SUPPLEMENTARY MATERIAL
Chemical reaction system used for the modelling of NOx-Air experiments. Rate constants are
taken from Atkinson et al., 2004, Atkinson et al., 2006, Atkinson et al., 2007
Reaction
NO2 → NO + O3P
Rate constante/unit/Status
J1 /s-1/ adjusted
O 3 → O 1D + O 2
J2 /s-1/ calculated from J1 value
HONO → OH + NO
J3 /s-1/ calculated from J1 value
HNO3 → OH + NO2
J4 /s-1/ calculated from J1 value
O 3 → O 3P + O 2
J5 /s-1/ calculated from J1 value
NO3 → NO2 + O3P
J6 /s-1/ calculated from J1 value
NO3 → NO + O2
J7 /s-1/ calculated from J1 value
O 2 + O 3P + M → O 3 + M
6.0×10-34 /cm6 molec-2 s-1
O 3 + O 3P → O 2 + O 2
8.0×10-15 /cm3 molec-1 s-1
NO2 + O3P → NO + O2
1.0×10-11 /cm3 molec-1 s-1
NO + NO + O2 → NO2 + NO2
2.0×10-38/cm6 molec-2 s-1
NO + O3 → NO2 + O2
1.8×10-14 /cm3 molec-1 s-1
NO2 + O3 → NO3 + O2
3.5×10-17 /cm3 molec-1 s-1
NO + NO3 → NO2 + NO2
2.6×10-11 /cm3 molec-1 s-1
O1D + M → O3P + M
2.6×10-11 /cm3 molec-1 s-1
OH + HNO3 → H2O + NO3
1.5×10-13 /cm3 molec-1 s-1
OH + HONO → H2O + NO2
6.0×10-12 /cm3 molec-1 s-1
OH + CO → CO2 + HO2
2.8×10-13 /cm3 molec-1 s-1
OH + O3 → HO2 + O3
7.3×10-14 /cm3 molec-1 s-1
HO2 + OH → H2O + O2
1.1×10-10 /cm3 molec-1 s-1
HO2 + HO2 → H2O2 + O2
1.6×10-12 /cm3 molec-1 s-1
HO2 + O3 → OH + O2 + O2
2.0×10-15 /cm3 molec-1 s-1
HO2 + NO → NO2 + OH
8.8×10-12 /cm3 molec-1 s-1
HO2 + NO → HNO3
1.6×10-14 /cm3 molec-1 s-1
H2O + N2O5 → HNO3 + HNO3
2.5×10-22 /cm3 molec-1 s-1
H2 + OH → H2O + HO2
6.7×10-15 /cm3 molec-1 s-1
HO2NO2 → HO2 + NO2
1.8×10-1 /s-1
NO + O3P → NO2
2.3×10-12 /cm3 molec-1 s-1/ recalculated from 3rd order equation
NO2 + O3P→ NO3
2.9×10-12 /cm3 molec-1 s-1/ recalculated from 3rd order equation
OH + NO2 → HNO3
1.0×10-11 /cm3 molec-1 s-1/ recalculated from 3rd order equation
OH + NO → HONO
8.3×10-12 /cm3 molec-1 s-1/ recalculated from 3rd order equation
H + O2 → HO2
1.4×10-12 /cm3 molec-1 s-1/ recalculated from 3rd order equation
HO2 + NO2 → HO2NO2
1.2×10-12 /cm3 molec-1 s-1/ recalculated from 3rd order equation
NO2 + NO3 → N2O5
2.1×10-12 /cm3 molec-1 s-1/ recalculated from 3rd order equation
N2O5 → NO2 + NO3
7.7×10-2 / s-1/ recalculated from 2nd order equation
O1D + H2O → OH + OH
2.2×10-10 /cm3 molec-1 s-1/ recalculated from 3rd order equation
6.0x1012
15.0x1012
5.0x1012
9.0x1012
3.0x1012
6.0x1012
2.0x1012
C3H6 (OBS)
C3H6 (MODEL)
NO (OBS)
NO (MODEL)
1.0x1012
0.0
3.0x1012
0.0
6.0x1012
6.0x1012
4.0x1012
3.0x1012
3.0x1012
2.0x1012
2.0x1012
1.0x1012
1012
0.0
1013
0
8.0x1012
HCHO (OBS)
HCHO (MODEL)
8.0x1012
CH3CHO (OBS)
CH3CHO (MODEL)
6.0x1012
6.0x1012
4.0x1012
4.0x1012
2.0x1012
2.0x1012
0
6.0x1011
0
2.1x1012
HCOOH (OBS)
HCOOH (MODEL)
5.0x1011
(molecule.cm-3)
(molecule.cm-3)
4.0x1012
[O3]
5.0x1012
PAN (OBS)
PAN (MODEL)
1.8x1012
1.5x1012
4.0x1011
1.2x1012
3.0x1011
9.0x1011
2.0x1011
6.0x1011
11
10
3.0x1011
0
0
0
1000
2000
3000
Time (second)
4000
5000 0
1000
2000
3000
4000
5000
