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


CH3C(O)O2 + NO2 + MCH3C(O)O2NO2 + M(1) Δ Hο = -119 kJ mol-1

Rate Coefficient Data: Low-pressure rate coefficients

Absolute Rate Coefficients

Rate Coefficient (k0) / Temperature / ReferenceTechniques and Comments
cm3molecule-1s-1Kelvin
5.1 × 10 -29 [N 2 ]298Basco and Parmar, 1987FP-AS (a)
(2.7 ± 1.5) × 10 -28 (T/298) -7.1 [air]248–393Bridier et al., 1991FP-AS (b)

Comments

(a) Photolysis of Cl 2 -CH 3 CHO-O 2 -N 2 and NO 2 at total pressures of 100 mbar to 800 mbar. Extrapolation of falloff curve with theoretically modeled value of F c =0.19.

(b) The falloff curves were fitted using F c =0.30. The discrepancy with the data of Basco and Parmar (1987) is attributed to an oversimplified kinetic scheme used in Basco and Parmar (1987).

Preferred Values

k0cm3molecule-1s-1{2.8-28 N_2[N2] 2.8×10-28±0.4 N_2[N2]   if   T 298 2.7-28 T 300 PlusMinus -7.1 2 N_2[N2]2.7×10-28 (T/ 300 )( -7.1 ±2) N_2[N2]  if   250 T 300

Comments on Preferred Values

The data from Basco and Parmar (1987) and Addison et al. (1980) are a factor of 2–3 lower than those from Bridier et al. (1991). The more extensive and internally consistent study of CH 3 C(O)OONO 2 (PAN) formation and dissociation in Bridier et al. (1991) is preferred. Falloff extrapolations were performed with a modeled value of F c =0.3.

Rate Coefficient Data: High-pressure rate coefficients

Absolute Rate Coefficients

Rate Coefficient (k) / Temperature / ReferenceTechniques and Comments
cm3molecule-1s-1Kelvin
6.1 × 10 -12 298Basco and Parmar, 1987FP-AS (a)
(1.21 ± 0.05) × 10 -11 (T/298) -0.9 248–393Bridier et al., 1991FP-AS (b)
(1.0 ± 0.2) × 10 -11 (0.93 bar)295Sehested et al., 1998PR-A (c)

Comments

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

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

(c) CH 3 C(O)O 2 radicals were generated from the pulsed radiolysis of CH 3 CHO-O 2 -CO 2 -NO 2 and CH 3 CHO-SF 6 -O 2 -NO 2 mixtures and the disappearance rate of NO 2 monitored by absorption at 400.5 and 452 nm.

Preferred Values

kcm3molecule-1s-11.0-111.0×10-11  if   T 298   and   P 1 bar of air kcm3molecule-1s-1{1.2-111.2×10-11±0.2  if   T 298 1.2-11 T 300 PlusMinus -0.9 11.2×10-11 (T/ 300 )( -0.9 ±1)  if   250 T 300

Comments on Preferred Values

See comments on k 0 . The measurement of Sehested et al. (1998) is in very good agreement with the results from Bridier et al. (1991) which form the basis of the preferred value.

References

  • Addison, M. C., Burrows, J. P., Cox, R. A. and Patrick, R. , Chem. Phys. Lett. , 73 , 283 , 1980.
  • Basco, N. and Parmar, S. S. , Int. J. Chem. Kinet. , 19 , 115 , 1987.
  • Bridier, I., Caralp, F., Loirat, H., Lesclaux, R., Veyret, B., Becker, K. H., Reimer, A. and Zabel, F. , J. Phys. Chem. , 95 , 3594 , 1991.
  • Sehested, J., Christensen, L. K., Møgelberg, T., Nielsen, O. J., Wallington, T. J., Guschin, A., Orlando, J. J. and Tyndall, G. S. , J. Phys. Chem. A , 102 , 1779 , 1998.