IUPAC Subcommittee on Gas Kinetic Data Evaluation

Providing evaluated kinetic data on the web since 1999.

IUPAC Subcommittee on Gas Kinetic Data Evaluation

Website: http://www.iupac-kinetic.ch.cam.ac.uk/ See website for latest evaluated data. Datasheets can be downloaded for personal use only and must not be retransmitted or disseminated either electronically or in hardcopy without explicit written permission.

This datasheet last evaluated: 2002-03-09 ; last change in preferred values: 2002-03-09 ; last peer-reviewed publication: 2004-03-09


N2O5 + MNO2 + NO3 + M(1) Δ Hο = 95.6 kJ mol-1

Rate Coefficient Data: Low-pressure rate coefficients

Absolute Rate Coefficients

Rate Coefficient (k0) / Temperature / ReferenceTechniques and Comments
s-1Kelvin
1.04×10 -3 (T/300) -3.5 exp(-11000/T) [N 2 ]253–384Cantrell et al., 1993(a)

Comments

(a) Thermal decomposition of N 2 O 5 in the presence of NO in N 2 . FTIR analysis of N 2 O 5 in a stainless steel cell equipped with multiple path optics. Falloff curves over the gas density 4.3×10 14 to 1.1×10 20 molecule cm -3 were analyzed using F c = [2.5 exp(-1950/T) + 0.9 exp(-T/430)] [F c (298 K) = 0.45]. In the analysis, data from Connell and Johnston (1979) and Viggiano et al. (1981) were also taken into account.

Preferred Values

k0s-1{1.2-19 N_2[N2] 1.2×10-19 ±0.2 N_2[N2]   if   T 298 1.3-3 T 300 -3.5 -11000 T N_2[N2]1.3×10-3 (T/ 300) -3.5 exp -11000 /T N_2[N2]  if   200 T 400

Comments on Preferred Values

The preferred values are based on the study of Cantrell et al. (1993), derived from the kinetic data. However, instead of F c = 0.45, the modeled value of F c = 0.35 independent of the temperature was used for extrapolation to the low pressure limit. The recombination and dissociation rate coefficients are internally consistent. At room temperature, the equilibrium constant K c = 2.3×10 -11 cm 3 molecule -1 compares well with the values from Hjorth et al. (1992) and Pritchard (1994).

Rate Coefficient Data: High-pressure rate coefficients

Absolute Rate Coefficients

Rate Coefficient (k) / Temperature / ReferenceTechniques and Comments
s-1Kelvin
6.22×10 14 (T/300) -0.2 exp(-11000/T)253–384Cantrell et al., 1993(a)

Comments

(a) See comment (a) for k 0 .

Preferred Values

ks-1{6.9-26.9×10-2±0.3  if   T 298 9.714 T 300 0.1 -11080 T9.7×1014 (T/ 300) 0.1 exp -11080 /T  if   200 T 300

Comments on Preferred Values

The preferred values are based on the evaluation of Malko and Troe (1982), which agrees well with the recent determination of Cantrell et al. (1993). For the equilibrium constant, see comments on preferred values for k 0 .

References

  • Cantrell, C. A., Shetter, R. E., Calvert, J. G., Tyndall, G. S. and Orlando, J. J. , J. Phys. Chem. , 97 , 9141 , 1993.
  • Connell, P. and Johnston, H. S. , Geophys. Res. Lett. , 6 , 553 , 1979.
  • Hjorth, J., Notholt, J. and Restelli, G. , Int. J. Chem. Kinet. , 24 , 51 , 1992.
  • Malko, M. W. and Troe, J. , Int. J. Chem. Kinet. , 14 , 399 , 1982.
  • Pritchard, H. O. , Int. J. Chem. Kinet. , 26 , 61 , 1994.
  • Viggiano, A. A., Davidson, J. A., Fehsenfeld, F. C. and Ferguson, E. E. , J. Chem. Phys. , 74 , 6113 , 1981.