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Envr 890 Organic Aerosols: Lecture 2. What questions do we have to start asking if we are to build a kinetics model to predict aerosol formation from isoprene reactions? [email protected] http://www.unc.edu/~kamens. Objective. - PowerPoint PPT Presentation
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Envr 890 Organic Aerosols: Lecture 2. What questions do we have to start asking if we are to build a kinetics model to predict aerosol formation from isoprene reactions?
[email protected]://www.unc.edu/~kamens
Objective
• To describe a predictive technique for the formation of aerosols from biogenic hydrocarbons based on fundamental principals and apply it to isoprene
• Have the ability to embrace a range of different atmospheric chemical and physical conditions which bring about aerosol formation.
Chemical System
-pinene
+ NOx+ sunlight + ozone----> aerosols
Overview
• This reaction system produces low vapor pressure reaction products that distribute between gas and particle phases.
Gas Particle Partitioning
particle
gas phase products
COOHO
cis-pinonicacid
• Equilibrium partitioning between the gas and particle phases is assumed for all products.
• Kinetically this is represented as forward and backward reactions.
• Kp = kon/koff
Kpart TSP
gasp
[ ] /
[ ]
KR T
p M wpLo
7 5 0 1
1 0 9
. fom
The equilibrium constant Kp can be calculated from
[gas] + [surface] [particle]
Overview
• Gas and particle phase reactions were linked in one mechanism and a chemical kinetics solver was used to simulate the reaction over time
• Model simulations were compared with aerosol concentrations obtained by reacting -pinene with either O3 or NOx in
sunlight in an outdoor chamber.
-pinene-O3 experiments in the UNC 190m3
outdoor chamber
1. added O3 O3
O3
O3
O3
-pine
O3
O3
2. added -pinene-pine
-pine
-pinene-O3 experiments in the UNC 190m3
outdoor chamber
1. added O3 O3
O3
O3
O3
-pine
O3
O33. immediate burst of particles
2. added -pinene-pine
-pine
Products
• pinald -
• pinacid -
• diacid -
• oxy-pinald -
• oxy-acid-
pinonaldehyde
CHOO
CHO
O
nor-pinonaldehyde
Pinic acid
HOOC
COOH
HOOC COO
C8 diacid
O CHO
OHO COOH
OH
Pinonic acid
O COOH
COOH
O
Norpinonic acid
CHOOO
CH3
OO
O
Criegee2
Criegee1OO O
-pinene
O3
COOHCOOH
pinic acid
+ otherproducts
O
pinonic acid
CHOO
COOH
+ CO, HO2, OH
COOHO
norpinonaldehyde
norpinonic acid
Mechanism
• Now you need to know about the reactions of alkenes with O3
• C=C +O3
• See pages Pitts and Pitts, 2000, pages 179-206
1st the reaction of O3 with an alkene generates an aldehyde +a high energy bi-radical called a Criegee bi-radical
2nd a certain fraction of these “hot” Criegee’s stabilize and the rest decomposes. (see page 198 of Pitts and Pitts, Table 6.10)
3rd “Hot” Criegee’s R-(H)C.-00. decompose to OH, CO and an R. group
How do we chemically represent his reaction scheme?
propylene +O3 two Criegee’s
C-C=C +O3 H2C.OO.* + CH3C.HOO.*
+ what two aldehydes?
For the propylene +O3 reaction (page 198
Pitts and Pitts)
CH3C.HOO.* 0.15 Stabilized Criegee
0.54 (CH3. + CO +OH.)
CH3. + CO2+ H.
HCO +CH3O 0.17
0.14 (CH4 + CO2)
apine + O3 0.4*crieg1 + 0.6*crieg2 min-1 or ppm-1min-1
1.492 e-732/T
More highly substituted Criegee’s are more stable
How do we chemically represent this for the -pinene system?
crieg1 = 0.47*pinacid + 0.13*stabcrieg1 1x106
+ 0.8*OH + 0.3*HO2 + 0.37*pinald + 0.01*oxypinald + 0.03*O. + 0.19*CO
What would we do for isoprene (see Kamens et al, IJKS, 1982?
OH attack on -pinene
CHO
O
OH
HOOOHOO CHO
OH
+ OH
O2
OOOH
-pinene
pinonaldehyde
Each Reaction can be represented as a differential equation
-pinene + ozone --> pinald
d[-pinene]/dt = -krate1 [-pinene][O3]
d[pinald]/dt = -krate2[pinal][OH]
Particle formation-self nucleation
Particle formation-self nucleation
Criegee’s can react with aldehydes and carboxylic groups to form secondary ozonides and anhydrides.
