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: 2005-01-12 ; last change in preferred values: 2005-01-12 ; last peer-reviewed publication: 2006-09-06


HO + COH + CO2 (1) Δ Hο = -102.3 kJ mol-1
HO + CO + MHOCO + M(2) Δ Hο = -114.6 kJ mol-1

Rate Coefficient Data

Absolute Rate Coefficients

Rate Coefficient (k) / Temperature / ReferenceTechniques and Comments
cm3molecule-1s-1Kelvin
k(P 0)
1.37 × 10 -13 300Greiner, 1969FP-RA
1.35 × 10 -13 300Stuhl and Niki, 1972FP-RF
1.66 × 10 -13 300Mulcahy and Smith, 1971DF-MS
1.33 × 10 -13 298Westenberg and deHaas, 1973DF-EPR
1.39 × 10 -13 298Smith and Zellner, 1973FP-RA
1.58 × 10 -13 298Davis et al., 1974FP-RF
1.56 × 10 -13 296Howard and Evenson, 1974DF-LMR
1.20 × 10 -13 298Trainor and von Rosenberg, 1974FP-RA
0.90 × 10 -13 298Gordon and Mulac, 1975PR-RA
1.54 × 10 -13 299Atkinson et al., 1977FP-RF (e)
1.63 × 10 -13 296Overend and Paraskevopoulos, 1977FP-RA
1.41 × 10 -13 299Perry et al., 1977FP-RF (g)
1.46 × 10 -13 300Biermann et al., 1978FP-RA (h)
1.50 × 10 -13 298Dreier and Wolfrum, 1981DF (i)
1.46 × 10 -13 298Husain et al., 1982FP-RF
1.28 × 10 -13 298Ravishankara and Thompson, 1983FP-RF (j)
1.50 × 10 -13 298Paraskevopoulos and Irwin, 1984FP-RA
1.58 × 10 -13 298Hofzumahaus and Stuhl, 1984FP-RA (k)
1.23 × 10 -13 298Jonah et al., 1984PR-RA (l)
0.88 × 10 -13 298Beno et al., 1985PR-RA (l)
1.47 × 10 -13 299Hynes et al., 1986PLP-LIF
1.50 × 10 -13 298Stacknik and Molina, 1988PLP-RA
1.26 × 10 -13 298Wahner and Zetsch, 1988PLP-A (m)
1.49 × 10 -13 298Brunning et al., 1988FP-LIF (n)
1.30 × 10 -13 298Forster et al., 1995PLP-LIF
1.53 × 10 -13 298Golden et al., 1998PLP-LIF
1.57 × 10 -13 220–400McCabe et al., 2001PLP-LIF
4lk/k(P 0) with [N 2 ] in molecule cm -3
1 + [N 2 ]/5.4 × 10 19 298Paraskevopoulos and Irwin, 1984FP-RA
1 + [N 2 ]/4.1 × 10 19 298Hofzumahaus and Stuhl, 1984FP-RA (o)
1 + [N 2 ]/4.8 × 10 19 298Hynes et al., 1986PLP-LIF
1 + [N 2 ]/4.6 × 10 19 298Wahner and Zetsch, 1988PLP-A (m)
1 + [N 2 ]/4.4 × 10 19 220–400McCabe et al., 2001PLP-LIF
1 + [N 2 ]/4.0 × 10 19 200–300Fulle et al., 1996PLP-LIF (p)

Comments

(a) Extrapolation for P0 with pressure dependence from Golden et al. (1998).

(b) Extrapolation for P0 with pressure dependence from Paraskevopoulos and Irwin (1984).

(c) Measurements at 100 Torr of He giving k=1.43×10 -13 cm 3 molecule -1 s -1 .

(d) Measurements at 760 Torr of Ar giving k=1.54×10 -13 cm 3 molecule -1 s -1 .

(e) No pressure dependence detected between 25 and 650 Torr of Ar. Value taken as indicated.

(f) Measurements at 50 Torr of He giving k=1.66×10 -13 cm 3 molecule -1 s -1 .

(g) Measurements at 25 Torr of SF 6 giving k=1.53×10 -13 cm 3 molecule -1 s -1 .

(h) Measurements at 25 Torr of N 2 giving k=1.51×10 -13 cm 3 molecule -1 s -1 .

(i) Measurements of CO 2 yields accounting for loss of HO by other reactions.

