Caltech isoprene scheme
NOTE: This page is for documentation of new isoprene chemistry to be included in v9-02.
'Previous page of description can be found here New isoprene scheme prelim.
Contents
Implementation of the Paulot isoprene scheme
A full reference of all reactions used can be found in this document.
Species
New species added
Species | Formula | Note |
MAOPO2 | CH2OH-CHOO*CH3C(O)OOH | Peroxy radical from MAOP (addition on the double bond) |
ISOPNB | C5H9NO4 | Isoprene nitrate Beta |
ISOPND | C5H9NO4 | Isoprene nitrate Delta |
HC5 | C55H8O2 | Hydroxycarbonyl with 5C |
DIBOO | Dibble peroxy radical | |
MF3 | Methyl furan but I didn’t use it | |
HC5OO | Peroxy radical from HC5 (old IAO2?) | |
DHMOB | C5H8O4 | See Paulot et al., ACP (2009) |
MOBA | 5C acid from isoprene | |
MOBAOO | RO2 from MOBA | |
ISOPNBO2 | RO2 from ISOPND | |
ISOPNDO2 | RO2 from ISOPND | |
PROPNN | Propanone nitrate | |
ETHLN | Ethanal nitrate | |
DHB | Dihydroxybutanone (but removed) | |
MACRN | Nitrate from MVK | |
MVKN | Nitrate from MACR | |
PYAC | Pyruvic acid | |
IEPOX | Isoprene epoxide | |
IEPOXOO | RO2 from IEPOX | |
PYPAN | Pyruvic acid PAN | |
PYPO2 | RO2 associated with PYPAN | |
ATOOH | ATO2 peroxide | |
DRYPMNN | Dry deposition for the different species | |
DRYALPH | ||
DRYLIMO | ||
DRYISOPND | ||
DRYISOPNB | ||
DRYRIP | ||
DRYIEPOX | ||
DRYMACRN | ||
DRYMVKN | ||
DRYPROPNN | ||
DRYHCOOH | ||
DRYACTA | ||
DRYPYPAN |
Species emitted and deposited
Species emitted | Species deposited |
NO | NO2 |
NO2 | O3 |
CO | PAN |
ALK4 | HNO3 |
ISOP | CH2O |
ACET | N2O5 |
PRPE | H2O2 |
C3H8 | PMN |
C2H6 | PPN |
MEK | R4N2 |
ALD2 | |
CH2O | PMNN |
HNO3 | IEPOX |
O3 | RIP |
ISOPND | |
ISOPNB | |
PROPNN | |
MACRN | |
MVKN | |
HCOOH | |
ACTA |
Henry's law constant
Species | Heff(moles L-1 atm-1 ) | ΔH/R (K) | Reference |
HCOOH | 167,000 (pH = 5) | -6100 | Ito et al., 2007 |
CH3COOH | 11,400 (pH = 5) | -6300 | Ito et al., 2007 |
MOBA | 23000 | -6300 | Ito et al., 2007 |
GLYC | 41000 | -4600 | Ito et al., 2007 |
GLYX | 360000 | -7200 | Schweitzer et al., 1998 |
MGLY | 3700 | -7500 | Ito et al., 2007 |
δ-ISOPN (ISOPND) | 17000 | -9200 | Ito et al., 2007 |
β-ISOPN (ISOPND) | 17000 | -9200 | Ito et al., 2007 |
MACRN | 17000 | -9200 | Ito et al., 2007 |
MVKN | 17000 | -9200 | Ito et al., 2007 |
PROPNN | 1000 | 0 | R. Sander (NITROOXYACETONE) |
RIP | 1.7e6 | 0 | Marais et al., 2012 |
IEPOX | 1.3e8 | 0 | Marais et al., 2012 |
MAP | 840 (f0 =1, reactive) | -5300 | R. Sander |
HNO3 | 210000 | -8700 |
Species removed from standard chemistry
Species | Formula | Note |
GCO3 | HOCH2C(O)OO | hydroxy peroxyacetyl radical |
GLCO3 | HCOHC(O)OO | peroxyacyl from GLYX |
GLP | HCOHC(O)OOH | peroxide from GLCO3 |
GLPAN | HCOHC(O)OONO2 | peroxyacylnitrate from GLCO3 |
GP | HOCH2C(O)OOH | peroxide from GCO3 |
GPAN | HOCH2C(O)OONO2 | peroxyacylnitrate from GCO3 |
ISN1 | HOCH2C(OO)(CH3)CH(ONO2)CH2OH | RO2 from ISN2 |
RIO1 | HOCH2C(OO)(CH3)CH=CHOH | RO2 from isoprene oxidation products |
IAO2 | HOCH2C(CH3)(OO)CH(OH)CHO | RO2 from isoprene oxidation products |
MVN2 | O2NOCH2CH(OO)C(O)CH3 | RO2 from MVK+NO3 |
Species Activated from standard chemistry
Species | Formula | Note |
GLYX | CHOCHO | glyoxal |
HCOOH | HCOOH | formic acid |
