Ce666a-2022-Lecture 7

Atmospheric Chemistry of CO and NOx
O3 +hυ → O+O 2 λ>315 nm

→ O(1D)+O 2 λ<315 nm
O+O 2 → O3 quickly combines (no net change)
O(1D) can have two routes:
(i) O(1D)+M → O+M

O+O 2 → O3
(ii) O(1D)+H 2O → 2OH.
(hydroxyl radical)
Contd….
This OH radical fundamental is responsible for the photo chemical/chemical

reactions:
CO + OH. → CO2+ H.
H. + O2 + M →HO2. + M
HO2. → hydroperoxyl radical
Or Simply combine:-
CO+OH. ⎯⎯
O2
→ CO 2 +HO 2
.
HO2. + NO → NO2 + OH.

This is one more route for NO oxidation
OH. radical regenerated. to NO2
Contd….
Finally, OH and NO2 may react to form nitric acid,

OH. + NO2 → HNO3
All the reactions involved in the CO-NOx chemistry are summarized
in the following table:
Summary
• The basic reaction mechanism of the CO/NOx system
exhibit many of the key features of those involving much
more complex organic molecuels.
• In particular, the role of OH as the oxidizing species and the

NO to NO2 conversion by HO2 are central to virtually every
atmospheric organic/NOx mechanism.
• It is useful to proceed to a molecule that is somewhat more

complicated than CO to see how the similar NOx
mechanism develops.
Atmospheric Chemistry of HCHO and NOx
• Formaldehyde (HCHO) is a primary pollutant and also an oxidation
product of hydrocarbons.
• These are basically emitted from automobiles.
• Formaldehyde undergoes two routes for the primary reactions in the
atmosphere: (i) Photolysis and (ii) Ordinary chemistry
Route (i):
HCHO + hυ → H. + CHO. (Formyl radical)
H. + O 2 → HO 2.
HCO. + O 2 → HO 2. + CO
Overall: HCHO + hυ ⎯⎯
O2
→ 2HO 2. + CO
→ H 2 + CO
Contd….
Route 2:
HCHO + OH. ⎯⎯
O2
→ HO2. + CO + H 2 O
Summary
• All reactions are because of photochemistry and reaction with OH.
• HCHO/HC/CO → HO2.
• HO2 to oxidize NO to NO2 .
• NOx removal from system is through OH. to HNO3
Contd….
All the reactions involved in the CO-NOx chemistry are

summarized in the following table:
Contd….
Here the CO-OH reaction is omitted from the previous Table, as it is
generally slower than those involving HCHO. Applying the PSSA, then:
Contd….
The behavior (concentration in ppm) of the system as a function of its
initial conditions for HCHO and NOx are calculated by using the models
and explained in the figures
CASE 1: (Figure 1)
[NO2]0=0.1, [NO]0=0.01,
[HCHO]0=0.1.
Then during first two minutes:
[NO2]=0.069, [NO]=0.0405,
[O3]=0.032
Over the 600 minute period, it can
be observed that after the first 20
minutes NO2 continually
decreases , since even though
NO is continually being
converted to NO2 by O3, there is
such an excess of NO2 that the
NO2-OH reaction is removing
NO2 to HNO3 at rate such that it
dominates the NO2
Contd….
This figure shows the concentration versus time for the
initial conditions: [NO2]0=0.1, [NO]0=0.1, [HCHO]0=1.0
Contd….
This figure shows the concentration versus time for the initial
conditions: [NO2]0=0.1, [NO]0=1.0, [HCHO]0=1.0
Contd….
• The conversion of NO to NO2 and the formation of O3 are

therefore driven by HCHO through its production of HO2.
Thus, the theoretical maximum amount of O3 that could be
produced in this system is:
[O3]=[HCHO]0 + [NO2]0
• When all the NOx is converted to HNO3, the system ceases
reacting. In a sense, a given system can be characterized
by its ability to produce O3.
• The effect of [HCHO]0 on NO2 dynamics is shown in the
following figure.
Contd….
Oxidation of Methane
O3 + hυ → O 2 +O(1D)
O(1D) +H 2 O → 2OH.
Then hydroxyl radicals react with CH 4 and CO
present in the atmosphere.
CH 4 + OH. → CH 3. +H 2 O
(methyl radical)
CO + OH. → CO 2 + H.
Then instantaneously the following reaction takes place
H. + O 2 +M → HO 2. +M
CH 3. +O 2 +M → CH 3O 2. +M
(methylperoxy radical)
Contd…
So that the CH 4 and CO-OH reactions may be written simply as:

