithium Nitrite in Acetonitrile with Quantum Chemical Methods

Predicting the Electrochemical Behavior of Lithium Nitrite in Acetonitrile with Quantum Chemical Methods

Lithium Nitrate As Regenerable SEI Stabilizing Agent for Rechargeable Li/O₂ Batteries

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

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Electrochemical and thermodynamic behaviour of oxygenated nitrogen compounds and aromatic hydrocarbons in nitromethane, and the nitration process with NO+2 (solvation phenomena)

Cited by 7 publications

References 26 publications

Predicting the Electrochemical Behavior of Lithium Nitrite in Acetonitrile with Quantum Chemical Methods

Predicting the Electrochemical Behavior of Lithium Nitrite in Acetonitrile with Quantum Chemical Methods

Lithium Nitrate As Regenerable SEI Stabilizing Agent for Rechargeable Li/O2 Batteries

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

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Lithium Nitrate As Regenerable SEI Stabilizing Agent for Rechargeable Li/O₂ Batteries