IALD | HOCH2C(CH3)=CHCHO | hydroxy carbonyl alkenes from isoprene |
Reactions
New reactions
No | Reaction | Rate Constant | Reference | Note |
---|---|---|---|---|
1 | ATOOH +OH=ATO2 +H2O | 2.66E-12exp(200/T) | FP2009,New | Rate uses MP+OH |
2 | ATOOH +OH=MGLY +OH +H2O | 1.14E-12exp(200/T) | FP2009,New | Rate uses MP+OH |
3 | RIO2+NO=0.883NO2 +0.783HO2 +0.660CH2O +0.400MVK +0.260MACR +0.070ISOPND+0.047ISOPNB+0.123HC5 +0.100DIBOO | 2.7E-12 exp(350/T) | FP2009ACP | HNO3 channel deleted since nitrate is treated explicitly;paulothn2009;neglect methylfuran formation (increase the yield of other products) |
4 | VRO2 +NO=0.88NO2 +0.35HO2 +0.35CH2O +0.53MCO3 +0.53GLYC +0.35MGLY +0.12MVKN | 2.7E-12 exp(350/T) | replace old one | |
5 | MRO2 +NO=0.850NO2+0.850HO2+0.122MGLY+0.728HAC+ 0.728CO+0.122CH2O+0.150MACRN | 2.7E-12 exp(350/T) | replace old one | This is modified based on Chuong et al. (2004).It was equally yield for MGLY and HAC in Paulot 2009 ACP, according to Peeters decomposition scheme. |
6 | MAN2+NO = 1.5NO2+0.5CH2O+0.5MGLY+0.5PROPNN+0.5CO+0.5OH | 2.7E-1 exp(350/T) | Tyndall ETO2+NO | |
7 | ATO2 +HO2 =0.15MCO3 +0.15OH +0.15CH2O +0.85ATOOH | 8.60E-13 exp(700/T) | Tyndall, Dillon et al. (ACP 2008) cycling 15% reduce the recyling by 5% compared to previous version to be fully consistent with Dillon et al. | |
8 | KO2+HO2 =OH +ALD2 +MCO3 | 7.40E-13 exp(700/T) | replace old one | |
9 | RIO2 +HO2=0.880RIP+0.120OH +0.047MACR +0.073MVK +0.120HO2+0.120CH2O | 7.40E-13 exp(700/T) | replace old one | |
10 | VRO2+HO2 =0.100VRP+0.680OH +0.578GLYC +0.578MCO3 +0.187MEK+0.102HO2+0.102CH2O +0.102MGLY +0.033RCHO | 7.40E-13 exp(700/T) | replace old one crounse2010 | |
11 | MRO2 +HO2 =0.020MRP+0.980OH +0.980HO2+0.294CH2O+0.686HAC +0.294MGLY +0.686CO | 7.40E-13 exp(700/T) | crounse2010 | |
12 | MAN2+HO2 =0.5PROPNN+0.5CO+0.5HO2+0.5MGLY+0.5CH2O+0.5NO2+OH | 7.40E-13 exp(700/T) | ||
13 | INO2 +HO2 =0.5INPN +0.5ISOPND+0.5OH +0.5HO2 | 7.40E-13 exp(700/T) | ||
14 | RIO2+MO2=1.100HO2+1.220CH2O+0.280MVK+0.180MACR+0.300HC5+0.240MOH+0.240ROH | 8.37E-14 | ||
15 | RIO2 +RIO2 =1.280HO2+0.920CH2O +0.560MVK+0.360MACR+0.480ROH+0.500HC5 | 1.54E-13 | FP2009,New | |
16 | HC5OO+MO2 = 0.50HO2+0.33CO+0.09H2+0.18HAC+0.13GLYC+0.29MGLY+0.25MEK+0.95CH2O+0.25MOH+0.25ROH+0.5HO2 | 8.37E-14 | FP2009 | Tyndall MO2+MO2 Atkinson97 RO2+RO2 replace old one HC5OO=old IAO2 |
17 | MRO2+MO2 =0.595HAC+0.255MGLY+0.595CO+1.255CH2O+1.700HO2+0.150ROH | 8.37E-14 | ||
18 | MAN2+MO2=0.375PROPNN +0.375CO +0.375HO2+0.375MGLY +0.375CH2O +0.375NO2 +0.250CH2O +0.250R4N2 | 8.37E-14 | ||
19 | INO2+MO2 = 0.55NO2+0.40HO2+0.425R4N2+0.025NO2+0.05MACR + 0.08CH2O+0.03MVK+0.25RCHO+0.75CH2O+0.25MOH+0.25ROH+0.5HO2 | 8.37E-14 | ||
20 | RCO3+HO2=0.410RP+0.150RCOOH+0.150O3 +0.440OH+0.440ETO2 | 4.3E-13exp(1040/T) | ||
21 | MAO3+HO2 =0.870OH +0.030O3 +0.435CH2O +0.435MO2 +0.1MAOP +0.030RCOOH+0.283HAC+0.152ATO2 +0.870CO2+0.435CO | 4.3E-13exp(1040/T) | ||
22 | PMN+OH=1.000PMNO2 | 3.20E-11 | ||
23 | PMNO2+NO=0.6CO2+0.6HAC+0.6NO3+0.4CH2O+0.4HO2+0.4PYPAN +0.900NO2 | K* (1-YN) where YN isreturned from fyrno3.f; K=2.7E-12 exp(350/T) (Xcarbn=4.0E00) | FP2009,New | J. Orlando, AE 2002 |
24 | PMNO2+NO=PMNN | K* YN where YN is returned from fyrno3.f ; K=2.7E-12 exp(350/T) (Xcarbn=4.0E00) | FP2009,New | |
