Difference between revisions of "Caltech isoprene scheme"
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===Henry's law constant=== | ===Henry's law constant=== | ||
− | + | ||
+ | |GLYX|| 360000||-7200||1.0|| Schweitzer et al., 1998 | ||
|- | |- | ||
− | | | + | |MGLY|| 3700|| -7500||1.0|| Ito et al., 2007 |
− | | | + | |
− | | | + | |
− | + | ||
|- | |- | ||
− | | | + | |PROPNN||1000|| 0||1.0||R. Sander (NITROOXYACETONE) |
|- | |- | ||
− | | | + | |
+ | |MAP|| 840 (f0 =1, reactive)|| -5300|| R. Sander | ||
|- | |- | ||
− | | | + | |HNO3|| 210000||-8700||0 || |
+ | |} | ||
+ | |||
+ | {| border="1" bordercolor="#000000" cellpadding="5" cellspacing="0" | ||
+ | |-bgcolor="#cccccc" | ||
+ | !width="100pt" | Species | ||
+ | !width="100pt" | H*(moles L-1 atm-1 ) | ||
+ | !width="200pt" | ΔH/R (K) | ||
+ | !width="200pt" | Reactivity factor (f0) | ||
+ | !width="200pt" | Reference | ||
|- | |- | ||
− | | | + | |NO2||0.01 || ||0.1|| |
|- | |- | ||
− | | | + | |Ox ||0.01 || ||1.0|| |
|- | |- | ||
− | | | + | |PAN ||3.6 || ||1.0|| |
|- | |- | ||
− | | | + | |HNO3 ||1.0d+14|| ||0.0|| |
|- | |- | ||
− | | | + | |H2O2 ||1.0d+5 || ||1.0|| |
|- | |- | ||
− | | | + | |PMN || as PAN|| || || |
|- | |- | ||
− | | | + | |PPN || as PAN|| || || |
|- | |- | ||
− | | | + | |R4N2 || as PAN|| || || |
|- | |- | ||
− | | | + | |CH2O || 6.0e+3|| ||1.0|| |
|- | |- | ||
− | | | + | |GLYX|| 360000||-7200||1.0|| Schweitzer et al., 1998 |
|- | |- | ||
− | | | + | |MGLY|| 3700|| -7500||1.0|| Ito et al., 2007 |
|- | |- | ||
− | | | + | |GLYC|| 41000 ||-4600||1.0|| Ito et al., 2007 |
− | | | + | |
− | + | ||
− | + | ||
− | + | ||
|- | |- | ||
− | | | + | |MPAN||as PAN || || || |
− | | | + | |
− | | | + | |
|- | |- | ||
− | | | + | |N2O5 ||as HNO3 || || || |
|- | |- | ||
− | | | + | |HCOOH ||1.67d+5 ||-6100 ||1.0 ||Ito et al., 2007 |
|- | |- | ||
− | | | + | |ACTA ||1.14d+4 ||-6300 ||1.0||Ito et al., 2007 |
|- | |- | ||
− | | | + | |ISOPND||1.7d+4 ||-9200||1.0||Ito et al., 2007 |
|- | |- | ||
− | | | + | |ISOPNB||1.7d+4 ||-9200||1.0||Ito et al., 2007 |
|- | |- | ||
− | | | + | |MVKN+MACRN||1.7d+4 ||-9200||1.0||Ito et al., 2007 |
|- | |- | ||
− | | | + | |PROPNN||1.0d+3 || ||1.0||NITROOXYACETONE IN SANDER TABLE |
|- | |- | ||
− | | | + | |RIP ||1.7e6|| ||1.0||Marais et al., 2012 |
|- | |- | ||
− | | | + | |IEPOX ||1.3e8|| ||1.0||Marais et al., 2012 |
|- | |- | ||
− | | | + | |MAP ||8.4d+2 ||-5300 ||1.0 ||R. Sander |
− | | | + | |
− | + | ||
− | + | ||
|- | |- | ||
− | | | + | |MVK ||4.4d1 || ||1.0 || from R.Sander |
− | | | + | |
− | | | + | |
|- | |- | ||
− | | | + | |MACR ||6.5d0 || ||1.0|| from R.Sander |
|- | |- | ||
− | | | + | |MOBA|| 23000|| -6300||1.0|| Ito et al., 2007 |
|- | |- | ||
− | | | + | |SO2 ||1.0d+5 || ||0.0 || |
|} | |} | ||
+ | |||
+ | Karl, T., Harley, P., Emmons, L., Thornton, B., Guenther, A., Basu, C., Turnipseed, A., and Jardine, K.: Efficient Atmospheric Cleansing of Oxidized Organic Trace Gases by Vegetation, Science, 330, 816-819, 10.1126/science.1192534, 2010. | ||
==Reactions== | ==Reactions== |
Revision as of 22:13, 7 February 2013
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
This chemistry is largely base on Paulot et al.(2009a, ACP) for high-NOx regime and Paulot et al.(2009b, Science) for low-NOx regime. Other additions include:
- Isomerization of RIO2 base on Peeters et al. (2009, 2010) an Crounse et al. (2011).
- Isomerization of MRO2 base on Crounse et al. (2012).
- Nighttime isoprene oxidation based on Rollins et al. (2009) and Xie et al. (2012).
- Updates to the reactions of isoprene nitrates + O3 base on Lockwood et al. (2010).
If you have any questions, please let us know (Fabien Paulot, Jingqiu Mao ).