O=C
C=O
CH3
+C
C=O.
CH3
oo.
C
C=O
CH3
C
C=O
CH3
O
oo
• Estimating rates that gas phase products enter and leave the particle
• The equilibrium between the gas and particle phases is:
• Kp = kon/koff
• The equilibrium constant Kp can be calculated from
• [gas] + [surface] [particle]
KR T
p M wpLo
7 5 0 1
1 0 9
. fom
Kp = kon/koff
A general Flux expression for evaporation from a liquid surface is
is the energy barrier for single molecule to evaporate from the surface (Joules)
koff = k evap
in koff = e -Ea/RT is: kbT/h
From koff and Kp the rate coefficient kon can now be calculated
jk T
h k Tk
evapevapb
b
exp
Overall Mechanism
• linked gas and particle phase rate expressions
diacidgas + pinacidpart --> pinacidpart + diacidpart 68
diacidpart diacidgas
3.73x1014 e-10285/T
Diacid is generated in the gas phase. How do we get it on and off the particle phase??
Where do the rate coefficients come from??
KR T
p M wpLo
7 5 0 1
1 0 9
. fom
• Kp = kon/koff
koff = e -Ea/RT
We need vapor pressure (poL ) to calculate Kp
for koff , we need kbT/h for and an
activation energy, Ea
To calculate vapor pressures see Chapter 4 of (Schwarzenbach et al, Environmental Organic Chemistry, 2003)
)]()([TT
ln.TT
.R
S*pln bbvapT
iLb 80181
if we substitute Svap Tb= 88J mol-1 K-1 and R =8.31 Jmol-1 K-1
)]()( ln.ln *
T
T
T
Tp bb
iL 58119
This means we need Tb or boiling point
Boiling points can be estimated based on chemical structure (Joback, 1984)
Tb= 198 + Tb
T (oK)
-CH3 = 23.58 K-Cl = 38.13-NH2 = 73.23
C=O = 76.75CbenzH- = 26.73
C-OH = 93 Joback obs
(K) (K)acetonitrile 347 355acetone 322 329benzene 358 353amino benzene 435 457benzoic acid 532 522toluene 386 384pentane 314 309methyl amine 295 267trichlorethylene 361 360phenanthrene 598 613
Stein, S.E., Brown, R.L. Estimating Normal boiling Points from Group Contributions, J.Chem. Inf Comput. Sci, 34, 581-587, 1994
Chamber Data
• First look at experiments with different temperatures and gas phase concentrations of -pinene and ozone
A high concentration warm experiment
• 0.82 ppmV -pinene + 0.60 ppm O3
• Temp = ~295K
• %RH = ~61%
0
0.2
0.4
0.6
0.8
1
pp
mV
9 9.2 9.4 9.6 9.8 10 Time in hours
Gas Phase -pinene and O3 data and model
-pinene
A
MODEL
Particle concentration. Warm high concentration experiment
0
1
2
3
4
5
9 10 11 12 13 time in hours
A
model
Observed
Reacted -pinene
mg
/m3
Other Conditons
0.82 ppmv -pinene + 0.60 ppm O3(295K)
0.60 ppmv -pinene + 0.65 ppm O3 (284K)
0.35 ppmv -pinene + 0.25 ppm O3 (295K)
0.88 ppmv -pinene + 0.47 ppm O3(269K)
Lower concentration experiments
0.20 ppm -pinene + 0.11 ppm O3
TSP data vs model
0
20
40
60
80
100
120
140
160
180
200
21 21.5 22 22.5 23 23.5 24time in hours
ug/m
3
filter mass model TSP
model
data
How do we start to build an Isoprene + O3 mechanism??
The initail attack of O3 on an olefin (alkene) generates two possible Criegee high energy bi-radicals and two possible aldehydes.
A general rule is that the more highly substituted carbon will form a higher fraction of Criegee’s
C=C-C=CH
HCH3
H
HH
+ O3 MACR + H2C.OO.
CI1.OO. + HCHO
MVK + H2C.OO. CI2.OO. + HCHO
What would we do for isoprene (see Kamens et al, IJKS, 1982?