25 | PMNO2+HO2=0.6CO2 +0.6HAC+0.6NO3+0.4CH2O +0.4HO2+0.4PYPAN+0.5R4P+0.5OH | 7.4E-13exp(700/T) | FP2009,New | |
26 | PYPO2 +NO2+M=PYPAN | LPL: 9.0E-28(300/T)^8.9 HPL:7.70E-12(300/T)^0.2 Fc: 0.6 | FP2009,New | same as RCO3+NO2 = PPN |
27 | PYPAN =PYPO2 +NO2 | 9.0E-29exp(14000/T) | FP2009,New | follow PPN |
28 | PYPO2 +NO =CO2+MCO3 +NO2 | 2.7E-12 exp(350/T) | FP2009,New | |
29 | PYPO2 +HO2 =CO2+MCO3 +OH | 7.40E-13 exp(700/T) | FP2009,New | |
30 | GLYC +OH=0.850CH2O +0.260CO2+0.580CO +0.260OH+0.740HO2+0.155GLYX | FRAC=1-11.0729*exp(-1/73T) Rate=8.00E-12*FRAC | FP2009,New | Butkovskaya 2006 companion paper and Paulot 2009 |
31 | GLYC +OH=HCOOH +0.190OH +0.190CO +0.810CO2+0.810HO2 | FRAC=1-11.0729*exp(-1/73T) Rate=8.00E-12*(1-FRAC) | FP2009,New | Butkovskaya 2006 companion paper and Paulot 2009 |
32 | GLYX+OH = HO2+2CO | 3.1E-12exp(340/T) | IUPAC2008 | JMAO |
33 | MACR + OH = 0.53MAO3 +0.47MRO2 | 8.0E-12exp(380/T) | FP2009,ACP | MAO3(=MCO3 in the paper); MRO2(=MACROO in the paper) |
34 | HAC+OH=MGLY +HO2 | FRAC=1-23.7*exp(1/60T) Rate=2.15E-12exp(305/T)*FRAC | replace old one | Butkovskaya JPC A (a,b)2006 and Paulot 2009 |
35 | HAC+OH=0.500HCOOH +OH +0.500ACTA +0.500CO2+0.500CO +0.500MO2 | FRAC=1-23.7*exp(1/60T) Rate=2.15E-12exp(305/T)*(1-FRAC) | replace old one | Butkovskaya JPC A (a,b)2006 and Paulot 2009 |
36 | INPN+OH=1.0OH+1.0NO2+1.0MEK | 1.9E-11exp(390/T) | two reactions because of the double bond (rate is from RIP +OH) | |
37 | INPN+OH=0.36INO2+0.64R4N2+0.64OH | 5.18E-12exp(200/T) | abstraction of the H of the hydroperoxide | |
38 | PRPN+OH=0.209PRN1+0.791OH+0.791PROPNN | 8.78E-12exp(200/T) | ||
39 | ETP+OH=0.64OH+0.36ETO2+0.60ALD2 | 5.18E-12exp(200/T) | ||
40 | RA3P+OH=0.64OH+0.36A3O2+0.64RCHO | 5.18E-12exp(200/T) | ||
41 | RB3P+OH=0.791OH+0.209B3O2+0.791ACET | 8.78E-12exp(200/T) | ||
42 | R4P+OH=0.791OH+0.209R4O2+0.791RCHO | 8.78E-12exp(200/T) | ||
43 | RP+OH=RCO3 | 6.13E-13exp(200/T) | same as MAP+OH | |
44 | PP+OH=0.791OH+0.209PO2+0.791RCHO | 8.78E-12exp(200/T) | ||
45 | RIP+OH=0.387RIO2+0.613OH+0.613HC5 | 4.75E-12exp(200/T) | ||
46 | RIP+OH=OH +IEPOX | 1.9E-11exp(390/T) | FP2009, Science | the yield of IEPOX is > 70% assumed to be 100% |
47 | IEPOX+OH=IEPOXOO | 5.78e-11exp(-400/T) | FP2009, Science | |
48 | IEPOXOO+HO2 =0.725HAC+ .275GLYC+0.275GLYX+0.275MGLY+1.125OH+0.825HO2+0.200CO2+0.375CH2O+0.074HCOOH +0.251CO | 7.4E-13exp(700/T) | FP2009, Science unconstrained use HO2 reaction | |
49 | IEPOXOO +NO=0.725HAC+0.275GLYC+0.275GLYX +0.275MGLY +0.125OH +0.825HO2+0.200CO2+0.375CH2O +0.074HCOOH +0.251CO +NO2 | 2.7E-12exp(350/T) | FP: No peroxide was observed | |
50 | IAP+OH =0.654OH+0.654DHMOB+0.346HC5OO | 5.31E-12 exp(200/T) | ||
51 | VRP+OH=0.791OH+0.791MEK+0.209VRO2 | 8.78E-12exp(200/T) | ||
52 | MRP+OH=MRO2 | 1.84E-12exp(200/T) | ||
53 | MRP+OH=CO2+HAC+OH | 4.40E-12exp(380/T) | ||
54 | MAOP + OH = MAO3 | 6.13E-13exp(200/T) | same as MAP+OH | |
55 | MAOP+OH=MAOPO2 | 3.60E-12exp(380/T) | ||
56 | MCO3+MAOPO2=1.0HAC+2.0CO2+OH+MO2 | 1.68E-12exp(500/T) | ||
57 | MCO3+MAOPO2=1.0ACTA+1.0MEK | 1.87E-13 exp(500/T) | ||
58 | MAOPO2+MO2=0.7HAC +0.7CO2+0.7OH+1.0CH2O+0.7HO2+0.3ROH | 8.37E-14 | ||
59 | MAOPO2+MAOPO2=2.0HAC+2.0CO2+2.0OH | 8.37E-14 | ||
60 | MAOPO2+HO2=1.0HAC+1.0CO2+2.0OH | 7.4E-13exp(700/T) | ||