Species
Species
Species | Formula | Note |
---|---|---|
A3O2 | CH3CH2CH2OO | primary RO2 from C3H8 |
ACET | CH3C(O)CH3 | acetone |
ACTA | CH3C(O)OH | acetic acid |
ALD2 | CH3CHO | acetaldehyde |
ALK4 | RH | ≥C4 alkanes |
ATO2 | CH3C(O)CH2O2 | RO2 from acetone |
ATOOH | CH3C(O)CH2OOH | ATO2 peroxide |
B3O2 | CH3CH(OO)CH3 | secondary RO2 from C3H8 |
C2H6 | C2H6 | ethane |
C3H8 | C3H8 | propane |
CH2O | CH2O | formaldehyde |
CH4 | CH4 | methane |
CO | CO | carbon monoxide |
CO2 | CO2 | carbon dioxide |
DHMOB | HOCH2C(CH3)(OH)C(=O)CHO | See Paulot et al., ACP (2009) |
DIBOO | Dibble peroxy radical | |
EOH | C2H5OH | ethanol |
ETHLN | CHOCH2ONO2 | Ethanal nitrate |
ETO2 | CH3CH2OO | ethylperoxy radical |
ETP | CH3CH2OOH | ethylhydroperoxide |
GLYC | HOCH2CHO | glycoaldehyde (hydroxyacetaldehyde) |
GLYX | CHOCHO | glyoxal |
H2 | H2 | hydrogen atom |
H2O | H2O | water vapor |
H2O2 | H2O2 | hydrogen peroxide |
HAC | HOCH2C(O)CH3 | hydroxyacetone |
HCOOH | HCOOH | formic acid |
HC5 | HOCH2CH=C(CH3)CHO | Hydroxycarbonyl with 5C |
HC5OO | Peroxy radical from HC5 (old IAO2?) | |
HNO2 | HONO | nitrous acid |
HNO3 | HNO3 | nitric acid |
HNO4 | HNO4 | pernitric acid |
HO2 | HO2 | hydroperoxyl radical |
IALD | HOCH2C(CH3)=CHCHO | hydroxy carbonyl alkenes from isoprene |
IAP | HOCH2C(CH3)(OOH)CH(OH)CHO | peroxide from IAO2 |
IEPOX | Isoprene epoxide | |
IEPOXOO | RO2 from IEPOX | |
INO2 | O2NOCH2C(OO)(CH3)CH=CH2 | RO2 from ISOP+NO3 |
INPN | O2NOCH2C(OOH)(CH3)CH=CH2 | peroxide from INO2 |
ISN1 | nighttime isoprene nitrate | |
ISNOOA | peroxy radical from ISN1 | |
ISNOOB | peroxy radical from ISN1 | |
ISNOHOO | peroxy radical from ISN1 | |
ISNP | HOCH2C(OOH)(CH3)CH(ONO2)CH2OH | peroxide from ISOPNBO2 and ISOPNDO2 |
ISOP | CH2=C(CH3)CH=CH2 | isoprene |
ISOPNB | C5H9NO4 | Isoprene nitrate Beta |
ISOPND | C5H9NO4 | Isoprene nitrate Delta |
KO2 | RO2 from >3 ketones | RO2 from >3 ketones |
M | for three body reactions | |
MACR | CH2=C(CH3)CHO | methacrolein |
MACRN | HOCH2C(ONO2)(CH3)CHO | Nitrate from MVK |
MAN2 | HOCH2C(ONO2)(CH3)CHO | RO2 from MACR+NO3 |
MAO3 | CH2=C(CH3)C(O)OO | peroxyacyl from MVK and MACR |
MAOP | CH2=C(CH3)C(O)OOH | peroxide from MAO3 |
MAOPO2 | CH2OH-CHOO*CH3C(O)OOH | Peroxy radical from MAOP (addition on the double bond) |
MAP | CH3C(O)OOH | peroxyacetic acid |
MCO3 | CH3C(O)OO | peroxyacetyl radical |
MEK | RC(O)R | >3 ketones |
MGLY | CH3COCHO | methylglyoxyal |
MNO3 | CH3ONO2 | methylnitrate |
MOBA | HOC(=O)C(CH3)=CHCHO | 5C acid from isoprene |
MOBAOO | RO2 from MOBA | |
MO2 | CH3O2 | methylperoxy radical |
MOH | CH3OH | methanol |
MP | CH3OOH | methylhydroperoxide |
MRO2 | HOCH2C(OO)(CH3)CHO | RO2 from MACR+OH |
MRP | HOCH2C(OOH)(CH3)CHO | peroxide from MRO2 |
MVK | CH2=CHC(=O)CH3 | methylvinylketone |
MVKN | HOCH2CH(ONO2)C(=O)CH3 | Nitrate from MACR |
N2 | N2 | nitrogen |
N2O | N2O | nitrous oxide |
N2O5 | N2O5 | dinitrogen pentoxide |
NH2 | NH2 | ammonia radical |
NH3 | NH3 | ammonia |
NO | NO | nitric oxide |
NO2 | NO2 | nitrogen dioxide |
NO3 | NO3 | nitrate radical |
O2 | O2 | molecular oxygen |
O2CH2OH | O2CH2OH | produced by CH2O+HO2 |
O3 | O3 | ozone |
OH | OH | hydroxyl radical |
PAN | CH3C(O)OONO2 | peroxyacetylnitrate |
PMN | CH2=C(CH3)C(O)OONO2 | peroxymethacryloyl nitrate (MPAN) |
PO2 | HOCH2CH(OO)CH3 | RO2 from isoprene |
PP | HOCH2CH(OOH)CH3 | peroxide from PO2 |
PPN | CH3CH2C(O)OONO2 | peroxypropionylnitrate |
PRN1 | O2NOCH2CH(OO)CH3 | RO2 from propene + NO3 |
PRPE | C3H6 | ≥C4 alkenes |
PRPN | O2NOCH2CH(OOH)CH3 | peroxide from PRN1 |
PROPNN | CH3C(=O)CH2ONO2 | Propanone nitrate |
PYAC | CH3COCOOH | Pyruvic acid |
R4N1 | RO2 from R4N2 | RO2 from R4N2 |
R4N2 | RO2NO | ≥C4 alkylnitrates |
R4O2 | RO2 from ALK4 | RO2 from ALK4 |
R4P | CH3CH2CH2CH2OOH | peroxide from R4O2 |
RA3P | CH3CH2CH2OOH | peroxide from A3O2 |
RB3P | CH3CH(OOH)CH3 | peroxide from B3O2 |
RCHO | CH3CH2CHO | >C2 aldehydes |
RCO3 | CH3CH2C(O)OO | peroxypropionyl radical |
RCOOH | C2H5C(O)OH | >C2 organic acids |
RIO1 | HOCH2C(OO)(CH3)CH=CHOH | RO2 from isoprene oxidation products |