CH 4 + OH. → CH 3O 2. +H 2O
CO+OH. → HO 2. +CO 2
The peroxy radicals in turn, participate in a chain-propagating

sequence that converts NO to NO2 and in the process, produces
additional OH and peroxy radical species:
CH 3O 2. + NO → NO 2 +CH 3O.
(methoxy radical)
HO 2. + NO → NO 2 +OH.
CH 3O. + O 2 → HCHO + HO 2.
(Hydroperoxyl radical)
Contd…
The major chain terminating steps include nitric acid and hydrogen
peroxide formation,
OH. + NO 2 → HNO3
HO 2. + HO 2. → H 2O 2 +O 2
The CH 3O 2 radical can react with either NO or HO 2 ,

the later reaction being:
CH 3O 2. + HO 2. → CH 3COOH+O2
The following figure shows the atmospheric degradation path for

methane.
Contd…
Generalized –Chemistry for O3 formation
NO 2 + h → NO + O
O+O 2 → O3
O3 + NO → NO 2 + O 2
RH + OH. → R . +H 2O
(general HC)
R . + O 2 → RO 2. (peroxy radical)
RO 2. + NO → RO. + NO 2
RO. + O 2 → RCHO +HO 2.
(It follows aldehyde chemistry)
→ Eventually will lead to CO 2
→ Stabilize NO 2 to HNO3
→ Form H 2 O 2 (highly oxidizing agent)
Contd…
Figure: Formation of ozone

O2
RO. RO2. R.
RH
NO
NO2+hu O
NO
O3 O2
O2
Aromatic Chemistry
Peroxyacetyl Nitrate (PAN): Consider Acetaldehyde (CH3CHO)
CH3CHO + h v CH3O2. + HO2 . +CO …. and
CH 3CHO + OH . → CH3CO. + H 2 O
(Acetyl radical)
CH 3CO. + O 2 → CH 3COO 2.
(Acetyl peroxy radical)
Pungent smell,
CH 3COO 2 + NO 2 → CH 3COO 2 NO2
.
Eye irritation,
(Peroxyacetyl Nitrate) Decomposes very
quickly in the
atmosphere
Peroxybenzyol- Nitrate (PBN)
C OO NO2
Chemistry of Sulfur Dioxide
Gas-phase reaction
OH. + SO 2 → HOSO 2.
(Rate limiting step, does not happen so easily)
HOSO 2. O 2 → HO 2. +SO3
HO 2. + NO → NO 2 +OH.
SO3 + H 2 O → H 2SO 4
Aqueous-phase reaction
HSO3-
SO2
SO42-
Through series of complex reactions, e.g. H2O2, O3, O2 → eventually
oxidized to SO4
Chemistry of Iron (Fe)
Fe:
0.19 – 0.51 μg/m3
1.1 – 2.1 μg/m3 (Urban)
Fe2O3 + SO2→ SO4 (Gas-solid phase interaction)
Solid particle with Fe Dissolved O2 can oxidize

the SO2 in presence of Fe
Aqueous phase
CO
NO NO2 O3
HC
Conc
7 AM 8 AM 12 Noon 2-3 PM 6 PM
Time
EKMA (Empirical Kinetic Modeling Approach)
Low VOC/NOx ratio ?
i.e. low O3 VOC limited
High VOC/NOx ratio?
Low O3 consumed by organic radicals
(VOC/NOx)=4
VOC
limited
NOx
(VOC/NOx)=15
200
(ppb)
KNEE 400
Region O3
Isopleths
300
In ppb
NOx
200
limited
50
150
200 1000
VOC (ppb)
Assignment/Example
Alkylperoxy nitrate decomposes in the following way
k K
RO2 NO2 ⎯⎯→
1
⎯⎯
2
RO2 + NO2
k3
RO2 + RO2 ⎯⎯→ 2 RO + O2
k4
RO + NO2 ⎯⎯→ RONO2
Assume that RO2NO2 are decomposing in a chamber and its decay is
observed. We wish to estimate k1 from the experiment. Assume RO2 and
NO2 are at pseudo-steady state and [RO2]=[NO2]. Show that first order
rate constant for RO2 NO2 decay is related to fundamental rate
constants of the system in the following way

Ce666a-2022-Lecture 7

Uploaded by

Copyright:

Available Formats

Ce666a-2022-Lecture 7

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Ce666a-2022-Lecture 7

Uploaded by

Copyright:

Available Formats

Atmospheric Chemistry of CO and NOx

O3 +hυ → O+O 2 λ>315 nm

(i) O(1D)+M → O+M

This OH radical fundamental is responsible for the photo chemical/chemical

HO2. → hydroperoxyl radical

HO2. + NO → NO2 + OH.

Finally, OH and NO2 may react to form nitric acid,

• In particular, the role of OH as the oxidizing species and the

• It is useful to proceed to a molecule that is somewhat more

All the reactions involved in the CO-NOx chemistry are

• The conversion of NO to NO2 and the formation of O3 are

So that the CH 4 and CO-OH reactions may be written simply as:

The peroxy radicals in turn, participate in a chain-propagating

The CH 3O 2 radical can react with either NO or HO 2 ,

The following figure shows the atmospheric degradation path for

Figure: Formation of ozone

Fe2O3 + SO2→ SO4 (Gas-solid phase interaction)

Solid particle with Fe Dissolved O2 can oxidize

Alkylperoxy nitrate decomposes in the following way

You might also like