61 | MAOPO2+NO=1.0HAC+1.0CO2+1.0OH+1.0NO2 | K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) | ||
62 | MAOPO2+NO=1.000HNO3 | K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) | Not treated explicitly | |
63 | OH+MAP=1.0MCO3 | 6.13E-13exp(200/T) | From J. Orlando (unpublished results), how confident is this temperature dependence? | |
64 | HC5+O3 = 0.60MGLY+0.10OH+0.12CH2O+0.28GLYC+0.30O3+0.40CO+0.20H2+0.20HAC+0.20HCOOH | 6.16E-15 exp(-1814/T) | HC5=old IALD?? | |
65 | R4O2+MCO3 = MO2 +0.32ACET+0.19MEK+0.27HO2+0.32ALD2+0.13RCHO+0.05A3O2+0.18B3O2+0.32ETO2 | 1.68E-12 exp(500/T) | ||
66 | ATO2+MCO3 = MCO3 +CH2O +MO2 | 1.68E-12 exp(500/T) | IUPAC06 | |
67 | RIO2+MCO3=0.887HO2+0.747CH2O+0.453MVK+0.294MACR+0.140HC5 +0.113DIBOO +CO2+MO2 | 1.68E-12 exp(500/T) | Follow RIO2+NO without the yield of nitrate and NO2 and then rescale it. | |
68 | HC5OO +MCO3=0.216GLYX +0.234MGLY+0.234GLYC+0.216HAC +0.29DHMOB+0.17MOBA+0.09RCHO+HO2+0.09CO+MO2 | 1.68E-12 exp(500/T) | HC5OO=old IAO2, this radical channel use the same as HC5OO+NO without NO2 yield. | |
69 | VRO2+MCO3=0.4HO2+0.4CH2O+0.6MCO3+0.6GLYC+0.4MGLY+1.0MO2 | 1.68E-12 exp(500/T) | this radical channel use the same as VRO2+NO without NO2 and MVKN yield. And carbon balance. | |
70 | MRO2 +MCO3 =0.850HO2 +0.143MGLY+0.857HAC +0.857CO+0.143CH2O +1.0MO2 | 1.68E-12 exp(500/T) | this radical channel use the same as MRO2+NO without NO2 and MACRN yield. | |
71 | MAN2+MCO3 = MO2 +.5NO2+.5CH2O+.5MGLY+.5PROPNN+.5CO+.5HO2 | 1.68E-12 exp(500/T) | ||
72 | ATO2 +MCO3 =MGLY+ACTA | 1.87E-13exp(500/T) | IUPAC06 | replace MEK with MGLY |
73 | HC5OO+MCO3 = MEK +ACTA | 1.87E-13 exp(500/T) | ||
74 | ISOPNB+O3=0.610MVKN +0.390MACRN +0.270OH +CH2O | 1.06E-16 | Lockwood et al., 2010 ACP | |
75 | ISOPND+O3=0.500PROPNN+0.500ETHLN +0.270OH +0.500GLYC+0.500HAC | 5.3E-17 | Lockwood et al., 2010 ACP | |
76 | HC5+OH=HC5OO | 3.35E-11exp(380/T) | FP2009,ACP | |
77 | HC5OO+NO=NO2+0.216GLYX+0.234MGLY+0.234GLYC+0.216HAC+0.290DHMOB+0.170MOBA+0.090RCHO+HO2+0.090CO | K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) | ||
78 | HC5OO +NO=HNO3 | K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00) | ||
79 | HC5OO +HO2 =0.1IAP+0.9OH +0.9MGLY +0.9GLYC +0.9HO2 | 7.4E-13exp(700/T) | 90% recycling, no experimental data. Somewhat based upon the high recycling rate observed for MVK/MACR | |
80 | ISOPND+OH=ISOPNDO2 | 2.64E-11exp(380/T) | FP2009,ACP | |
81 | ISOPNB+OH=ISOPNBO2 | 3.61E-12exp(380/T) | FP2009,ACP | |
82 | ISOPNDO2+NO=0.070MACRN+0.310HCOOH+0.440HAC+0.130ETHLN+0.650CH2O +1.340NO2+0.150GLYC+0.310NO3+0.150PROPNN+0.340MEK+0.350HO2 | K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) | FP2009,ACP | |
83 | ISOPNDO2+NO=HNO3 | K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00) | Nitrates from ISOPND could not be observed in this experiment | |
84 | ISOPNDO2+HO2=0.035MACRN+0.155HCOOH+0.22HAC+0.065ETHLN +0.325CH2O+0.170NO2+0.075GLYC+0.155NO3+0.075PROPNN+0.170MEK+0.175HO2+0.5OH+0.5ISNP | 7.4E-13exp(700/T) | Assume 50% recycling from HO2+RO2 (no experimental data - check Ng et al. for better estimates) | |
85 | ISOPNBO2+NO=0.6GLYC+0.6HAC+0.4CH2O +1.6NO2+0.26MACRN+0.4HO2+0.14MVKN | K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) | FP2009,ACP | |