There are 4 general product channels by which high energy Criegee’s (Criegee intermediates) decompose:
1. Stabilized Criegee biradicals
2. an Ester Channel
3. O-atom elimination
4. Hydroperoxide channel
The hydroperoxide channel is a source of dark OH
Homework 3: For MVK write a set of Chemical equations to show it’s decomposition
MVK + O3
H2C=C - C-CH3
H O (MVK)MVK + O3 MGLY+ H2C.OO.*
.OOC.C(H)-C(=O)-CH3 +HCHO
let’s assign splitting ratios
2. MVK + O3 0.4 MGLY+ 0.4 H2C.OO.*
0.6 CI2*+0.6 HCHO
MVK + O3
MVK + O3 0.4 MGLY+ 0.4 H2C.OO.*
0.6 CI2 * +0.6 HCHO
how does H2C.OO. decompose??
(look at page 197 of Pitts and Pitts,2000)
H2C.OO.* 0.37 Stabcrieg1 +0.12 HCO+
0.12 OH. +0.38 CO+ 0.38 H2O
Stabilized Criegee’s usually react with water
Stabcrieg + H2O Aldehyde +H2O2
H2C.OO.* + H2O H2C=O + H2O2
Stabcrieg + Aldehyde secondary ozonide
How do we add rate constants??
Adding Rate constants
MVK + O3 MGLY+ H2C.OO.
.OOC.C(H)-C(=O)-CH3 +HCHO
6X10-3 ppm-1 min-1
H2C.00. + H2O H2C=O + H2O2
5.4x10-2 ppm-1 min-1
look in Pitts and Pitts to convert
ppm-1 min-1 to cm3molecule-1sec-1
Does OH attack Isoprene, MACR,MVK,MGLY and HCHO???
isoprene + OH products
MACR+ OH products
MVK + OH products
MGLY +OH products
H2C=O +OH products
NO3+alkenes products
radical +radicals stable products
aldehydes photolyze
Light model for -pinene + NOx
• -pinene + OH Noizoire et al.
• -pinene + NO3 Martinez et al., Wangberg et al.
• -pinene(OH)-OO + NOx--> products Aschmann et al.
• pinonaldehyde +OH or NO3 Calogirou et al.
• pinonaldehyde photolysis Hallquist et al
• acyl peroxy + NO2 --> PAN analogues Noizoire et al.
• partition nitrate products
pinonaldehyde
OH
OO
O2
+
(a)(b)
(c)
(d)
(e)
pinonaldehyde
acetone
O
OO.
NO2NO
O
O.
pinald-oo
OH
pinonic acid
O
pinO2
OO.
NO2
NO
organic nitrate
+HO2
+NO2
pinald-PAN
=o
=o
=o
=o
=o
=o
=o
OO.
O2
=o
OO=C8=O
C8-oo.
O2
NO2NO
O
+ h
+
+CO+HO2=o
OO.
NO2NO
=o
=o+HO2
+ h
NO2NO
=o
OO.
C8-oo. (C8O2)
+CO+HO2
NO2
NO
(f)
(g)
CO2+
pinO2H2O+
+HO2
O2
OO
H3C-OO.
+oxygenated products
+NO2
+H3C-OONO2PAN
(stab-oxy)
+HO2
norpinonaldehyde
OOH
O=o+
pin-ooH
+OH
O
OO.
