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 + C2H4 + MC2H4OH + M(1) Δ Hο = -23 kJ mol-1

Rate Coefficient Data: Low-pressure rate coefficients

Absolute Rate Coefficients

Rate Coefficient (k0) / Temperature / ReferenceTechniques and Comments
cm3molecule-1s-1Kelvin
5.5 × 10 -29 [Ar]296Zellner and Lorenz, 1984PLP-RF (a)
(6.1±1.2) × 10 -29 [N 2 ]300Kuo and Lee, 1991DF-RF (b)
(5.2±1.1) × 10 -29 [O 2 ]300
4.1 × 10 -29 (T/300) -3.4 [He]300–800Fulle et al., 1997PLP-LIF (c)
(2.8±0.1) × 10 -29 (T/300) -3.5 [He]300–423Chuong and Stevens, 2000DF-LIF (d)
(11.6±1.8) × 10 -29 [N 2 ]296Vakhtin et al., 2003PLP-LIF (e)

Relative Rate Coefficients

Rate Coefficient (k0) / Temperature / ReferenceTechniques and Comments
cm3molecule-1s-1Kelvin
(9.5 -2.4 +3.2 ) × 10 -29 [air]295Klein et al., 1984RR (f)
(5.9 -1.0 +3.0 ) × 10 -29 [Ar]295

Comments

(a) Pressure range 4 mbar to 130 mbar, temperature range 296 K to 524 K. Falloff extrapolation using F c =0.8.

(b) Pressure range 0.4 mbar to 66 mbar. HO radicals were generated by reaction of H atoms with excess NO 2 . Data extrapolated using F c =0.7.

(c) The pressure was varied between 1 mbar and 150 bar. Falloff curves were also constructed using earlier rate data with a calculated F c =0.21 exp(-220/T)+exp(-T/305) and F c (300)=0.47. The value ΔH (0 K)=-(123±6) kJ mol -1 was derived from a third-law analysis of the equilibrium constant K c for which K c =2.1×10 -2 T -0.95 exp(14 780/T) bar -1 was obtained from measurements performed at 646–803 K and He pressures up to 140 bar.

(d) Pressure range 2.6 mbar to 8 mbar. Falloff extrapolation using F c =0.6 and k =1.96×10 -12 exp(438/T) cm 3 molecule -1 s -1 from Klein et al. (1984). Differences to the results from Fulle et al. (1997) due to the use of a larger F c .

(e) Experiments with pulsed Laval nozzle supersonic expansion over the range 2 × 10 16 [N 2 ] 3 × 10 18 cm 3 molecule -1 s -1 at 296 K. Single experiments at (2–3) × 10 16 cm 3 molecule -1 s -1 also at 96, 110, and 165 K. Falloff extrapolation with F c = 0.65 and k (296 K) = 7.5 × 10 -12 cm 3 molecule -1 s -1 .

(f) HO 2 NO 2 -NO system used as source of HO radicals. Reaction of HO radicals with C 2 H 4 was studied in 420 L glass reactor relative to HO + n-hexane where the latter reaction was calibrated against absolute measurements of the reaction HO + n-butane [k(295 K)=2.53×10 -12 cm 3 molecule -1 s -1 ]. Pressure range 1.3–1000 mbar, falloff curves constructed with F c =0.7.

Preferred Values

k0cm3molecule-1s-1{8.8-29 N_2[N2] 8.8×10-29±0.3 N_2[N2]   if   T 298 8.6-29 T 300 PlusMinus -3.1 2 N_2[N2]8.6×10-29 (T/ 300 )( -3.1 ±2) N_2[N2]  if   200 T 300

Comments on Preferred Values

Preferred values are based on an average of the data from Zellner and Lorenz (1984), Kuo and Lee (1991), Fulle et al. (1997), Chuong and Stevens (2000), Klein et al. (1984), Atkinson (1994), Tully (1983), Davis et al. (1975), Howard (1976), Greiner (1970), Morris et al. (1971), Overend and Paraskevopoulos (1977), Atkinson et al. (1977), Lloyd et al. (1976), Cox (1975) and Vakhtin et al. (2003), where the latter work showed the lowest scatter and, therefore, is given the highest weight. Falloff curves are constructed with the calculated F c =0.48 from Fulle et al. (1997).