RIO2 | HOCH2C(OO)(CH3)CH=CH2 | RO2 from isoprene |
RIP | HOCH2C(OOH)(CH3)CH=CH2 | peroxide from RIO2 |
ROH | C3H7OH | >C2 alcohols |
RP | CH3CH2C(O)OOH | peroxide from RCO3 |
VRO2 | HOCH2CH(OO)C(O)CH3 | RO2 from MVK+OH |
VRP | HOCH2CH(OOH)C(O)CH3 | peroxide from VRO2 |
DMS | (CH3)2S | dimethylsulfide |
SO2 | SO2 | sulfur dioxide |
SO4 | SO4 | sulfate radical |
MSA | CH4SO3 | methanesulfonic acid |
DRYDEP | generic entry for dry dep | |
DRYPMNN | Dry deposition for the different species | |
DRYALPH | ||
DRYLIMO | ||
DRYISOPND | ||
DRYISOPNB | ||
DRYRIP | ||
DRYIEPOX | ||
DRYMACRN | ||
DRYMVKN | ||
DRYPROPNN | ||
DRYHCOOH | ||
DRYACTA | ||
EMISSION | generic entry to do emissions |
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 | |
HAC | |
ALD2 |
Henry's law constant
|GLYX|| 360000||-7200||1.0|| Schweitzer et al., 1998 |- |MGLY|| 3700|| -7500||1.0|| Ito et al., 2007
|- |PROPNN||1000|| 0||1.0||R. Sander (NITROOXYACETONE) |-
|MAP|| 840 (f0 =1, reactive)|| -5300|| R. Sander |- |HNO3|| 210000||-8700||0 || |}
Species | H*(moles L-1 atm-1 ) | ΔH/R (K) | Reactivity factor (f0) | Reference |
---|---|---|---|---|
NO2 | 0.01 | 0.1 | ||
Ox | 0.01 | 1.0 | ||
PAN | 3.6 | 1.0 | ||
HNO3 | 1.0d+14 | 0.0 | ||
H2O2 | 1.0d+5 | 1.0 | ||
PMN | as PAN | |||
PPN | as PAN | |||
R4N2 | as PAN | |||
CH2O | 6.0e+3 | 1.0 | ||
GLYX | 360000 | -7200 | 1.0 | Schweitzer et al., 1998 |
MGLY | 3700 | -7500 | 1.0 | Ito et al., 2007 |
GLYC | 41000 | -4600 | 1.0 | Ito et al., 2007 |
MPAN | as PAN | |||
N2O5 | as HNO3 | |||
HCOOH | 1.67d+5 | -6100 | 1.0 | Ito et al., 2007 |
ACTA | 1.14d+4 | -6300 | 1.0 | Ito et al., 2007 |
ISOPND | 1.7d+4 | -9200 | 1.0 | Ito et al., 2007 |
ISOPNB | 1.7d+4 | -9200 | 1.0 | Ito et al., 2007 |
MVKN+MACRN | 1.7d+4 | -9200 | 1.0 | Ito et al., 2007 |
PROPNN | 1.0d+3 | 1.0 | NITROOXYACETONE IN SANDER TABLE | |
RIP | 1.7e6 | 1.0 | Marais et al., 2012 | |
IEPOX | 1.3e8 | 1.0 | Marais et al., 2012 | |
MAP | 8.4d+2 | -5300 | 1.0 | R. Sander |
MVK | 4.4d1 | 1.0 | from R.Sander | |
MACR | 6.5d0 | 1.0 | from R.Sander | |
MOBA | 23000 | -6300 | 1.0 | Ito et al., 2007 |
SO2 | 1.0d+5 | 0.0 |
Karl, T., Harley, P., Emmons, L., Thornton, B., Guenther, A., Basu, C., Turnipseed, A., and Jardine, K.: Efficient Atmospheric Cleansing of Oxidized Organic Trace Gases by Vegetation, Science, 330, 816-819, 10.1126/science.1192534, 2010.
Reactions
New reactions
No | Reaction | Rate Constant | Reference | Note |
---|---|---|---|---|
Reactions with OH | ||||
ISOP + OH = RIO2 | 3.1E-11exp(350/T) | Sander et al. 2012 | from JPL | |
MACR + OH = 0.53MAO3 +0.47MRO2 | 8.0E-12exp(380/T) | Paulot 2009a | MAO3(=MCO3 in the paper); MRO2(=MACROO in the paper) | |
MVK+OH = VRO2 | 2.6E-12exp(610/T) | |||
PMN + OH = HAC + CO + NO2 | 2.90E-11 | MCM v3.2 | rates and products all from MCM, originally from Orlando et al. (2002) | |
GLYC + OH = 0.732CH2O +0.361CO2 + 0.505CO + 0.227OH + 0.773HO2 + 0.134GLYX + 0.134HCOOH | FRAC=1-11.0729*exp(-1/73T) Rate=8.00E-12*FRAC | Paulot 2009a | Butkovskaya 2006 companion paper and Paulot 2009 | |
GLYC + OH = HCOOH + OH + CO | FRAC=1-11.0729*exp(-1/73T) Rate=8.00E-12*(1-FRAC) | Paulot 2009a | Butkovskaya 2006 companion paper and Paulot 2009 | |
GLYX+ OH = HO2+2CO | 3.1E-12exp(340/T) | IUPAC2008 | JMAO | |
HAC + OH = MGLY +HO2 | FRAC=1-23.7*exp(1/60T) Rate=2.15E-12exp(305/T)*FRAC | Paulot 2009a | Butkovskaya JPC A (a,b)2006 and Paulot 2009a | |
HAC + OH = 0.5HCOOH + OH +0.5ACTA +0.5CO2 + 0.5CO + 0.5MO2 | FRAC=1-23.7*exp(1/60T) Rate=2.15E-12exp(305/T)*(1-FRAC) | Paulot 2009a | Butkovskaya JPC A (a,b)2006 and Paulot 2009a | |
PRPN + OH =0.209PRN1+0.791OH+0.791PROPNN | 8.78E-12exp(200/T) | Branching ratio is determined by alpha and beta Hydrogen position (Kwok et al., 1995). | ||
ETP + OH =0.64OH+0.36ETO2+0.60ALD2 | 5.18E-12exp(200/T) | Branching ratio is determined by alpha and beta Hydrogen position (Kwok et al., 1995). | ||
RA3P + OH =0.64OH+0.36A3O2+0.64RCHO | 5.18E-12exp(200/T) | Branching ratio is determined by alpha and beta Hydrogen position (Kwok et al., 1995). | ||
