Appendix

B1

Chemistry of Atmospheric Reactions of VOCs Leading to Smog

atmosphere and is a potent toxin in the respiratory tract.

NO2 is not very water soluble and penetrates readily to the
alveoli of lungs where it forms nitrous acid (HNO2), and
nitric acid (HNO3).
Nitric oxide, or nitrogen monoxide, (NO) is relatively
nontoxic at ambient concentrations. Nitric oxide is
a colorless gas that is visible to the human eye at high
concentrations (above about 1 ppm).
Oxidation of nitric oxide (NO) to nitrogen dioxide
(NO2) occurs naturally.
NO2 v <380 nm/O NO

B1  3

In the troposphere, nitrogen dioxide (NO2) will decompose (dissociate) with energy supplied by ultraviolet (UV1)
light, as is shown in Equation B1-3.
This reaction starts (or is part of) the CRS formation
process. The specie O* is an oxygen atom or oxygen free
radical2.
What causes the reaction shown in Equation B1-3 to
occur? Why does the dissociation of NO2, as in Equation
B1-3, occur in the troposphere?
The answer is that the sunlight striking the NO2 molecule
needs to have a certain amount of energy to initiate and
maintain the dissociation reaction. That amount is about
72 kilocalorie/g-mole at 25 C (129.6 K BTU/lb-mole at
77 F).
Sunlight in the visible (>380 nanometer [nm]) range
and infrared radiation (>1000 nm) do not have sufcient
energy to support the reaction in Equation B1-3. This is
shown in Figure B1-1, as the energy content of radiation is
inversely dependent upon wavelength. Only sunlight in the
UV frequency range (<380 nm wavelength) has enough
energy to produce combustion-related smog.
The dissociation reaction of Equation B1-3 allows
production of ozone (O3), as in Equation B1-4. This
happens faster than one can read about it because the
oxygen atom is very reactive.
O2 O /O3

Figure B1-1 Variation of Radiation Energy with Frequency

The combination of these three equations (B1-3, B1-4, and

B1-5) is a circular chemical process, shown as Equation B1-6B:
NO2 O2 v <380 nm/O NO/O3 NO5NO2
O2
B1  6
This mixture of reactants and reaction products, plus suspended particulate matter, carbon monoxide (CO) emitted
from the same sources as is NOx, corollary oxides of sulfur,
aerosols with water in which all the above can dissolve, and
unreacted VOC, is known as smog3. CRS adds a browncolored tint to air (Figure B1-2) because of the presence of
oxides of nitrogen (NOx, especially NO2).
The circular process of Equation B1-6 means that at any
time there are always reactive oxidizers present (oxygen
atoms [O*] or ozone molecules [O3]). In a sense, Equation
B1-6 is the basic engine for smog production, ready and
primed for the interactions with VOCs.

B1  4

But the nitric oxide (NO) produced by the reaction shown

in Equation B1-3 isn't stable either. It reacts with ozone to
regenerate NO2 as in Equation B1-5.
NO O3 5NO2 O2

B1  5

1
The presence of photons (light of any frequency) in chemical reactions
is often noted as the lower case Greek character nu (n). The reason is
due to the relationship between the energy content of light and its
frequencydthe Plank-Einstein Equationdwhich is that Energy hn,
where h is a measurable constant named after the Nobel Prize winning
physicist Max Planck, one of the founders of quantum theory.
2
This specie is decient in electrons in its outer electron shell, and is
aggressively seeking an electron in some other molecule that it can share
in order to temporarily complete its outer electron shell. There is more
information on this topic in Chapter 11.4.2.1 where this same situation
is faced in stabilizing cleaning solvents.

548

Figure B1-2 Combustion-Related Smog

3

This mixture is named combustion-related smog in this book to

distinguish it from smog produced from VOCs, known as photochemical
smog.