Difference between revisions of "Caltech isoprene scheme"

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(New reactions)
(New reactions)
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| ||PMN + OH = HAC + CO + NO2||2.90E-11||MCM v3.2 || rates and products all from MCM
 
| ||PMN + OH = HAC + CO + NO2||2.90E-11||MCM v3.2 || rates and products all from MCM
 
|-
 
|-
| ||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 ||Paulot 2009a ||Butkovskaya 2006 companion paper and Paulot 2009
+
| ||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
 
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| ||GLYC  + OH = HCOOH + 0.190OH +0.190CO + 0.810CO2 + 0.810HO2 ||FRAC=1-11.0729*exp(-1/73T)  Rate=8.00E-12*(1-FRAC) ||Paulot 2009a ||Butkovskaya 2006 companion paper and Paulot 2009
 
| ||GLYC  + OH = HCOOH + 0.190OH +0.190CO + 0.810CO2 + 0.810HO2 ||FRAC=1-11.0729*exp(-1/73T)  Rate=8.00E-12*(1-FRAC) ||Paulot 2009a ||Butkovskaya 2006 companion paper and Paulot 2009

Revision as of 15:24, 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.

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:

  1. Isomerization of RIO2 base on Peeters et al. (2009, 2010) an Crounse et al. (2011).
  2. Isomerization of MRO2 base on Crounse et al. (2012).
  3. Nighttime isoprene oxidation based on Rollins et al. (2009) and Xie et al. (2012).
  4. 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

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
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
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 + 0.190OH +0.190CO + 0.810CO2 + 0.810HO2 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) Rate uses MP+OH
ATOOH + OH = MGLY + OH +H2O 1.14E-12exp(200/T) Rate uses 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)
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 = MO2 +.5NO2+.5CH2O+.5MGLY+.5PROPNN+.5CO+.5HO2 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
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)
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
RIP = OH + HO2 + 0.710CH2O + 0.425MVK + 0.285MACR + 0.29HC5
MACRN = NO2 + HAC + MGLY + 0.500CH2O + HO2 + 0.500CO
MVKN = GLYC + NO2 + MCO3
ISOPNB = HC5 + NO2 + HO2
ISOPND = HC5 + NO2 + HO2
PROPNN = CH2O + NO2 + CO + MO2
ATOOH = OH + CH2O +MCO3

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:

Ro2 ho2 rate.jpg

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
INPN+OH= 1.0OH + 1.0NO2 + 1.0MEK 1.9E-11exp(390/T) Now replaced by new nighttime chemistry
INPN+OH=0.36INO2+0.64R4N2+0.64OH 5.18E-12exp(200/T) Now replaced by new nighttime chemistry
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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