RB3P + OH =0.791OH+0.209B3O2+0.791ACET | 8.78E-12exp(200/T) | Branching ratio is determined by alpha and beta Hydrogen position (Kwok et al., 1995). | ||
R4P + OH =0.791OH+0.209R4O2+0.791RCHO | 8.78E-12exp(200/T) | Branching ratio is determined by alpha and beta Hydrogen position (Kwok et al., 1995). | ||
RP + OH = RCO3 | 6.13E-13exp(200/T) | same as MAP+OH | ||
PP + OH =0.791OH+0.209PO2+0.791HAC | 8.78E-12exp(200/T) | Branching ratio is determined by alpha and beta Hydrogen position (Kwok et al., 1995). | ||
RIP + OH = 0.387RIO2 + 0.613OH + 0.613HC5 | 4.75E-12exp(200/T) | Paulot 2009b | branching ratio is derived below | |
RIP + OH = OH + IEPOX | 1.9E-11exp(390/T) | Paulot 2009b | the yield of IEPOX is > 70% assumed to be 100% | |
IEPOX + OH = IEPOXOO | 5.78e-11exp(-400/T) | Paulot 2009b | ||
IAP + OH = 0.654OH + 0.654DHMOB + 0.346HC5OO | 5.31E-12 exp(200/T) | |||
VRP + OH =0.791OH+0.791MEK+0.209VRO2 | 8.78E-12exp(200/T) | |||
MRP + OH = MRO2 | 1.84E-12exp(200/T) | This channel is for the abstraction of peroxide H (OOH), which is slow and ignored in MCM v3.2 | ||
MRP + OH = CO2 + HAC + OH | 4.40E-12exp(380/T) | This second channel is for the abstraction of aldehydic H, much faster! The rate is from MACR + OH. | ||
MAOP + OH = MAO3 | 6.13E-13exp(200/T) | same as MAP+OH | ||
MAOP + OH = MAOPO2 | 3.60E-12exp(380/T) | |||
OH + MAP = 1.0MCO3 | 6.13E-13exp(200/T) | From J. Orlando (unpublished results), how confident is this temperature dependence? | ||
HC5 + OH =HC5OO | 3.35E-11exp(380/T) | Paulot 2009a | ||
ISOPND + OH =ISOPNDO2 | 2.64E-11exp(380/T) | Paulot 2009a | ||
ISOPNB + OH =ISOPNBO2 | 3.61E-12exp(380/T) | Paulot 2009a | ||
ISNP + OH =0.612OH+0.612R4N1++0.193ISOPNBO2+0.193ISOPNDO2 | 4.75E-12exp(200/T) | replace the old ISNP+OH | ||
MVKN + OH = 0.650HCOOH+NO3+0.650MGLY+0.350CH2O+0.350PYAC | 1.5E-12exp(380/T) | Paulot 2009a | ||
MACRN + OH = 1.0MACRNO2 | 1.39E-11exp(380/T) | |||
DHMOB + OH = 1.5CO + 1.0HO2 + 0.5HAC + 0.5MEK | 2.52E-11exp(410/T) | |||
MOBA + OH =MOBAOO | 2.79E-11exp(380/T) | |||
ETHLN + OH =CH2O +CO2+NO2 | 1.00E-11 | |||
PROPNN+ OH =NO2+MGLY | 1.00E-15 | Paulot 2009a | IUPAC says < 1e-12;Experiment suggests it is slower than than 1e-13-1e-15 | |
ATOOH + OH = ATO2 + H2O | 2.66E-12exp(200/T) | Vaghjiani and Ravishankara (1989) | Abstraction of peroxide H, follow MP + OH | |
ATOOH + OH = MGLY + OH +H2O | 1.14E-12exp(200/T) | Vaghjiani and Ravishankara (1989) | Abstraction of alpha H, follow MP + OH | |
RO2 + NO reactions | ||||
RIO2 + NO = 0.883NO2 + 0.783HO2 + 0.660CH2O + 0.400MVK + 0.260MACR + 0.070ISOPND + 0.047ISOPNB + 0.123HC5 + 0.1DIBOO | 2.7E-12 exp(350/T) | Paulot 2009a | HNO3 channel deleted since nitrate is treated explicitly;paulothn2009;neglect methylfuran formation (increase the yield of other products) | |
VRO2 + NO = 0.88NO2 + 0.35HO2 + 0.35CH2O + 0.53MCO3 + 0.53GLYC + 0.35MGLY + 0.12MVKN | 2.7E-12 exp(350/T) | Paulot 2009a | ||
MRO2 + NO = 0.85NO2 + 0.85HO2 + 0.122MGLY + 0.728HAC + 0.728CO + 0.122CH2O + 0.15MACRN | 2.7E-12 exp(350/T) | Paulot 2009a | 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. | |
MAN2 + NO = 1.5NO2 + 0.5CH2O + 0.5MGLY + 0.5PROPNN + 0.5CO + 0.5OH | 2.7E-12 exp(350/T) | Tyndall ETO2+NO | ||
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 | ||
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) | |||
MAOPO2 + NO = 1.0HNO3 | K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) | Not treated explicitly | ||
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) | |||
HC5OO +NO=HNO3 | K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00) | |||
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) | Paulot 2009a | ||
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 | ||
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) | Paulot 2009a | ||
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 | ||
MACRNO2 + NO = 0.08ACTA + 0.08CH2O + 0.15NO3 + 0.07HCOOH + 0.070MGLY + 0.850HAC + 0.85NO2 + 0.93CO2 + 1.0NO2 | 2.7E-12exp(350/T) | no nitrate yield (acyl) | ||
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%) | ||