=o
NO2
NO
+CO2
norpinaldPAN
+NO2
+HO2
norpinonic acid+norpin-ooH
O
OONO2
=o
+O2
ONO2
=o
+
=o
ONO2
+
organic nitrate
Pinonaldehyde chemistry
Pinald +h = 0.65pinO2 + 1.35 CO + HO2 + 0.35*C8O2`
# hpinald
pinO2 + NO= .765pinald + .85 HO2 + 0.1*acetone +0.2C2O3 + .865NO2 # 6056 exp 180/T
C8O2 + NO = NO2 {+ C8-dicarb } # 6056 exp 180/T pinald + OH = . 8 pinald-oo + 0.1C3O2 + 0.1C8O2 + 0.1 acetone +0.3XO2 # 134417, pinald + NO3 = 0.95*pinald-oo +0.03*pinO2
+0.02*C8O2 + 0.07*CO +NO2 # 79
pinald-oo + NO = pinO2 +CO2 +NO 2 # 7915 exp250/T
pinald-oo + NO 2 = pinald-PAN #3885exp380/T
pinald-PAN = pinald-oo + NO2 # 1.067e11 exp-8864/T pinald-oo + pinald-oo = 2*pinO2 # 2551
pinald-oo + HO2 = Pinacid
# 677 @1040
kphototyis = ( I)
By adding pinonaldehyde to the chamber in clear sunlight in the presence of an OH scavenger and measuring its rate of decay
can be fit to the decay data assuming
a shape with wave length similar to other aldehydes
Pinonaldehyde quantum yields in natural sunlight
Pinonaldehyde quantum yields in sunlight
0
0.2
0.4
0.6
0.8
1
280 310 340 370Wavelenght /nm
quan
tum
yie
ld
CH2=O
CH3CH2CH2=O
OO
pinonaldehyde
CH3CH2=O
0
0.4
0.8
1.2
280 300 320 340
Normalized to one
pinonaldehyde
0.97 ppm -pinene + 0. 48ppm NOx;
October Sunlight
O3
NO
NO2
NO2
-pinene data vs. model
model
data
-pinene
Gas phase pinonaldehye
model
data
OO
=o
=o
pinonaldehyde
norpinonaldehyde
Particle phase pinonic acid
model
pinonic acid data
norpinonic acid
OH
pinonic acid
O=o
Measured particle mass vs. model
model
products
Particle phase
filter data
mg
/m3
0.95 ppm -pinene + 0. 44ppm NOx
O3
NO
NO2
NO2
model
data
Measured particle mass vs. model
reacted -pinene
data
model
Gas phase pinonaldehye
OO
particle phase pinonaldehye
model
data
OO
d-limonene + O3
(Sirakarn Leungsakul, ES&T 2004)
8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.000
500000
1000000
1500000
2000000
2500000
3000000
3500000
4000000
4500000
5000000
5500000
T ime-->
AbundanceT IC: 3S1F1FD.D
keto-limononaldehyde
limononaldehyde
7OH-limononaldehyde
7OH-keto-limononaldehyde
keto-limononic acid
7OH-keto-limononic acid
7OH-limononic acid
Major particle phase productsMajor particle phase products
+ O3O
O
OOO
OOO
OO
OO
O
+ CH2-OO
O
OH
O
OO
O
O
O
O
O
O
HO
CH3-OH +
+ H2O
+ OH
O
OO
O
O
+ H2O
O
O
+ H2O
0.15
0.500.35
0.65
0.200.25
0.20
0.10
0.68
0.85
0.32
0.30
keto-limonene
limononaldehyde
limonalic acid
keto-limald
7OH-limononaldehyde
Crieg1*
Crieg2* Stab-Crieg2
Stab-Crieg1
OH
+ H2O
limononic acid0.37
0.63
d-limonene
O3
Filter data and Model
d-limonene + Od-limonene + O33
(Sirakarn Leungsakul, 2004)
aero
sol
(mg
/m3)
v
p
pm
V
.00
.02
.04
.06
.08
.10
18 19 20 21 22 23 24 1:00
LDT (hour)
(p
pm
)
0.00
30
60
90
120
150
aero
sol (
g/m
3 )
OO33
Filter
d-limonene + O3
(Sirakarn Leungsakul, 2004)(Sirakarn Leungsakul, 2004)
Model
-pinene + O3
(Mohammed Jaoui, 2003)
-pinene + O3
CH3
OH OHCH2.
NO NO2
+O2
CH3
H
OH
H .
*
O2
+ toluene
O=CHCH3
OH
+ HO2
+ H2O
CH3
O
o-cresolbenzaldehyde
CH3
H
OH
H
CH3
O
O
.CH3
H
OH
H
.O
NO
NO2
+O2
rearrangement
oxygen bridge
OH
H
O .
H
H
O
H
OH
H
O
H
+O2
CH3H+
methylglyoxalbutenedial
+ HO2
ring cleavageradical
Aerosol concentration from -pinene-NOx-sunlight
0
2000
4000
6000
8000
10000
0.01 0.1 1
particle diameter (m)
par
ticl
e co
nc.
(# /
cm)
5:19am(background)
initial
6.5 hours later
3 hours later
Experiments that explore heterogeneous carbonyl reactions (Myoseon Jang et al., Science, 2002)
• Nebulizes NH4(SO4)2 acid coated aerosols into Teflon bags
• Reacts aldehydes on the surface of the acid coated particles (~2% H2SO4 by weight)
• Diesel exhaust is 1-5% sulfuric acid
nebulizer
(NH4)2SO4
Solution
aldehydesalcoholsglyoxal
aldehydesalcoholsglyoxal
(NH4)2SO4+H2SO4
Solution
500 liter Teflon bag
•The aldehyde phenomenon can be explained as follows:
• Aldehyde functional groups can further react in the aerosol phase through heterogeneous reactions via hydration, polymerization, and hemiacetal/acetal formation with alcohols.