86 | ISOPNBO2+NO=HNO3 | K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00) | Nitrates from ISOPND could not be observed in this experiment | |
87 | ISOPNBO2+HO2=0.300GLYC+0.300HAC+0.200CH2O+0.130MACRN+0.070MVKN+0.300NO2+0.200HO2+0.500OH+0.500ISNP | 7.4E-13exp(700/T) | Assume 50% recycling from HO2+RO2 (no experimental data - check Ng et al. for better estimates) | |
88 | ISNP+OH=0.612OH+0.612R4N1++0.193ISOPNBO2+0.193ISOPNDO2 | 4.75E-12exp(200/T) | replace the old ISNP+OH | |
89 | MVKN+OH=0.650HCOOH+NO3+0.650MGLY+0.350CH2O+0.350PYAC | 1.5E-12exp(380/T) | FP2009,ACP | |
90 | MACRN +OH=1.000MACRNO2 | 1.39E-11exp(380/T) | ||
91 | MACRNO2+NO=0.080ACTA+0.080CH2O+0.150NO3+0.070HCOOH+0.070MGLY+0.850HAC+0.850NO2+0.930CO2+1.000NO2 | 2.7E-12exp(350/T) | no nitrate yield (acyl) | |
92 | MACRNO2+HO2=0.080ACTA +0.080CH2O+0.150NO3+0.070HCOOH+0.070MGLY+0.850HAC+0.850NO2+0.930CO2+1.000OH | 7.4E-13exp(700/T) | Assume 100% recycling. No experiment data. Inferred from the very high recycling observed for MAO2+HO2 | |
93 | MACRNO2+NO2=1.000PMNN | LPL: 9.00E-28(300/T)^8.9 HPL:7.70E-12(300/T)^0.2 Fc: 0.6 | ||
94 | PMNN =1.000MACRNO2 +1.000NO2 | 9e-29*exp(14000/T) | ||
95 | DHMOB+OH=1.500CO+1.000HO2+0.500HAC++0.500MEK | 2.52E-11exp(410/T) | ||
96 | DIBOO +NO=HO2+NO2+0.520GLYC +0.520MGLY +0.480HAC+0.480GLYX | K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) | Dibble, 2004 Note that the yield of DIBOO Is likely overestimate (~30%) | |
97 | DIBOO +NO=HNO3 | K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00) | ||
98 | DIBOO+HO2=HO2+OH +0.520GLYC+0.520MGLY+0.480HAC+0.480GLYX | 7.4E-13exp(700/T) | Assume 100% recycling. No experimental data. Somewhat derived from the high recycling in MVK/MACR | |
99 | MOBA +OH=MOBAOO | 2.79E-11exp(380/T) | ||
100 | MOBAOO+NO=RCHO+CO2+HO2+NO2 | K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) | ||
101 | MOBAOO+NO=HNO3 | K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00) | ||
102 | MOBAOO+HO2=0.500OH+0.500HO2+0.500RCHO+0.500CO2+0.500R4P | 7.4E-13exp(700/T) | FP2009,ACP | No experimental constraint. Assume 50% recycling and go to R4P for the peroxide channel to avoid carrying another peroxide |
103 | MOBA +O3=OH +HO2+CO2+MEK | 2.00E-17 | FP2009,ACP | Weak constraint on the rate constant - no constraint on the products |
104 | ETHLN +OH=CH2O +CO2+NO2 | 1.00E-11 | ||
105 | PROPNN+OH=NO2+MGLY | 1.00E-15 | FP2009,ACP | IUPAC says < 1e-12;Experiment suggests it is slower than than 1e-13-1e-15 |
Photolysis | RIP = OH + HO2 + 0.710CH2O + 0.425MVK + 0.285MACR + 0.29HC5 | |||
Photolysis | MACRN=NO2+HAC+MGLY+0.500CH2O+HO2+0.500CO | |||
Photolysis | MVKN=GLYC +NO2+MCO3 | |||
Photolysis | ISOPNB=HC5+NO2+HO2 | |||
Photolysis | ISOPND=HC5+NO2+HO2 | |||
Photolysis | PROPNN=CH2O +NO2+CO +MO2 | |||
Photolysis | ATOOH=OH +CH2O +MCO3 | |||
Photolysis | PYPAN=0.300NO3+0.700NO2+MCO3 +CO2 | |||
Photolysis | PYPAN=NO3++MCO3 +CO2 |
Removed reactions from standard chemistry
No | Reaction | Rate Constant | Reference | Note |
---|---|---|---|---|
1 | RIO2 + NO = 0.90NO2 + 0.90HO2 + 0.34IALD + 0.34MVK + 0.22MACR + 0.56CH2O | K=2.7E-12 exp(350/T) | Atkinson 97&DBM(MCM 3.1) | |
2 | RIO1+NO=NO2+IALD+HO2+0.75CH2O | K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) | Atkinson 97&DBM(MCM 3.1) | |