DIBOO + NO =HNO3 | K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00) | |||
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) | |||
MOBAOO + NO =HNO3 | K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00) | |||
MAN2 + NO = 1.5NO2 + 0.5CH2O + 0.5MGLY + 0.5PROPNN + 0.5CO + 0.5OH | 2.7E-12 exp(350/T) | |||
RO2 + HO2 reactions | ||||
RIO2 + HO2= 0.88RIP + 0.12OH + 0.047MACR + 0.073MVK + 0.12HO2 + 0.12CH2O | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | Paulot 2009b | Rate is from Saunders et al. (2003) | |
VRO2 + HO2 = 0.1VRP + 0.68OH + 0.578GLYC + 0.578MCO3 + 0.187MEK + 0.102HO2 + 0.102CH2O + 0.102MGLY + 0.033RCHO | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=4 | ??? | crounse2010 | |
MRO2 + HO2 = 1.0MRP | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=4 | isomerization of MRO2 is included in another reaction. | ||
MAN2 + HO2 = 0.075PROPNN + 0.075CO + 0.075HO2 + 0.075MGLY + 0.075CH2O + 0.075NO2 + 0.15OH + 0.85ISNP | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)],n=4 | assume 15% recycling of OH, the rest goes to ISNP | ||
ATO2 + HO2 = 0.15MCO3 + 0.15OH + 0.15CH2O + 0.85ATOOH | 8.60E-13 exp(700/T) | Dillon et al. (2008) | 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. | |
KO2 + HO2 = 0.15OH +0.15ALD2 +0.15 MCO3 + 0.85 ATOOH | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=4 | MCM | assuming 15% recycling of OH | |
RCO3 + HO2 = 0.410RP + 0.150RCOOH + 0.150O3 + 0.440OH + 0.440ETO2 | 4.3E-13exp(1040/T) | MCM v3.2 | Branching ratio is from MCMv3.2 | |
MAO3 + HO2 = 0.44OH +0.15O3 + 0.59CH2O + 0.39MO2 + 0.41MAOP + 0.39CO | 4.3E-13exp(1040/T) | use MCM, 44% OH channel, 15% O3 channel, 41% peroxide channel. | ||
IEPOXOO + HO2 = 0.725HAC + 0.275GLYC + 0.275GLYX + 0.275MGLY + 1.125OH + 0.825HO2 + 0.200CO2 + 0.375CH2O + 0.074HCOOH + 0.251CO | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | Paulot 2009b | ||
MAOPO2 + HO2 = 1.0HAC+1.0CO2+2.0OH | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=4 | |||
HC5OO + HO2 = 0.1IAP + 0.9OH + 0.9MGLY + 0.9GLYC + 0.9HO2 | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | 90% recycling, no experimental data. Somewhat based upon the high recycling rate observed for MVK/MACR | ||
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 | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | Assume 50% recycling from HO2+RO2 (no experimental data - check Ng et al. for better estimates) | ||
ISOPNBO2 + HO2 = 0.3GLYC + 0.3HAC + 0.2CH2O + 0.13MACRN + 0.07MVKN + 0.3NO2 + 0.2HO2 + 0.5OH + 0.5ISNP | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | Assume 50% recycling from HO2+RO2 (no experimental data - check Ng et al. for better estimates) | ||
MACRNO2 + HO2 = 0.08ACTA + 0.08CH2O + 0.15NO3 + 0.07HCOOH + 0.07MGLY + 0.85HAC + 0.85NO2 + 0.93CO2 + 1.0OH | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=4 | Assume 100% recycling. No experiment data. Inferred from the very high recycling observed for MAO2+HO2 | ||
MACRNO2 + HO2 = 0.08ACTA + 0.08CH2O + 0.15NO3 + 0.07HCOOH + 0.07MGLY + 0.85HAC + 0.85NO2 + 0.93CO2 + 1.0OH | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=4 | Assume 100% recycling. No experiment data. Inferred from the very high recycling observed for MAO2+HO2 | ||
MOBAOO + HO2 = 0.500OH+0.500HO2+0.500RCHO+0.500CO2+0.500R4P | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | Paulot 2009a | No experimental constraint. Assume 50% recycling and go to R4P for the peroxide channel to avoid carrying another peroxide | |
RO2 + MO2/RO2 reactions | ||||
RIO2 + MO2 = 1.1HO2 + 1.22CH2O + 0.280MVK + 0.180MACR + 0.3HC5 + 0.24MOH + 0.24ROH | 8.37E-14 | |||
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 | Tyndall MO2+MO2 Atkinson97 RO2+RO2; HC5OO=old IAO2 | ||
MRO2 + MO2 = 0.595HAC + 0.255MGLY + 0.595CO + 1.255CH2O + 1.7HO2 + 0.150ROH | 8.37E-14 | |||
MAN2 + MO2 = 0.375PROPNN + 0.375CO + 0.375HO2 + 0.375MGLY + 0.375CH2O + 0.375NO2 + 0.250CH2O + 0.250R4N2 | 8.37E-14 | |||
MAOPO2 + MO2 = 0.7HAC +0.7CO2+0.7OH+1.0CH2O+0.7HO2+0.3ROH | 8.37E-14 | |||
