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Chemistry of Atmospheric Reactions of VOCs Leading to Smog

VOC molecules are the perfect feedstock for oxidation


In summary this situation is not benecial to humans as

these reactive oxidizers are available to react with VOCs
and produce what we know as photochemical smog4.


In bright sunlight nitrogen oxides, VOCs, and oxygen react
chemically to produce powerful oxidants such as
ozone (O3), oxygen free radicals (O*), and intermediate
compounds such as peroxyacetyl nitrates (PANs). Since
there is no sunlight, this does not happen at night. Ozone
and PANs are temporarily created, but destroyed in
subsequent reactions. PANs are primarily responsible for
the eye irritation so characteristic of this type of smog. Both
pollutants have signicant effects on human health.
The path to smog formed from VOCs starts with the
reactive oxidizers (O3 and O*) available from the chemistry associated with pollution byproducts from combustion (Equations B1-3, B1-4, and B1-5).
An oxygen free radical O* reacts with water (humidity)
to produce another free radical, as in Equation B1-75,6
(or Equation 11.3).
O H2 O52HO

B1  7

Yet in this process, a tiny amount of light of UV frequency is also

removed from sunlight (which is slightly benecial to humans).
There are two types of oxygen atoms (both identied as O* above)
involved in the smog system, which differ in their electronic state or the
level of internal energy they contain. The lowest energy oxygen atoms,
called O3P (O-triplet P) are formed from NO2 + hn and mainly react with
oxygen to form ozone. However, this form of oxygen atom doesn't
have enough energy to react with H2O to form HO* as shown in
Equation B1-7.
The second reaction can only occur with an excited, or high-energy,
form of oxygen atoms called O1D (O-singlet D). This high-energy form is
produced from the photolysis of ozone at the shortest wavelength UV
light (highest energy from Figure B1-1), not from the photolysis of NO2
at the light wavelengths present in the atmosphere. Most of the O1D
that is formed is deactivated to O3P when it collides with O2 or N2 in the
atmosphere, but some of it reacts with H2O to form HO*. These two
forms of O* are different.
The reaction of O1D oxygen atoms with H2O isn't the only source of
HO* or even the largest in many urban smog systems. Most of the HO*
comes from the reactions of HOO (HO2) with NO [HOO + NO e> HO* +
NO2]. This is a free radical propagation reaction (producing HO*) that is
part of the radical chain reactions involved in the smog-creation system.
The radical chain reaction aspect of the smog oxidation reactions is one
of its most important characteristics.
Even though the reaction rate is lower, the formation of HO* from
reaction of O1D oxygen with H2O is important because it is a radical
initiation reaction. Initiation reactions are important because they start
the chain reactions involving HO* and VOC oxidation. O1D + H2O isn't
the only initiation reaction. Others include the photolysis of aldehydes or
other photoreactive VOC products, photolysis of HONO, and so on. But
the reaction of O1D with H2O is important under cleaner (less
VOC-polluted) conditions.



The HO* specie (called a hydroxyl radical7) is unstable

and quickly reacts with hydrocarbons8, as shown in
Equation B1-8, regenerating water but also producing
another free radical9.
R  H HO /H2 O R 

B1  8

The specie R* in Equation B1-8 (or Equation 6.2A or Equation 11.14) is called a hydrocarbon radical. Like other free
radicals it is extremely reactive, as is shown in Equation B1-9.
R  O2 /ROO

B1  9

The specie ROO* in Equation B1-9 is called a peroxide

radical. A peroxide is a pair of linked oxygen atoms attached
to a hydrocarbon10. This species exists because there are free
oxygen atoms (O* as in Footnote 5) which produce its
precursors R* and HO*. But the peroxide radical doesn't
exist for very long.
Next it reacts, in two steps, with nitric oxide pollution
from combustion (NO) and oxygen to make a stable compounddan aldehyde (R-CHO), and another free radical.
Note that Equation B1-10 is the rst in which pollution
byproducts of combustion, nitric oxide (NO), and VOCs
(ROO*) interact. Unfortunately, Equation B1-10 is not
a reversible reaction11.
The group HOO*12 is called a hydroperoxide. Equation
B1-11 shows its production. Equation B1-11 is a reversible

B1  10

The hydroxyl radical, HO*, is not the same as the hydroxyl ion OH
(Chapter 1, Footnote 19). The former is neutral. The latter has a negative
charge. Some identify the hydroxyl radical as just OH, which can be confusing.
In this description, hydrocarbon solvents will be described as R-H,
where R is the main solvent structure (Figure 1.2) and H is
a hydrogen atom attached to that structure.
This description applies to all solvents except those which don't have
hydrogen atoms. Perchloroethylene is such an exception. Recall that the
unsaturated double bond between the two carbon atoms is very
reactive. Therefore, these compounds have a short atmospheric lifetime
and don't signicantly penetrate the upper atmosphere. In other words,
R doesn't exist in the upper atmosphere; R-H does exist.
This reaction is very important since it is the primary reaction pathway
by which most organic compounds initially participate in atmospheric
photochemical reaction processes. If the reaction of Equation B1-8 could
be impeded, VOCs would not form photochemical smog.
The reaction rate constant for Equation B1-8, called kOH, has been
and can be used to determine whether a solvent is VOC exempt. The
literature kOH value for ethane is 2.54 x 1013 cm3/molecule-sec.
Petitions for VOC exemption of solvents with kOH values larger than 2.54
x 1013 would likely be denied. kOH data may be found in Professor
Carter's XLS spreadsheet SAPRC07.XLS (Tab B) which is available from
his collection of materials referenced in Chapter 6, Endnote S.
R is the HC to which the aldehyde is attached (Figure 1.2).
There is a reaction between RO* and NO2, but it is relatively
unimportant in the atmosphere because of the many other ways that the
RO* radical can react. It also forms RONO2 (an organic nitrate), not RO2
+ NO. However, there is a second reaction of RO2 (ROO) with NO, [RO2 +
NO e> RONO2] that is a minor pathway for most RO2 radicals but
becomes increasingly important as the size of the RO2 radical increases.
This reaction is radical terminating and is the reason that the MIRs tend
to decrease as the size of the molecule increases.
Sometimes the hydroperoxide (H-O-O-*) is referred to as HO2.