(j) Measurements at 100 Torr of Ar giving k=1.4×10 -13 cm 3 molecule -1 s -1 .

(k) Measurements at 760 Torr of N 2 giving k=2.3×10 -13 cm 3 molecule -1 s -1 .

(l) Measurements at 760 Torr of Ar giving k=2.1×10 -13 cm 3 molecule -1 s -1 .

(m) Measurements at 760 Torr of N 2 giving k=2.15×10 -13 cm 3 molecule -1 s -1 .

(n) Measurements at 25 Torr of Ar giving k=1.53×10 -13 cm 3 molecule -1 s -1 .

(o) Referred to k 0 =1.44×10 -13 cm 3 molecule -1 s -1 .

(p) Measurements up to 700 bar of He with data representation between 90 and 3000 K. Conversion to the bath gas N 2 with efficiency relative to He at 298 K, see comments on preferred values. Temperature dependence from theoretical modelling of the experimental results, see Troe (1998).

Preferred Values

kcm3molecule-1s-1{ 1.44 -13 1 N_2[N2] 4.219 1.44 ×10( -13 ±0.05){1+ N_2[N2] 4.2×1019}  if   T 298   and   P 0 to 1 bar of N_2 1.44 -13 1 N_2[N2] 4.219 1.44 ×10( -13 ±0.1){1+ N_2[N2] 4.2×1019}  if   200 T 300   and   P 0 to 1 bar of N_2

Comments on Preferred Values

The preferred values at P0 represent a weighted average of all low pressure data excluding pulse radiolysis results which show larger scatter. The preferred values at P=1 bar of N 2 correspond to an average over those results for which k/k(P 0) is given in the table (except the results from Fulle et al., 1996, which were obtained in the bath gas He).

The preferred values for k cannot be used over larger pressure and temperature ranges where more complicated expressions have to be employed. One may, e.g. take the representation k 1 =k 1,0 [1-[x/(x+1)]F c 1/[1+(logx) 2 ] ], k 2 =k 2,0 [1+y/(1+x)]F c 1/[1+(logx) 2 ] ] with x=k 2,0 /(k 2, -k 1.0 ) and y=k 1,0 /(k 2, -k 1.0 ), F c 0.7, k 1,0 =1.8×10 -12 exp(-2720/T) + 1.6×10 -13 exp(-60/T), k 2,0 =[He] 2.0×10 -32 (T/300) -2.7 exp(-490/T) and k 2, =1.8×10 -11 exp(-1850/T) + 1.5×10 -12 exp(-130/T), see Fulle et al. (1996) and Troe (1998). For N 2 instead of He, k 2,0 should be increased by a factor of 1.6. These expressions also give the partitioning of k into k 1 and k 2 . For the limited temperature and pressure range of the present evaluation, the simplified model from the introduction for complex-forming bimolecular reactions can be used. At low pressures this gives a relative HOCO yield of approximately [k-k(P0)]/[k(P)-k(P0)] which at 298 K and 1 bar of N 2 corresponds to about 12% (Troe, 1998). As HOCO under excess of O 2 rapidly reacts to HO 2 +CO 2 (Miyoshi et al., 1994) and as other reactions of HOCO presumably proceed similarly as reactions of H, k probably in effect can be used as if it would correspond to Reaction (1) alone. At higher temperatures, thermal decomposition of HOCO would occur which would lead to more complex kinetic rate laws, see Forster et al. (1996). This can be neglected at temperatures below 300 K.

The present evaluation was based on absolute rate coefficients only, neglecting relative rate measurements and measurements in other bath gases such as H 2 O. Reference to this work is found in the given literature. Since the reaction has been studied very extensively, the present evaluation also cannot be exhaustive. The thermochemistry of HOCO is based on the new determination by Feller et al. (2003). There is extensive modelling of the reaction, see Golden et al. (1998) and Troe (1998), which provide excellent representations of the experimental data with empirically fitted potential parameters. Increasingly reliable quantum-chemical determinations of the HOCO potential (see e.g. Yu et al., 2001 and Lakin et al., 2003) allows also for more basic treatments of the dynamics, see e.g. Medvedev et al. (2004), He et al. (2004), Valero and Kroes (2002), Valero et al. (2004). However, this work does not yet replace the experiments on which this evaluation is based.

References

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