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: 2003-06-12 ; last change in preferred values: 2003-06-12 ; last peer-reviewed publication: 2006-09-06


CH3O2NO2 + MCH3O2 + NO2 + 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
s-1Kelvin
9.0 × 10 -5 exp(-9694/T)[N 2 ]248–273Zabel et al., 1989(a)
6.7 × 10 -19 [N 2 ]298*

Comments

(a) Rate of decomposition of CH 3 O 2 NO 2 followed by FTIR spectroscopy after generation in a reaction chamber, with subsequent addition of NO to scavenge CH 3 O 2 radicals. Falloff curves were fitted with F c =0.4.

Preferred Values

k0s-1{6.8-19 N_2[N2] 6.8×10-19 ±0.3 N_2[N2]   if   T 298 9-5PlusMinus -9690500 T N_2[N2]9×10-5exp( -9690±500)/T N_2[N2]  if   250 T 300

Comments on Preferred Values

The preferred values correspond to the data and analysis from Zabel et al. (1989). A theoretical analysis of these data and those of the reverse reaction from Sander and Watson (1980) and Ravishankara et al. (1980) in Destriau and Troe (1990) gave an internally consistent picture (with ΔH = 88.5 kJ mol -1 ). Slightly lower limiting rate coefficients were obtained in Bridier et al. (1992) where a value of F c =0.6 was used. Direct measurements of the equilibrium constant K c =k/k 1 =2.73×10 -28 exp(10910/T) cm 3 molecule -1 from Bridier et al. (1992) lead to ΔH=92.7 kJ mol -1 and provide an indication for the internal consistency of the rate data.

Rate Coefficient Data: High-pressure rate coefficients

Absolute Rate Coefficients

Rate Coefficient (k) / Temperature / ReferenceTechniques and Comments
s-1Kelvin
2.1 × 10 16 exp(-10920/T)256–268Bahta et al., 1982(a)
2.6298*
1.1 × 10 16 exp(-10560/T)248–273Zabel et al., 1989(b)
4.5298*

Comments

(a) CH 3 O 2 NO 2 generated by photolysis of Cl 2 in the presence of NO 2 , CH 4 and O 2 . Kinetics were monitored in the presence of NO by UV absorption at 250 nm. At 460 mbar, k=6×10 15 exp(-10620/T) s -1 . The given value of k is derived with F c =0.6. The data depend to some extent on the rate coefficient for the reaction CH 3 O 2 +NOCH 3 O+NO 2 .

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

Preferred Values

ks-1 1.8 1.8   if   T 298   and   P 1 bar of air ks-1{ 4.5 ×10±0.3  if   T 298 1.116PlusMinus -10560500 T1.1×1016exp( -10560±500)/T  if   250 T 300

Comments on Preferred Values

See comments on preferred values of k 0 .

References

  • Bahta, A., Simonaitis, R. and Heicklen, J. , J. Phys. Chem. , 86 , 1849 , 1982.
  • Bridier, I., Lesclaux, R. and Veyret, B. , Chem. Phys. Lett. , 191 , 259 , 1992.
  • 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.
  • Zabel, F., Reimer, A., Becker, K. H., and Fink, E. H. , J. Phys. Chem. , 93 , 5500 , 1989.