•Aldehyde reactions can be radically accelerated by acid catalysts such as particle sulfuric acid
H
OH
OH
H
H
OH
H OH
OH
H
H
O OH
H
H
OH H
O O
H
H
OH H
OH
H
H
O OH
H
H
OH-H+
+
+-H+
Polyimerization
H H
OH
H H
OH
H H
O
H H
OHH
+
Acid catalyzing step
H H
OH
+
H O
OH
H
HH
H OH
OH
H+ H2 O
-H+Hydration
H H
OH+
Hemiacetal and acetal formation
H O
OH
H
RH
H OR
OHH
H OR
OHH
H OR
OH2+
H
+ ROH-H+
H+ -H2O
H H
OH
H H
OR
hemiacetal
+H O
OR
H
RH
H OR
ORH
H H
ORROH
-H+
acetal
Aerosol yields from aldehydes
0.0
1.0
2.0
3.0
4.0
glyoxal hexanal octanal decanal
Aer
oso
l Yie
lds
(%)
non-acid seedacid seed
*Yield data and method from Jang et al. 2001
Acid seed experiments with O3 + organics
Nebulizer
Ozone Ozone
(NH4)2SO4
Solution
(NH4)2SO4+H2SO4
Solution
Volatilized organics
Volatilized organics
OzoneOzone
Yields from Teflon bag experiments
0.000
0.100
0.200
0.300
0.400
0.500
% y
ield
non acid seed
acid seed
isoprene isoprene/ decanol
-pinene acrolein acrolein/ decanol
Aldehyde acid catalyzed heterogeneous reactions
• Acid catalyzing step
• Hydration
• Polymerization
H
O
H
OH
H
OH
O
OH
H
H
H
OH
OHH
H
OH
+ H2O
H
OH
OH
OHH
O
OHH
H
OH
+
Etc...
H+
Particle Phase reactions
particleC=OO
polymers
Gas phase reactions
C=OO
cis-pinonaldhyde
Particle Phase reactions
particle
C=OO
cis-pinonaldhyde
C=OO
polymers
Gas phase reactions
Particle Phase reactions
C=OO
polymers
Gas phase reactions
C=OO
cis-pinonaldhyde
MS Analysis of Filter Samples from the reaction of acid seed particles with a-pinene + O3
ESI-QTOF mass spectrum of SOA from reaction of -pinene + O3 + acid seed aerosol (Tolocka et. al., 2004)
200 300 400 500 600 700 800 900 1000
m/z
337.
18 351.
18
361.
21
377.
2
393.
2
407.
2
423.
2
439.
2
453.
21 489.
32
300 320 340 360 380 400 420 440 460 480 500
321.
21
m/z
17
7.0
7
19
1.1
2 20
7.1
1
22
5.1
12
33
.14
24
5.1
2
25
5.1
82
61
.11
28
9.1
8
30
1.1
8
31
3.2
3
32
7.1
6
34
1.2
35
9.2
36
0.2
150 200 250 300 350
Inte
nsity,
A.U
.
m/z
O
OH
O
H2C
O
177
207
341
261289
91
77
.07
19
1.1
2 20
7.1
1
22
5.1
12
33
.14
24
5.1
2
25
5.1
82
61
.11
28
9.1
8
30
1.1
8
31
3.2
3
32
7.1
6
34
1.2
35
9.2
36
0.2
150 200 250 300 350
Inte
nsity,
A.U
.
m/z
O
OH
O
H2C
O
177
207
341
261289
9
M Na+ (ESI-QTOF Tolocka et al, 2003)
Particle phase pinonaldehyde dimers from -pinene +O3 on acid particles
Similar results were obtain by Hartmut Herrmann’s group (Atmos Envir, 2004)
• Kalberer and Baltensperger et al. (Science, 2004) identified polymers as the main constituents of SOA formed from the photo-oxidation of 1,3,5-trimethylbezene. These account for about 50% of the aerosol mass after 30 hours of aging.
LDI-TOFMS Spectrum of SOA from Photo-oxidation of 1,3,5-
Trimethylbezene
Time Evolution of Polymer in SOA Measured by LDI-MS
Where do we go from here for isoprene??
1. Learn what products it makes that go into the particle phase
2. Begin to describe the chemistry
3. Start to collect papers on isoprene and SOA