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: 2005-05-09 ; last change in preferred values: 2005-05-09 ; last peer-reviewed publication: 2006-09-06


CH3O2 + NO2 + MCH3O2NO2 + M(1) Δ Hο = -92.7 kJ mol-1

Rate Coefficient Data: Low-pressure rate coefficients

Absolute Rate Coefficients

Rate Coefficient (k0) / Temperature / ReferenceTechniques and Comments
cm3molecule-1s-1Kelvin
(2.33 ± 0.08) × 10 -30 [N 2 ]298Sander and Watson, 1980FP-AS (a)
2.2 × 10 -30 (T/300) -2.5 [N 2 ]253–353Ravishankara et al., 1980FP-AS (b)
(1.46 ± 0.50) × 10 -30 [SF 6 ]295Wallington et al., 1999PR-AS (c)

Comments

(a) Pressure range 70 mbar to 900 mbar for the bath gases He, N 2 , and SF 6 . Analysis of the falloff curve was carried out with a theoretical F c value of 0.39, in good agreement with the fitted value of F c =0.4±0.10.

(b) Pressure range 100 mbar to 950 mbar. Analyses of the falloff curves at 253 K, 298 K and 353 K were carried out with F c =0.4 independent of temperature.

(c) Pulse radiolysis study in 0.5–14 bar of SF 6 . Evaluating the falloff curve with F c =0.40.

Preferred Values

k0cm3molecule-1s-1{2.6-30 N_2[N2] 2.6×10-30±0.3 N_2[N2]   if   T 298 2.5-30 T 300 PlusMinus -5.5 1 N_2[N2]2.5×10-30 (T/ 300 )( -5.5 ±1) N_2[N2]  if   250 T 350

Comments on Preferred Values

The preferred values are based on the results from Sander and Watson (1980) and the theoretical analysis from Destriau and Troe (1990). These values are based on a theoretically determined value of F c =0.36 at 300 K.

Rate Coefficient Data: High-pressure rate coefficients

Absolute Rate Coefficients

Rate Coefficient (k) / Temperature / ReferenceTechniques and Comments
cm3molecule-1s-1Kelvin
(8.0 ± 1.0) × 10 -12 298Sander and Watson, 1980FP-AS (a)
7 × 10 -12 (T/298) -3.5 253–353Ravishankara et al., 1980FP-AS (b)
(1.8 ± 0.25) × 10 -11 295Wallington et al., 1999PR-AS (c)

Comments

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

(b) See comment (b) for k 0 . The large negative temperature coefficient is probably an artifact of the interpretation. If a larger negative temperature exponent for k 0 and a smaller F c value at higher temperature are used, the large negative temperature exponent of k will decrease.

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

Preferred Values

kcm3molecule-1s-14.0-124.0×10-12  if   T 298   and   P 1 bar of air kcm3molecule-1s-1{1.8-111.8×10-11±0.3  if   T 298 T30001.8×10-11(T/300)0exp  if   250 T 350

Comments on Preferred Values

The preferred values are based on the high pressure study from Wallington et al. (1999). An experimental value of F c =0.36 at 298 K appears well established. Less complete information on the falloff range is obtained from the experiments by Cox and Tyndall (1980), who measured k=1.6×10 -12 cm 3 molecule -1 s -1 at 700 mbar of N 2 and 1.2×10 -12 cm 3 molecule -1 s -1 at 66 mbar of Ar at 275 K, and Bridier et al. (1992) who measured k=(4.4±0.4)×10 -12 cm 3 molecule -1 s -1 at 298 K in 1 bar of air. The apparent observation of a pressure independent rate coefficient k over the range 66 mbar to 760 mbar of Ar reported by Adachi and Basco (1980) is not confirmed by Sander and Watson (1980) and Ravishankara et al. (1980). ΔH is taken from the equilibrium measurements of Bridier et al. (1992).

References

  • Adachi, H. and Basco, N. , Int. J. Chem. Kinet. , 12 , 1 , 1980.
  • Bridier, I., Lesclaux, R. and Veyret, B. , Chem. Phys. Lett. , 119 , 259 , 1992.
  • Cox, R. A. and Tyndall, G. S. , J. Chem. Soc. Faraday Trans. , 76 , 153 , 1980.
  • Destriau, M. and Troe, J. , Int. J. Chem. Kinet. , 22 , 915 , 1990.
  • Ravishankara, A. R., Eisele, F. L. and Wine, P. H. , J. Chem. Phys. , 73 , 3743 , 1980.
  • Sander, S. P. and Watson, R. T. , J. Phys. Chem. , 84 , 1664 , 1980.
  • Wallington, T. J., Nielsen, O. J. and Sehested, K. , Chem. Phys. Lett. , 313 , 456 , 1999.