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: 2005-12-05 ; last change in preferred values: 2005-12-05 ; last peer-reviewed publication: 2006-09-06


HO + C3H6 + MC3H6OH + M(1) Δ Hο = -134 kJ mol-1

Rate Coefficient Data: Low-pressure rate coefficients

Absolute Rate Coefficients

Rate Coefficient (k0) / Temperature / ReferenceTechniques and Comments
cm3molecule-1s-1Kelvin
8 × 10 -28 [Ar]298Zellner and Lorenz, 1983PLP-RF (a)
9 × 10 -27 [N 2 ]298Vakhtin et al., 2003PLP-LIF (b)

Relative Rate Coefficients

Rate Coefficient (k0) / Temperature / ReferenceTechniques and Comments
cm3molecule-1s-1Kelvin
8 × 10 -27 [Ar]298Klein et al., 1984(c)
8 × 10 -27 [air]

Comments

(a) Pressure range 1.3 mbar to 170 mbar. Falloff behavior detected, and evaluated with F c =0.8. Rough estimate of k 0 because of the only limited extent of observed falloff.

(b) Experiments with pulsed Laval nozzle supersonic expansion over the range 2 × 10 -16 [N 2 ] 3 × 10 18 molecule cm -3 at 296 K. Single experiments at (2–3) × 10 16 molecule cm -3 of N 2 were also carried out at 96, 103, and 165 K. Rough estimate of k 0 because of limited extent of observed falloff. Falloff curves constructed with F c = 0.5 and k (296 K) = 2.6 × 10 -11 cm 3 molecule -1 s -1 . See also comment (d) for k .

(c) HO 2 NO 2 -NO system used as source of HO radicals. Reaction studied relative to HO + n-hexane, with the latter reaction calibrated against absolute measurements of the reaction HO + n-butane (k=2.53×10 -12 cm 3 molecule -1 s -1 at 295 K). Pressure range 1.3 mbar to 1000 mbar; falloff effects could be detected. Evaluation with F c =0.5 gives the present k 0 value. Rough estimate of k 0 because of the only limited extent of observed falloff.

Preferred Values

k0cm3molecule-1s-1{8.2-27 N_2[N2] 8.2×10-27±1.0 N_2[N2]   if   T 298 8-27 T 300 PlusMinus -3.5 1 N_2[N2]8×10-27 (T/ 300 )( -3.5 ±1) N_2[N2]  if   200 T 300

Comments on Preferred Values

The uncertainty of the extrapolated k 0 is large, because the reaction is close to the high-pressure limit at the pressures studied. The preferred values follow the falloff extrapolation from Klein et al. (1984) which shows the smallest scatter. Falloff extrapolations are made using F c =0.5 at 300 K. The temperature coefficient of k 0 is estimated by analogy to the reaction HO+C 2 H 4 +MC 2 H 4 OH+M.

Rate Coefficient Data: High-pressure rate coefficients

Absolute Rate Coefficients

Rate Coefficient (k) / Temperature / ReferenceTechniques and Comments
cm3molecule-1s-1Kelvin
(3.0±0.5) × 10 -11 298Zellner and Lorenz, 1984PLP-RF (a)
(8.1±1.8) × 10 -11 103Vakhtin et al., 2001(b)
(2.95±0.10) × 10 -11 (T/300) -1.06 96-296Vakhtin et al., 2003PLP-LIF (c)

Relative Rate Coefficients

Rate Coefficient (k) / Temperature / ReferenceTechniques and Comments
cm3molecule-1s-1Kelvin
(3.0±0.2) × 10 -11 295Klein et al., 1984(d)

Comments

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

(b) Pulsed Laval nozzle supersonic expansion of nitrogen with admixed reactants. HO generated by photolysis of H 2 O 2 [N 2 ]=2.1×10 16 molecule cm -3 . Reaction observed very close to the high pressure limit.

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

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

Preferred Values

kcm3molecule-1s-12.9-112.9×10-11  if   T 298   and   P 1 bar of air kcm3molecule-1s-1{3.0-113.0×10-11±0.1  if   T 298 3.0-11 T 300 PlusMinus -1 13.0×10-11 (T/ 300 )( -1 ±1)  if   200 T 300

Comments on Preferred Values

The preferred values are based on Zellner and Lorenz (1984), Klein et al. (1984), Vakhtin et al. (2003), Nielsen et al. (1990) and Tully and Goldsmith (1985). There is an uncertainty about the extent of falloff at temperatures above 300 K and there is the possibility of a small activation barrier, such as observed in the reaction HO+C 2 H 2 +MC 2 H 2 OH+M. The preferred temperature dependence is derived by combining the results from Zellner and Lorenz (1984), Klein et al. (1984) and Vakhtin et al. (2003), confirming the suggestions from Atkinson (1994) and Tsang (1991). F c =0.5 serves for estimating the extent of falloff.

References

  • Atkinson, R. , J. Phys. Chem. Ref. Data Monograph , 2 , 1 , 1994.
  • Klein, Th., Barnes, I., Becker, K. H., Fink, E. H. and Zabel, F. , J. Phys. Chem. , 88 , 5020 , 1984.
  • Nielsen, O. J., Jørgensen, O., Donlon, M., Sidebottom, H. W., O'Farrell, D. J. and Treacy, J. , Chem. Phys. Lett , 168 , 319 , 1990.
  • Tsang, W. , J. Phys. Chem. Ref. Data , 20 , 221 , 1991.
  • Tully, F. P. and Goldsmith, J. E. M. , Chem. Phys. Lett. , 116 , 345 , 1985.
  • Vakhtin, A. B., Lee, S., Heard, D. E., Smith, I. W. M. and Leone, S. R. , J. Phys. Chem. A , 105 , 7889 , 2001.
  • Vakhtin, A. B., Murphy, J. E. and Leone, S. R. , J. Phys. Chem. A , 107 , 10055 , 2003.
  • Zellner, R. and Lorenz, K. , J. Phys. Chem. , 88 , 984 , 1984.