Influence of the medium on the ionic dissociation of N2O4 and the kinetics of decomposition of N2O3 in aprotic solvents

Coumare, A.; Fischer, J.; Wartel, M.

doi:10.1016/0022-0728(86)90057-4

Cited by 12 publications

(2 citation statements)

References 25 publications

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“…Indeed, several mechanisms had been previously proposed to interpret nitration phenomena, nevertheless not any good evidence was obtained, and hereby many questions are yet to be resolved. The second application of this work has been the working out of high-energy N,O,/lithium electrochemical cells [161 (by employing sulfolane or propylene carbonate as the solvent), not polarized by nitric oxide, which inhibits the use of these cells due to the low solubility of this gas in organic media [16,251. Indeed, the formation of the NO gas, throughout the use of these cells, can be consumed immediately by the Red/Ox process (10) because of the high rate of this reaction.…”

Section: Resultsmentioning

confidence: 99%

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

Coumare¹,

Fischer²,

Wartel³

1988

Int J of Chemical Kinetics

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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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Section: Resultsmentioning

confidence: 99%

“…This latter reaction is fast [15,16] and equal to K(C) = 4.0 X mol dm-, at 303 K in sulfolane [ E l . Thus, it is possible to consider Cl, reacting as an activated oxidizer, "Cl~".…”

Section: Mechanistic Study Of the First Nocl-reduction Step In Sulfomentioning

confidence: 99%

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

Coumare¹,

Fischer²,

Wartel³

1988

Int J of Chemical Kinetics

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Electrooxidation of primary nitramine anions on platinum in MeCN

Frolovskii

Petrosyan

1999

Russ Chem Bull

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Oxidation of primary, nitramine anions RNNO2-Bu~N + (R = ,'vie, Et, Pr i, or methoxyfurazanyl) in 0.1 N BuzNCIO a in MeCN on a Pt anode was studied by voltammetry and controlled potential electrolysis. It was found that the first stage of oxidation affords the corresponding radicals, which are further stabilized due to hydrogen abstraction from the medium. These radicals are also involved in other reactions, includi~g those, which yield azo derivatives. The possibility of generation of nitrene species in these reactions is discussed.Key words: electrooxidation of nitramine anions, nitrenes, azo compounds.Previously. I we examined the possibility of cathode deprotonation of primary, nitramines. As part of continuing studies of the electrochemical behavior of nitramines, in the present work we studied the regularities of electrooxidation of nitramine anions containing a donor or acceptor substituent at the amine nitrogen atom. Judging from the published data, these processes are still poorly understood. However, radical intermediates, which are probable intermediates in the oxidation of nitramine anions, could be considered as potential sources of nitrene species. ExperimentalThe voltammetric measurements were carried out in a temperature-controlled (25 ~ glass cell with cathode and anode compartments separated by a porous-glass filter. The polarization curves were recorded on a rotating disk Pt electrode (7.61 -10 -3 cm 2) using a P-5827M potentiostat. A graphite rod was used as the auxiliary, electrode and Ag/0.1 N AgNO 3 was used as the reference electrode.The coulometric measurements and microelectrolysis were carried out in the same cell. A platinum plate (2 cm 2) was used as the working electrode, but the polarization curves were recorded in the course of electrolysis using a rotating disk Pt electrode.The preparative electrolysis was performed ma sealed cell analogous to that described above (but of a la~er volume). A Pt plate (28 cnt 2) was used as the anode. The auxiliary and r:efei'ence ek/~:frodes were the san'ie as those used in the voltammetric measurements.A 0.1 N Bu4NCIO 4 solution in anhydrous MeCN was used as the supporting electrolyte in the voltammetric measurements and in the electrolysis. The working solution was deaerated with argon before the polarization curves were recorded and the electrolysis was performed.Dehydration of MeCN was performed by distillation over P205 (five times) followed by distillation over calcined K2CO 3.Methyl-, ethyl-, and isopropylnitramines were prepared according to procedures reported previously, z,3 Tetrabutylammonium salts of the above-mentioned nitramines were prepared by adding an equimolar amount of KOH to their methanolic solutions followed by cation exchange upon addition of the calculated amount of tetrabutylammonium perchlorate. The alkali salts were precipitated with acetone, the filtrates were concentrated in vacuo, and the residues were recrystatlized from organic solvents. 4-Amino-3-methoxyfurazan was prepared according to a known procedure. 't A proc...

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Chemical and electrochemical activation of the nitration of naphthalene by N2O3 in aprotic media

Brémard

Wartel

1988

Electrochimica Acta

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Influence of the medium on the ionic dissociation of N2O4 and the kinetics of decomposition of N2O3 in aprotic solvents

Cited by 12 publications

References 25 publications

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

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

Electrooxidation of primary nitramine anions on platinum in MeCN

Chemical and electrochemical activation of the nitration of naphthalene by N2O3 in aprotic media

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