Rate Coefficient Data: High-pressure rate coefficients

Absolute Rate Coefficients

Rate Coefficient (k) / Temperature / ReferenceTechniques and Comments
cm3molecule-1s-1Kelvin
(8.47±0.24) × 10 -12 291Tully, 1993PLP-LIF (a)
3.3 × 10 -12 exp[(320 ± 150)/T]296–524Zellner and Lorenz, 1984PLP-RF (b)
9.7 × 10 -12 298
(9.4±1.6) × 10 -12 298Nielsen et al., 1990(c)
(7.7±1.0) × 10 -12 298Becker et al., 1991PLP-LIF (d)
1.0 × 10 -11 300–800Fulle et al., 1997PLP-LIF (e)
(8.7 ± 0.7) × 10 -12 (T/300) -0.85 96–296Vakhtin et al., 2003PLP-LIF (f)

Relative Rate Coefficients

Rate Coefficient (k) / Temperature / ReferenceTechniques and Comments
cm3molecule-1s-1Kelvin
(7.84±0.35) × 10 -12 299±2Atkinson et al., 1982RR (g)
(8.5 ±0.6) × 10 -12 295Klein et al., 1984RR (h)

Comments

(a) Higher end of falloff curve at 66 mbar to 790 mbar; temperature range 291–591 K.

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

(c) Pulse radiolysis of H 2 O-Ar mixtures. HO monitored by UV absorption at 309 nm. Rate coefficient determined at a total pressure of 1 bar.

(d) Experiments were carried out at a total pressure of 1 bar of synthetic air. Numerical simulation with a mechanism of 12 reactions.

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

(f) See comment (e) for k 0 .

(g) HO radicals were generated by photolysis of CH 3 ONO in presence of air containing NO. Concentrations of ethene and cyclohexane (the reference compound) were measured by GC. The rate coefficient ratio of k(HO + ethene)/k(HO + cyclohexane) = 1.12±0.05 is placed on an absolute basis by use of a rate coefficient of k(HO + cyclohexane) = 7.00 ×10 -12 cm 3 molecule -1 s -1 (Atkinson, 2003).

(h) See comment (e) for k 0 .

Preferred Values

kcm3molecule-1s-17.9-127.9×10-12  if   T 298   and   P 1 bar of air kcm3molecule-1s-1{9.1-129.1×10-12±0.3  if   T 298 9.0-12 T 300 PlusMinus -0.85 0.39.0×10-12 (T/ 300 )( -0.85 ±0.3)  if   100 T 500

Comments on Preferred Values

The preferred value is from Vakhtin et al. (2003), being similar to those selected in Fulle et al. (1997), Lloyd et al. (1976) and Nielsen et al. (1990). Falloff curves should be calculated with the theoretical expression for F 0 = 0.48 which probably applies to M = He as well as N 2 and is practically constant over the indicated temperature range.

References

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  • Atkinson, R. , Atmos. Chem. Phys. , 3 , 2233 , 2003.
  • Atkinson, R., Perry, R. A. and Pitts Jr., J. N. , J. Chem. Phys. , 66 , 1197 , 1977.
  • Atkinson, R., Aschmann, S. M., Winer, A. M. and Pitts Jr., J. N. , Int. J. Chem. Kinet. , 14 , 507 , 1982.
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  • Chuong, B. and Stevens, P. S. , J. Phys. Chem. A , 104 , 5230 , 2000.
  • Cox, R. A. , Int. J. Chem. Kinet. Symp. , 1 , 379 , 1975.
  • Davis, D. D., Fischer, S., Schiff, R., Watson, R. T. and Bollinger, W. , J. Chem. Phys. , 63 , 1707 , 1975.
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  • Klein, Th., Barnes, I., Becker, K. H., Fink, E. H. and Zabel, F. , J. Phys. Chem. , 88 , 5020 , 1984.
  • Kuo, C.-H. and Lee, Y.-P. , J. Phys. Chem. , 95 , 1253 , 1991.
  • Lloyd, A. C., Darnall, K. R., Winer, A. M. and Pitts Jr., J. N. , J. Phys. Chem. , 80 , 789 , 1976.
  • Morris Jr., E. D., Stedman, D. H. and Niki, H. , J. Am. Chem. Soc. , 93 , 3570 , 1971.
  • Nielsen, O. J., Jørgensen, O., Donlon, M., Sidebottom, H. W., O'Farrell, D. J. and Treacy, J. , Chem. Phys. Lett. , 168 , 319 , 1990.
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  • Vakhtin, A. B., Murphy, J. E. and Leone, S. R. , J. Phys. Chem. , 88 , 984 , 1984.