RIO2 + RIO2 = 1.28HO2 + 0.92CH2O + 0.56MVK + 0.36MACR + 0.48ROH + 0.5HC5 | 1.54E-13 | |||
MAOPO2 + MAOPO2 = 2.0HAC+2.0CO2+2.0OH | 8.37E-14 | |||
RO2 + MCO3 reactions | ||||
MAOPO2 + MCO3 = 1.0HAC + 2.0CO2 + OH + MO2 | 1.68E-12exp(500/T) | |||
MAOPO2 + MCO3 = 1.0ACTA+1.0MEK | 1.87E-13 exp(500/T) | |||
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) | |||
R4O2 + MCO3 = 1.0ACTA+1.0MEK | 1.87E-13 exp(500/T) | |||
ATO2+MCO3 = MCO3 + CH2O + MO2 | 1.68E-12 exp(500/T) | IUPAC06 | ||
ATO2 + MCO3 = MGLY+ACTA | 1.87E-13exp(500/T) | IUPAC06 | replace MEK with MGLY | |
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. | ||
HC5OO + MCO3 = MEK +ACTA | 1.87E-13 exp(500/T) | |||
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. | ||
VRO2 + MCO3 = MEK +ACTA | 1.87E-13 exp(500/T) | |||
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. | ||
MRO2 + MCO3 = MEK +ACTA | 1.87E-13 exp(500/T) | |||
MAN2 + MCO3 = 0.5PROPNN + 0.5CO + 0.5HO2 + 0.5MGLY + 0.5CH2O + 0.5NO2 + CO2 + MO2 | 1.68E-12 exp(500/T) | |||
MAN2 + MCO3 = RCHO + ACTA + NO2 | 1.87E-13 exp(500/T) | |||
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. | ||
RIO2 + MCO3 = MEK +ACTA | 1.87E-13 exp(500/T) | |||
Reactions with O3 | ||||
ISOP + O3 = 0.244MVK + 0.325MACR + 0.845CH2O + 0.110H2O2 + 0.522CO + 0.204HCOOH + 0.199MCO3 + 0.026HO2 + 0.270OH + 0.128PRPE + 0.051MO2 | 1.00E-14 *EXP(-1970/T) | MCM v3.2 | rate is from JPL 11, products from MCM, assuming CH2OO is dominated by reactions with H2O. ISOP + O3 in standard chem is not carbon-balanced. | |
MVK + O3 = 0.202OH + 0.202HO2 + 0.352HCOOH + 0.535CO + 0.050ALD2 + 0.950MGLY + 0.050CH2O | 8.5 E-16exp(-1520/T) | MCM? | Rate is from IUPAC06 | |
MACR + O3 = 0.261OH + 0.202HO2 + 0.326HCOOH + 0.569CO + 0.880MGLY + 0.120CH2O | 1.4 E-15exp(-2100/T) | MCM? | ||
HC5 + O3 = 0.6MGLY + 0.1OH + 0.12CH2O + 0.28GLYC + 0.3O3 + 0.4CO + 0.2H2 + 0.2HAC + 0.2HCOOH | 6.16E-15 exp(-1814/T) | HC5=old IALD?? | ||
ISOPNB + O3 = 0.610MVKN + 0.390MACRN + 0.27OH + CH2O | 1.06E-16 | Lockwood et al., 2010 ACP | use 1,2 for beta channel | |
ISOPND + O3 = 0.5PROPNN + 0.5ETHLN + 0.27OH + 0.5GLYC + 0.5HAC | 5.3E-17 | Lockwood et al., 2010 ACP | use 1,4 for delta channel | |
MOBA + O3 =OH +HO2+CO2+MEK | 2.00E-17 | Paulot 2009a | Weak constraint on the rate constant - no constraint on the products | |
PMN + O3 = NO2 + 0.6CH2O + HO2 | 8.0E-18 | ? | ||
Isomerization reactions | ||||
RIO2 = 2.0HO2 + 1.0CH2O + 0.5MGLY + 0.5GLYC + 0.5GLYX + 0.5GLYX + 0.500HAC + 1.0OH | 4.07E+08 exp(-7694/T) | Peeters et al. (2009, 2010) | Isomerization rate is adjusted according to Crounse et al. (2010), products follow Stavrakou et al. (2010). | |
MRO2 = 1.0CO + 1.0HAC + 1.0OH | 2.90E+07 exp(-5297/T) | Crounse et al. (2012) | 1,4-H-shift isomerization rate dominates over 1,5-H-shift. | |
Nighttime isoprene chemistry | ||||
ISOP + NO3 = INO2 | 3.3E-12exp(-450/T) | Sander et al. 2012 | from JPL | |
MACR + NO3 = MAN2 | 2.30E-15 | IUPAC06 | ||
MACR + NO3 = MAO3 + HNO3 | 1.10E-15 | IUPAC06 | IUPAC06 total rate is 3.4E-15, so use the ratio from Lurmann et al.,1986 | |
INO2 + NO = 0.70ISN1 + 0.035MVK + 0.035MACR + 0.07*CH2O + 0.80HO2 + 1.3NO2 + 0.23HC5 | 2.7E-12 exp(350/T) | Rollins et al. (2009) | ISN1 is the NIT1 in Rollins et al. (2009) | |
INO2 + NO3 = 0.70ISN1 + 0.035MVK + 0.035MACR + 0.07CH2O + 0.80HO2 + 1.3NO2 + 0.23*HC5 | 2.3E-12 | |||
INO2 + HO2 = INPN | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | Xie et al. (2012) | ||
INPN + OH = 1.0OH + 1.0NO2 + 1.0MEK | 1.9E-11exp(390/T) | |||
INPN + OH = 0.36INO2 + 0.64R4N2 + 0.64OH | 5.18E-12exp(200/T) | |||
INO2 + MO2=0.35*ISN1 + 0.0175*MVK + 0.0175*MACR + 0.15*NO2 + 0.40*HO2 + 0.035*HCHO + 0.115*HC5 + 0.25*ISN1 + 0.25*ISOPND + 0.5*HCHO + 0.5*HO2 + 0.25*HCHO + 0.25*MEOH | 1.30E-12 | |||
INO2 + MCO3 = MO2 + 0.70ISN1 + 0.035MVK + 0.035MACR + 0.07CH2O + 0.80HO2 + 0.3NO2 + 0.23HC5 | 1.68E-12 exp(500/T) | |||
INO2 + MCO3 = RCHO + ACTA + NO2 | 1.87E-13 exp(500/T) | |||
INO2 + INO2 = 0.3NO2 + 0.70ISN1 + 0.035MVK + 0.035MACR + 0.07CH2O + 0.8 HO2 + 0.23HC5 + 0.5ISN1 + 0.5ISOPND | 1.20E-12 | |||