3 | RIO1+NO = HNO3 | K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00) | Atkinson 97 | |
4 | IAO2+NO = 0.92HO2+0.61CO+0.17H2+0.33HAC+0.24GLYC +0.53MGLY+0.92NO2 +0.35CH2O+0.08HNO3 | 2.7E-12 exp(350/T) | Tyndall ETO2+NO | |
5 | ISN1+NO = 1.9NO2+0.95GLYC+0.95HAC +0.05HNO3+0.05NO2+0.05HO2 | Paulson&Seinfeld 1992 | ||
6 | VRO2+NO = NO2+0.28HO2+0.28CH2O+0.72MCO3+0.72GLYC+0.28MGLY | K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) | Atkinson 97 | |
7 | VRO2+NO = HNO3 | K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) | Atkinson 97 | |
8 | MRO2 + NO = NO2 + HAC + CH2O + HO2 | K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) | Atkinson 97&DBM(MCM 3.1) | |
9 | MRO2+NO = HNO3 | K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) | Atkinson 97 | |
10 | MVN2+NO = 1.90NO2 +0.30HO2+0.30CH2O+0.60MCO3+0.60GLYC+0.30MGLY+0.10HNO3 | 2.7E-12 exp(350/T) | ||
11 | INO2+NO = 1.10NO2+0.80HO2+0.85HNO3+0.05NO2+0.10MACR+0.15CH2O+0.05MVK | 2.7E-12 exp(350/T) | Tyndall ETO2+NO | |
12 | GLCO3+NO2 = GLPAN | LPL: 9.00E-28(300/T)^8.9 HPL:7.70E-12(300/T)^0.2 Fc: 0.6 | JPL02 Same as PPN | |
13 | GLPAN = GLCO3+NO2 | 9e-29*exp(14000/T) | JPL02 PPN | |
14 | GCO3+NO2 = GPAN | LPL: 9.00E-28(300/T)^8.9 HPL:7.70E-12(300/T)^0.2 Fc: 0.6 | JPL02 Same as PPN | |
15 | GPAN = GCO3+NO2N | 9e-29*exp(14000/T) | JPL02 PPN | |
16 | GCO3+NO = NO2+HO2 +CH2O | 6.70E-12 exp(340/T) | IUPAC02 | C2H5CO3+NO |
17 | GLCO3+NO = NO2+HO2+CO | 6.70E-12 exp(340/T) | IUPAC02 C2H5CO3+NO | This reaction doesn't exist in the manual but is in the input The rate is from IUPAC2006 (or 2003), using the rate of CH3CH2C(O)O2+NO=C2H5C(O)O+NO2. |
18 | MAO3 + NO=MCO3 + CH2O + NO2 | 6.7E-12exp(340/T) | IUPAC2006 | |
19 | ATO2+HO2 = MCO3 + MO2 | 8.60E-13 exp(700/T) | ||
20 | KO2+HO2 = MO2 + MGLY | 7.40E-13 exp(700/T) | Tyndall | Tyndall forms CH3C(O)CH2OOH ,this must then split and go to MCO3+MO2, the products in chem..dat ?? |
21 | RIO2+HO2 = RIP | 7.40E-13 exp(700/T) | Tyndall | |
22 | RIO1+HO2 = RIP | 7.40E-13 exp(700/T) | Tyndall | |
23 | IAO2 + HO2 = IAP | 7.40E-13 exp(700/T) | Tyndall | |
24 | ISN1+HO2 = ISNP | 7.40E-13 exp(700/T) | Tyndall | |
25 | VRO2+HO2 = VRP | 7.40E-13 exp(700/T) | ||
26 | MRO2+HO2 = MRP | 7.40E-13 exp(700/T) | ||
27 | MVN2 + HO2 = ISNP | 7.40E-13 exp(700/T) | ||
28 | RIO2+MO2 = 0.42HO2 +0.35CH2O+0.2MVK +0.14MACR + 0.07RIO1 +0.06IALD+0.25MEK+0.75CH2O+0.25MOH+0.25ROH + 0.5HO2 | 8.37E-14 | Tyndall | MO2+MO2 Atkinson97 RO2+RO2 |
29 | RIO1+MO2 = 0.50IALD+0.50HO2+0.38CH2O+0.25MEK+0.75CH2O+0.25MOH+0.25ROH+ 0.5HO2 | 8.37E-14 | Tyndall | MO2+MO2 Atkinson97 RO2+RO2 |
30 | IAO2+MO2 = 0.50HO2+0.33CO+0.09H2+0.18HAC+0.13GLYC+0.29MGLY+0.25MEK+0.95CH2O+0.25MOH+0.25ROH+0.5HO2 | 8.37E-14 | Tyndall | MO2+MO2 Atkinson97 RO2+RO2 |
31 | ISN1+MO2 = NO2+0.50GLYC+0.50HAC+0.25RCHO+0.75CH2O+0.25MOH+ 0.25ROH+0.50HO2 | 8.37E-14 | Tyndall | MO2+MO2 Atkinson97 RO2+RO2 |
32 | RCO3+HO2=0.3RCOOH+0.3O3+ 0.7RP | 4.30E-13 exp(1040/T) | ||
33 | GCO3 + HO2 = 0.71GP + 0.29O3 + 0.29CH2O | 4.30E-13 exp(1040/T) | DBM(MCM 3.1) | |
34 | MAO3+HO2=0.3RCOOH+0.3O3 + 0.7MAOP | 4.30E-13 exp(1040/T) | ||
35 | GLCO3+HO2=0.3RCOOH+0.3O3+0.7GLP | 4.30E-13 exp(1040/T) | ||
36 | GLYC+OH =0.800GCO3+0.400CO+0.200H2+0.200HO2 | 1.00E-11 | Atkinson 92,94 | |
37 | MACR + OH = 0.57MAO3 + 0.43MRO2 | 8.0E-12exp(380/T) | IUPAC06 | JMAO,DBM(MCM3.1) |
