Thermal Decomposition of Nitryl Chloride. I. Second-order Unimolecular Rate Study

Cordes, Herman F.; Johnston, Herrick L.

doi:10.1021/ja01646a003

Cited by 26 publications

(12 citation statements)

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“…This value is therefore in good agreement with that reported by us in a recent work [221: k*(sulf.) = 7.8 X lo4 t 2.0 x lo4 dm3 mo1-l s-l at 303 K (within the limits of error which are not negligible), and close enough t o t h a t found in gas medium: k*(gas) = 1.78 * 0.80 x lo4 dm3 mol-1 s-' at 298 K [21]. It is known that nitric oxide is weakly solvated in aprotic and inert solvents 116,231.…”

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

confidence: 75%

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: Mechanistic Study Of the First Nocl-reduction Step In Sulfosupporting

confidence: 75%

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 the temperature range of 400-500 K, our predicted values are slightly lower than those of Cordes and Johnston. [51] In the higher temperature range of 600-1300 K, our predicted results are slightly higher than the experimental values reported by Hiraoka and Hardwick. [52] The deviation may be ascribed to the uncertainties in both D 0 (ClNO 2 ) and experimental errors.…”

Section: Rate Constants For the Decomposition Of Clnocontrasting

confidence: 66%

Ab Initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO for the Forward and Reverse Processes

Zhu

Lin

2004

ChemPhysChem

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The mechanisms for ClO+NO and its reverse reactions were investigated by means of ab initio molecular orbital and statistical theory calculations. The species involved were optimized at the B3LYP/6-311 +G(3df) level, and their energies were refined at the CCSD(T)/6-311+ G(3df)//B3LYP/6-311 + G(3df) level. Five isomers and the transition states among them were located. The relative stability of these isomers is ClNO2 > cis-ClONO > trans-ClONO > cis-OClNO>trans-OClNO. The heats of formation of the three most-stable isomers were predicted using isodesmic reactions by different methods. The predicted bimolecular reaction rate constant shows that, below 100 atm, the formation of Cl+NO2 is dominant and pressure-independent. The total rate constant can be expressed as: k(ClO+NO)= 1.43 x 10(-9)T(-083)exp(92/ T) cm3 molecule(-1)s(-1) in the temperature range of 200-1000 K, in close agreement with experimental data. For the reverse reaction, Cl+NO2-->ClNO2 and ClONO (cis and trans isomers), the sum of the predicted rate constants for the formation of the three isomers and their relative yields also reproduce the experimental data well. The predicted total third-order rate constants in the temperature range of 200-1000 K can be represented by: k0(He) = 4.89 x 10(-6)T(-5.85) exp(-796/T) cm6 molecule(-1)s(-1) and k0(N2) =5.72 x 10(-15)T(-5.80) exp(-814/T) cm6 molecule(-1)s(-1). The predicted high- and low-pressure limit decomposition rates of CINO2 in Ar in the temperature range 400-1500 K can be expressed, respectively, by: k-(ClNO2) = 7.25 x 10(19)T(-1.89) exp(-16875/T) s(-1) and kd(ClNO2) = 2.51 x 10(38)T(-6.8) exp(-18409/T) cm3 molecule(-1) s(-1). The value of k0(ClNO2) is also in reasonable agreement with available experimental data.

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“…Chlorine atoms and nitrogen dioxide behave similarly; the second-order unimolecular decomposition of nitryl chloride proceeds by the exact reverse of the steps above (96) and the association…”

Section: Association With Atomsmentioning

confidence: 99%

The Reactivity And Structure Of Nitrogen Dioxide

Gray¹,

Yoffe²

1955

Chem. Rev.

131

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Thermal Decomposition of Nitryl Chloride. I. Second-order Unimolecular Rate Study

Cited by 26 publications

References 0 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

Ab Initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO for the Forward and Reverse Processes

The Reactivity And Structure Of Nitrogen Dioxide

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Thermal Decomposition of Nitryl Chloride. I. Second-order Unimolecular Rate Study

Cited by 26 publications

References 0 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

Ab Initio Studies of ClOx Reactions: Prediction of the Rate Constants of ClO+NO for the Forward and Reverse Processes

The Reactivity And Structure Of Nitrogen Dioxide

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Ab Initio Studies of ClO_x Reactions: Prediction of the Rate Constants of ClO+NO for the Forward and Reverse Processes