ISN1 + NO3 = 0.6*ISNOOA + 0.4* ISNOOB + 0.6*HNO3 | 3.15E-13*exp(-448/T) | Xie et al. (2012) | ISNOOA and ISNOOB correspond to NIT1NO3OOA and NIT1NO3OOB in Xie et al. (2012) | |
ISNOOA + NO3 = NO2 + R4N2 + CO +HO2 | 4.00E-12 | |||
ISNOOA + NO = NO2 + R4N2 + CO +HO2 | 6.70E-12*exp(340/T) | |||
ISNOOA + HO2 = 0.75RP + 0.25RCOOH + 0.25O3 | 5.20E-13*exp(980/T) | |||
ISNOOA + NO2 = MPAN | LPL: 9.00E-28(300/T)^8.9; HPL:7.70E-12(300/T)^0.2; Fc: 0.6 | |||
ISNOOB + NO3=R4N2 + GLYX + NO2 + NO2 | 2.30E-12 | |||
ISNOOB + NO = 0.94R4N2 + 0.94GLYX + 0.94 NO2 + 0.94 NO2 | 2.60*exp(380/T) | |||
ISNOOB + HO2 = INPN | 2.06E-13*exp(1300/T) | |||
ISNOOB + MO2 = 0.7R4N2 + 0.7GLYX + 0.7NO2 + 0.25HCHO + 0.25MOH + 0.5HO2 + 0.5HCHO | 2.0E-13 | |||
ISN1 + O3 = 0.3R4N2 + 0.45CO + 0.15OH + 0.45 HO2 + 0.7 GLYX + 0.7 OH + 0.7NO2 + 0.7MGLY | 4.15E-15*exp(-1520/T) | |||
ISN1 + OH = 0.345ISNOOA + 0.655ISNOHOO | 7.48E-12*exp(410/T) | ISNOHOO is NIT1OHOO in Xie et al. (2012). | ||
ISNOHOO + NO = 0.934R4N2 + 0.934HO2 + 0.919GLY | 2.60E-12*exp(380/T) | |||
ISNOHOO + HO2 = INPN | 2.06E-13*exp(1300/T) | |||
ISNOHOO + MO2 = 0.7R4N2 + 0.7 GLY + 0.7HO2 + 0.25 HCHO + 0.25MOH + 0.5 CH2O + 0.5 HO2 | 2.0E-13 | |||
Photolysis reactions | ||||
O3 + H2O = 2.0OH | JO1D | JPL2011 | Assume steady state of O1D. The rate is calculated in calcrate.F with the quenching from N2 and O2 taken into account. | |
NO2 = NO + O3 | JNO2 | |||
H2O2 = 2OH | JH2O2 | |||
MP = CH2O + HO2 + OH | J_ROOH | |||
CH2O = HO2 + HO2 + CO | ||||
CH2O = H2 + CO | ||||
HNO3 = OH + NO | ||||
HNO4 = OH + NO3 | J_HO2NO2*0.05 | Chemistry_Issues#near-IR_photolysis_of_HNO4 | ||
HNO4 = HO2 + NO2 | J_HO2NO2*0.95 | Chemistry_Issues#near-IR_photolysis_of_HNO4 | ||
NO3 = NO2 + O3 | ||||
NO3 = NO + O2 | ||||
N2O5 = NO3 + NO2 | ||||
N2O5 = NO3 + NO + O3 | 0 | turned off | ||
ALD2 = MO2 + HO2 + CO | ||||
ALD2 = CH4 + CO | ||||
PAN = 0.6MCO3 + 0.6NO2 + 0.4MO2 | ||||
RCHO = ETO2 + HO2 + CO | ||||
ACET = MCO3 + MO2 | ||||
ACET = 2.0MO2 + CO | ||||
MEK = 0.85MCO3 + 0.85ETO2 + 0.15MO2 + 0.15RCO3 | ||||
GLYC = CH2O + 2.0HO2 + CO | ||||
GLYX = 0.5H2 + CO + 0.5CH2O + 0.5CO | ||||
GLYX = 2.0CO + 2.0HO2 | ||||
MGLY = MCO3 + CO +HO2 | J_MGLY | |||
MGLY = ALD2 + CO | 0 | turned off | ||
MVK = PRPE + CO | J_MVK*0.6 | |||
MVK = MCO3 + CH2O + CO + HO2 | J_MVK*0.2 | |||
MVK = MO2 + MAO3 | J_MVK*0.2 | |||
MACR = MAO3 + HO2 | J_MACR*0.5 | |||
MACR = CO + HO2 + CH2O + MCO3 | J_MACR*0.5 | |||
HAC = MCO3 + CH2O + HO2 | ||||
INPN = OH + HO2 + RCHO + NO2 | J_ROOH | |||
PRPN = OH + HO2 + RCHO + NO2 | J_ROOH | |||
ETP = OH + HO2 + ALD2 | J_ROOH | |||
RA3P = OH + HO2 + RCHO | J_ROOH | |||
RB3P = OH + HO2 + ACET | J_ROOH | |||
R4P = OH + HO2 + RCHO | J_ROOH | |||
PP = OH + HO2 + ALD2 + CH2O | J_ROOH | |||
RP = OH + HO2 + ALD2 | J_ROOH | |||
RIP = OH + HO2 + 0.710CH2O + 0.425MVK + 0.285MACR + 0.29HC5 | J_ROOH | |||
IAP = OH + HO2 + 0.67CO + 0.190H2 + 0.36HAC + 0.26GLYC + 0.580MGLY | J_ROOH | |||
ISNP = OH + HO2 + RCHO + NO2 | J_ROOH | |||
VRP = OH + 0.3HO2 + 0.3CH2O + 0.7MCO3 + 0.7GLYC + 0.3MGLY | J_ROOH | |||
MRP = OH + HO2 + HAC + CO + CH2O | J_ROOH | |||
MAOP = OH + CH2O + MCO3 | J_ROOH | |||
R4N2 = NO2 + 0.320ACET + 0.190MEK + 0.180MO2 + 0.270HO2 + 0.320ALD2 + 0.130RCHO + 0.050A3O2 + 0.180B3O2 + 0.320ETO2 | J_MeNO3 | |||
MAP = OH + MO2 | J_ROOH | |||
MACRN = NO2 + HAC + MGLY + 0.5CH2O + HO2 + 0.5CO | J_ONIT1 | |||
MVKN = GLYC + NO2 + MCO3 | J_ONIT1 | |||
ISOPNB = HC5 + NO2 + HO2 | J_ONIT1 | |||
ISOPND = HC5 + NO2 + HO2 | J_ONIT1 | |||
PROPNN = CH2O + NO2 + CO + MO2 | J_ONIT1 | |||
ATOOH = OH + CH2O +MCO3 | J_ROOH |
RIP+OH
Follow SAR rules assuming a C(OOH) = 2* C(OH) = 7 (for the abstraction of the H alpha of the peroxide group). (see Kwok 1995 paper)
Assume that the abstraction of the peroxide H has a constant rate @298K of 3.6e-12
This gives for RIP:
43% 3.6e-12 (1,2) 28% 3.6e-12+7*1.94e-12 (4,3) 29% 3.6e-12+7*0.937e-12 (1,4)+(4,1) (I neglected 3,4 and 2,1) 9.3e-12@298K (4.75e-12*exp(200/T)) 0.387 not recycling
Therefore 0.387=3.6/9.3. RIP + OH = 0.387RIO2 + 0.613OH + 0.613HC5.