Time (second)
Comparison of simulated (solid lines) and experimental concentrations (symbols) for NO,
NO2, ozone, propene, formaldehyde, acetaldehyde, formic acid and peroxyacetyl nitrate
(PAN) in a propene-NOx-Air system (experiment # H0721)
(molecule.cm-3)
[NO2]
(molecule.cm-3)
(molecule.cm-3)
[HCHO]
O3 (OBS)
O3 (MODEL)
[CH3CHO]
(molecule.cm-3)
NO2 (OBS)
NO2 (MODEL)
5.0x1012
[HCOOH]
[C3H6]
12.0x1012
4.0x1012
(molecule.cm-3)
18.0x1012
[PAN]
(molecule.cm-3)
[NO]
7.0x1012
2.0x1012
500.0x109
NO2 (OBS)
NO2 (MODEL)
0.0
1.2x1012
O3 (OBS)
O3 (MODEL)
9.0x1011
6.0x1011
6.0x1011
11
4.0x10
3.0x1011
2.0x1011
0
2.1x1012
0
1.6x1012
[HCHO]
(molecule.cm-3)
(molecule.cm-3)
[HCOOH]
1.4x1012
CH3CHO (OBS)
CH3CHO (MODEL)
1.5x1012
1.2x1012
1012
1.2x1012
8.0x1011
9.0x1011
6.0x1011
6.0x1011
4.0x1011
3.0x1011
2.0x1011
0
1012
0
100x109
HCOOH (OBS)
HCOOH (MODEL)
8.0x1011
PAN (OBS)
PAN (MODEL)
[CH3CHO]
(molecule.cm-3)
HCHO (OBS)
HCHO (MODEL)
1.8x1012
80x109
6.0x1011
60x109
4.0x1011
40x109
2.0x1011
20x109
0
(molecule.cm-3)
(molecule.cm-3)
[NO2]
0.0
1012
8.0x1011
1.0x1012
C3H6 (OBS)
C3H6 (MODEL)
NO (OBS)
NO (MODEL)
(molecule.cm-3)
1.0x1012
[C3H6]
3.0x1012
(molecule.cm-3)
1.5x1012
[O3]
4.0x1012
[PAN]
(molecule.cm-3)
[NO]
2.0x1012
0
0
1000
2000
3000
Time (second)
4000
5000 0
1000
2000
3000
4000
5000
Time (second)
Comparison of simulated (solid lines) and experimental concentrations (symbols) for NO,
NO2, ozone, propene, formaldehyde, acetaldehyde, formic acid and peroxyacetyl nitrate
(PAN) in a propene-NOx-Air system (experiment # N0220). Black lines are the results of
modeling with an initial concentration of nitrous acid [HONO]0 = 2 ppb while continuous red
lines are for [HONO]0 = 3 ppb and dashed red lines for [HONO]0 = 1 ppb.
3.0x1012
3.0x1012
2.0x1012
2.0x1012
NO (OBS)
NO (MODEL)
1.0x1012
0.0
5.0x1012
NO2 (OBS)
NO2 (MODEL)
1.0x1012
O3 (OBS)
O3 (MODEL)
3.0x1011
0.0
3.5x1011
2.5x1011
3.0x1012
2.0x1011
2.0x1012
1.5x1011
1011
12
5.0x1010
0.0
2.0x1012
1.8x1012
1.6x1012
1.4x1012
1.2x1012
1012
8.0x1011
6.0x1011
4.0x1011
2.0x1011
0
2.5x109
HCHO (OBS)
HCHO (MODEL)
CH3CHO (OBS)
CH3CHO (MODEL)
HCOOH (OBS)
HCOOH (MODEL)
2.0x109
0
1.8x1012
1.6x1012
1.4x1012
1.2x1012
1012
8.0x1011
6.0x1011
4.0x1011
2.0x1011
0
5.0x1010
PAN (OBS)
PAN (MODEL)
[CH3CHO]
(molecule.cm-3)
[HCHO]
[HCOOH]
(molecule.cm-3)
(molecule.cm-3)
1.0x10
4.0x1010
1.5x109
3.0x1010
109
2.0x1010
5.0x108
1010
0
[PAN]
(molecule.cm-3)
[NO2]
4.0x1012
C3H6 (OBS)
C3H6 (MODEL)
(molecule.cm-3)
4.0x1012
[C3H6]
4.0x1012
(molecule.cm-3)
5.0x1012
[O3]
5.0x1012
0
0
1000
2000
3000
Time (second)
4000
5000 0
1000
2000
3000
4000
5000
Time (second)
Comparison of simulated (solid lines) and experimental concentrations (symbols) for NO,
NO2, ozone, propene, formaldehyde, acetaldehyde, formic acid and peroxyacetyl nitrate
(PAN) in a propene-NOx-Air system (experiment # N0306)
(molecule.cm-3)
[NO]
(molecule.cm-3)
6.0x1012