38 | HAC+OH = MGLY+HO2 | 3E-012 | IUPAC06 | |
39 | GCO3+MO2 = 2CH2O +2HO2 | 1.68E-12 exp(500/T) | T dep & B.R.Tyndall K298Villenave 98 | |
40 | GLCO3+MO2 = CH2O +2HO2+CO | 1.68E-12 exp(500/T) | T dep & B.R.Tyndall K298Villenave 98 | |
41 | GCO3+MO2 = RCOOH + CH2O | 1.87E-13 exp(500/T) | T dep & B.R.Tyndall K298Villenave 98 | |
42 | PP + OH = PO2 | 3.80E-12 exp(200/T) | DBM(MCM 3.1) | |
43 | GP + OH = GCO3 | 3.80E-12 exp(200/T) | DBM(MCM 3.1) | |
44 | GLP+OH = 0.50OH+0.50GLCO3+0.50CO | 3.80E-12 exp(200/T) | JPL97,MP+OH | |
45 | RIP + OH = 0.509IALD + 0.509OH + 0.491RIO2 | 3.80E-12 exp(200/T) | DBM,lumping from MCM3.1 | |
46 | IAP + OH = IAO2 | 3.80E-12 exp(200/T) | DBM(MCM 3.1) | |
47 | ISNP+OH = 0.50OH+0.50RCHO+0.50NO2+0.50ISN1 | 3.80E-12 exp(200/T) | JPL97,MP+OH | |
48 | VRP+OH = 0.50OH+0.50RCHO+0.50VRO2 | 3.80E-12 exp(200/T) | JPL97,MP+OH | |
49 | MRP + OH = MRO2 | 3.80E-12 exp(200/T) | DBM(MCM 3.1) | |
50 | MAOP + OH = MAO3 | DBM(MCM 3.1) | ||
51 | MNO3+OH =CH2O+NOMNO32 | 8.0E-13exp(-1000/T) | JPL06 | |
52 | IALD+OH = 0.44IAO2 +0.41MAO3+0.15HO2 | 3.70E-11 | Paulson &Seinfeld, 92 | |
53 | IALD+O3 = 0.60MGLY+0.10OH+0.12CH2O+0.28GLYC+0.30O3+0.40CO+0.20H2+0.20HAC+0.20HCOOH | 6.16E-15 exp(-1814/T) | Paulson &Seinfeld, 92 | MCO3+NO,MCO3,HO2,RCO3,GCO3,MAO3,GLCO3 rates are used for other radicals. |
54 | R4O2+MCO3 = MO2 +0.32ACET+0.19MEK+0.18MO2+0.27HO2+0.32ALD2+0.13RCHO+0.05A3O2+0.18B3O2+0.32ETO2 | 1.68E-12 exp(500/T) | T dep & B.R.Tyndall K298Villenave 98 | |
55 | RIO2+MCO3 = MO2+0.864HO2+0.690CH2O +0.402MVK+0.288MACR+0.136RIO1+0.127IALD | 1.68E-12 exp(500/T) | ||
56 | RIO1+MCO3 = MO2 +IALD+HO2+0.75CH2O | 1.68E-12 exp(500/T) | ||
57 | IAO2+MCO3 = MO2 +HO2+0.65CO+0.18H2+0.36HAC+0.26GLYC+0.58MGLY+0.4CH2O | 1.68E-12 exp(500/T) | ||
58 | ISN1+MCO3 = MO2+NO2+GLYC+HAC | 1.68E-12 exp(500/T) | ||
59 | ATO2+MCO3 = MEK +ACTA | 1.87E-13 exp(500/T) | ||
60 | KO2+MCO3 = MEK + ACTA | 1.87E-13 exp(500/T) | ||
61 | RIO1+MCO3 = MEK +ACTA | 1.87E-13 exp(500/T) | ||
62 | IAO2+MCO3 = MEK+ ACTA | 1.87E-13 exp(500/T) | ||
63 | VRO2+MCO3 = MEK +ACTA | 1.87E-13 exp(500/T) | ||
64 | MRO2+MCO3 = MEK +ACTA | 1.87E-13 exp(500/T) | ||
65 | R4N1+MCO3 = RCHO +ACTA + NO2 | 1.87E-13 exp(500/T) | ||
66 | ISN1+MCO3 = RCHO +ACTA + NO2 | 1.87E-13 exp(500/T) | ||
67 | MVN2+MCO3 = RCHO +ACTA + NO2 | 1.87E-13 exp(500/T) | ||
68 | MAN2+MCO3 = RCHO +ACTA + NO2 | 1.87E-13 exp(500/T) | ||
69 | INO2+MCO3 = RCHO +ACTA + NO2 | 1.87E-13 exp(500/T) | ||
70 | PRN1 + MCO3 = RCHO +ACTA + NO2 | 1.87E-13 exp(500/T) | ||
71 | GCO3+MCO3 = MO2 + HO2+ CH2O | 2.50E-12 exp(500/T) | Tyndall,MCO3+MCO3 | |
72 | MONX=3.000CH2O | 1.07E-5 | ||
73 | GLCO3+MCO3 = MO2+ HO2+ CO | 2.50E-12 exp(500/T) | Tyndall,MCO3+MCO3 | |
74 | MVN2+MO2 = NO2+0.50CH2O+0.25MCO3 +0.25MGLY+0.25HO2+0.25RCHO+0.75CH2O+0.25MOH+0.25ROH+0.50HO2 | 8.37E-14 | ||
75 | MVN2+MCO3 = MO2 +NO2+CH2O+0.5MCO3+0.5MGLY+0.5HO2 | 1.68E-12 exp(500/T) | ||
76 | MVN2+MCO3 = RCHO +ACTA + NO2 | 1.87E-13 exp(500/T) | ||
Photolysis | MNO3 = CH2O + H2O + NO2 | As in Wild et al., 2000. | ||
Photolysis | GP = OH + HO2 + CH2O | Uses MP cross-section | ||
Photolysis | GLP = OH + HO2 + CO | Uses MP cross-section | ||
Photolysis | PP = OH + HO2 + ALD2 + CH2O | DBM(MCM 3.1) | ||