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) Note: this is applied to RIO2, VRO2, MRO2, MAN2, INO2, HC5OO, ISOPNBO2, ISOPNDO2, MACRNO2, DIBOO, MOBAOO in the new isoprene chemistry, but not MAO3, MCO3, RCO3 radicals (acetyl peroxy type radicals.
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)
Updates 02/04/2013
These reactions are updated from the beta-version of Paulot scheme.
Old reaction | Old rate | New reaction | New rate | Note |
---|---|---|---|---|
KO2+HO2 =OH +ALD2 +MCO3 | 7.40E-13 exp(700/T) | KO2 + HO2 = 0.15OH +0.15ALD2 +0.15 MCO3 + 0.85 ATOOH | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=4 | Assuming 15% recycling of OH, consistent with MCM. Rate is also from Saunders et al. (2003). |
MRO2 +HO2 =0.020MRP+0.980OH +0.980HO2+0.294CH2O+0.686HAC +0.294MGLY +0.686CO | 7.40E-13 exp(700/T) | MRO2 + HO2 = 1.0MRP | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=4 | Isomerization of MRO2 is already taken into account in another reaction. |
MAN2 + HO2 = 0.5PROPNN + 0.5CO + 0.5HO2 + 0.5MGLY + 0.5CH2O + 0.5NO2 + OH | 7.40E-13 exp(700/T) | MAN2 + HO2 = 0.075PROPNN + 0.075CO + 0.075HO2 + 0.075MGLY + 0.075CH2O + 0.075NO2 + 0.15OH + 0.85ISNP | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=4 | assuming 15% recycling |
INO2 + HO2 = 0.5INPN + 0.5ISOPND + 0.5OH + 0.5HO2 | 7.40E-13 exp(700/T) | INO2 + HO2 = INPN | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | See nighttime chemistry |
MAO3 + HO2 = 0.87OH +0.03O3 + 0.435CH2O + 0.435MO2 + 0.1MAOP + 0.030RCOOH + 0.283HAC + 0.152ATO2 + 0.870CO2 + 0.435CO | 4.3E-13exp(1040/T) | MAO3 + HO2 = 0.44OH +0.15O3 + 0.59CH2O + 0.39MO2 + 0.41MAOP + 0.39CO | 4.3E-13exp(1040/T) | use MCM, 44% OH channel, 15% O3 channel, 41% peroxide channel. |
PMN + OH = 1.000PMNO2 | 3.20E-11 | PMN + OH = HAC + CO + NO2 | 2.90E-11 | from MCM |
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) | we now remove all reactions from PMN following MCM. | ||
PMNO2 + NO=PMNN | K* YN where YN is returned from fyrno3.f ; K=2.7E-12 exp(350/T) (Xcarbn=4.0E00) | |||
PMNO2 + HO2 = 0.6CO2 + 0.6HAC + 0.6NO3 + 0.4CH2O + 0.4HO2 + 0.4PYPAN + 0.5R4P + 0.5OH | 7.4E-13exp(700/T) | |||
PYPO2 + NO2 + M = PYPAN | LPL: 9.0E-28(300/T)^8.9 HPL:7.70E-12(300/T)^0.2 Fc: 0.6 | |||
PYPAN =PYPO2 +NO2 | 9.0E-29exp(14000/T) | |||
PYPO2 + NO = CO2+MCO3 +NO2 | 2.7E-12 exp(350/T) | |||
PYPO2 + HO2 = CO2+MCO3 +OH | 7.40E-13 exp(700/T) | |||
PYPAN = 0.300NO3+0.700NO2+MCO3 +CO2 | photolysis | |||
PYPAN = NO3 + MCO3 + CO2 | photolysis | |||
PP+OH=0.791OH+0.209PO2+0.791RCHO | 8.78E-12exp(200/T) | PP+OH=0.791OH+0.209PO2+0.791HAC | ||
DIBOO+HO2 = HO2 + OH + 0.52GLYC + 0.52MGLY + 0.48HAC + 0.48GLYX | 7.4E-13exp(700/T) | DIBOO + HO2 = 0.15HO2 + 0.15OH + 0.078GLYC + 0.078MGLY + 0.072HAC + 0.072GLYX + 0.85R4P | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | assume 15% recycling of OH, rest goes to R4P |
MOBAOO + HO2 = 0.5OH + 0.5HO2 + 0.5RCHO + 0.5CO2 + 0.5R4P | 7.4E-13exp(700/T) | MOBAOO + HO2=0.15OH + 0.15HO2 + 0.15RCHO + 0.15CO2 + 0.85R4P | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | assume 15% recycling of OH, rest goes to R4P |
IEPOXOO + HO2 = | 7.4E-13exp(700/T) | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | ||
MAOPO2 + HO2 = | 7.4E-13exp(700/T) | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=4 | ||
HC5OO + HO2 = | 7.4E-13exp(700/T) | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | ||
ISOPNDO2 + HO2 = | 7.4E-13exp(700/T) | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | ||
ISOPNBO2 + HO2 = | 7.4E-13exp(700/T) | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=5 | ||
MACRNO2 + HO2 = | 7.4E-13exp(700/T) | 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], n=4 |
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