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


C2H5C(O)O2NO2 + MC2H5C(O)O2 + NO2 + M(1) Δ Hοnot given

Rate Coefficient Data: Low-pressure rate coefficients

Absolute Rate Coefficients

Rate Coefficient (k0) / Temperature / ReferenceTechniques and Comments
s-1Kelvin
1.7 × 10 -3 exp(-11280/T) [N 2 ]291–320Kirchner et al., 1999(a)

Comments

(a) Experiments in a 420 L reaction chamber with photolytic generation of radicals forming peroxynitrates. Decomposition of propionyl peroxynitrate followed in the dark by FTIR spectrometry. Experiments between 11.5 and 1013 mbar of N 2 . Falloff extrapolations with F c =0.36.

Preferred Values

k0s-1{6.2-20 N_2[N2] 6.2×10-20 ±0.5 N_2[N2]   if   T 298 1.7-3PlusMinus -112802000 T N_2[N2]1.7×10-3exp( -11280±2000)/T N_2[N2]  if   290 T 320

Comments on Preferred Values

The only available low pressure data from Kirchner et al. (1999) appear consistent with the more extensive data base for the high-pressure range. The falloff curve is constructed with F c =0.36.

Rate Coefficient Data: High-pressure rate coefficients

Absolute Rate Coefficients

Rate Coefficient (k/Rate Coefficient (k_infty/s-1) / Temperature / ReferenceTechniques and Comments
s-1Kelvin
2 × 10 15 exp (-12800/T)300–315Mineshos and Glavas, 1991(a)
4.4 × 10 -4 298*
8.3 × 10 16 exp(-13940/T)291–320Kirchner et al., 1999(b)
4.0 × 10 -4 298

Comments

(a) Thermal decomposition of propionyl peroxynitrate (PPN) in a 4.5 liter glass flask in the presence of 1 bar of N 2 . PPN and the products ethyl nitrate, NO 2 , and methyl nitrate were analyzed by GC at 323 K. In the presence of NO, ethyl nitrate was the major product observed.

(b) See comment (a) for k 0 . Limited data from earlier work are also considered.

Preferred Values

ks-13.6-43.6×10-4  if   T 298   and   P 1 bar of air ks-1{4.0-44.0×10-4±0.2  if   T 298 8.316PlusMinus -139401000 T8.3×1016exp( -13940±1000)/T  if   290 T 320

Comments on Preferred Values

The values from Kirchner et al. (1999) and Minoshos and Glavas (1991) are in good agreement.

References

  • Kirchner, F., Mayer-Figge, A., Zabel, F. and Becker, K. H. , Int. J. Chem. Kinet. , 31 , 127 , 1999.
  • Mineshos, G. and Glavas, S , React. Kinet. Catal. Lett. , 30 , 5 , 1991.