Photolysis | RIP = OH + HO2 + 0.627CH2O + 0.368MVK + 0.259MACR + 0.373IALD | DBM(MCM3.1) | ||
Photolysis | VRP = OH + 0.3HO2 + 0.3CH2O + 0.7MCO3 + 0.7GLYC + 0.3MGLY | DBM(MCM3.1) | ||
Emission | EMISSION=ALPH | |||
Emission | EMISSION=LIMO |
- MVN2 reactions are removed because we deactivate the source MVK+NO3.
- MNO3 is removed because there is no source of MNO3 in the model.
Update One - RO2+HO2 Reaction Rate
Update applied to all >C2 RO2 species reaction with HO2. These include, in the standard scheme, R4O2, R4N1, KO2, RIO2, RIO1, IAO2,ISN1, VRO2, MRO2, MVN2, MAN2, B3O2, INO2, PRN1, A3O2, PO2.
Old RO2+HO2 reaction rate: k = 7.40E-13*EXP(700/T)
New RO2+HO2 reaction rate: k = 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], where n=no. of carbon atoms
Comparison of new and old RO2+HO2 reaction rates for C4 RO2 and C5 RO2:
Benchmarking for this update can be viewed at: (Benchmarking results for RO2+HO2 reaction)
Update Two - Transport of RIP
RIP = isoprene peroxide species formed at low-NOx (i.e. via the RO2+HO2 pathway)
This benchmark is done to understand the muted influence of the increased rate of the RO2+HO2 reaction on CH2O. Is this because the ultimate yield of CH2O is similar for all levels of NOx and RIP is not transported, leading to the realization of the ultimate yield of CH2O in the same grid box as its emission source?
Both schemes are run with initial concentrations of species set to zero. As RIP is added as an additional transported species this was viewed as the most effective way of comparing the two model runs.
Benchmarking for this update can be viewed at: (Benchmarking results for transporting RIP)
References
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- Crounse, J. D., Knap, H. C., Ørnsø, K. B., Jørgensen, S., Paulot, F., Kjaergaard, H. G., and Wennberg, P. O.: Atmospheric Fate of Methacrolein. 1. Peroxy Radical Isomerization Following Addition of OH and O2, The Journal of Physical Chemistry A, 116, 5756-5762, 10.1021/jp211560u, 2012.
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- Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kroll, J. H., Seinfeld, J. H., and Wennberg, P. O.: Isoprene photooxidation: new insights into the production of acids and organic nitrates, Atmos. Chem. Phys., 9, 1479-1501, 2009a.
- Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kurten, A., St Clair, J. M., Seinfeld, J. H., and Wennberg, P. O.: Unexpected Epoxide Formation in the Gas-Phase Photooxidation of Isoprene, Science, 325, 730-733, 10.1126/science.1172910, 2009b.
- Peeters, J., Nguyen, T. L., and Vereecken, L.: HOx radical regeneration in the oxidation of isoprene, Phys. Chem. Chem. Phys., 11, 5935-5939, 10.1039/b908511d, 2009.
- Peeters, J., and Müller, J. F.: HOx radical regeneration in isoprene oxidation via peroxy radical isomerisations. II: experimental evidence and global impact, Phys. Chem. Chem. Phys., 12, 14227-14235, 10.1039/c0cp00811g, 2010.
- Xie, Y., Paulot, F., Carter, W. P. L., Nolte, C. G., Luecken, D. J., Hutzell, W. T., Wennberg, P. O., Cohen, R. C., and Pinder, R. W.: Understanding the impact of recent advances in isoprene photooxidation on simulations of regional air quality, Atmos. Chem. Phys. Discuss., 12, 27173-27218, 10.5194/acpd-12-27173-2012, 2012.