Appendix

B1

Chemistry of Atmospheric Reactions of VOCs Leading to Smog

Table B1-1 Major Pollutants and Reaction Products

Pollutant

Description

Effects

Nitric Oxide (NO)

Nontoxic, colorless,
odorless gas.

Easy to oxidize to NO2.

Nitrogen Dioxide (NO2)

Toxic gas

Gives polluted air a yellow to reddishbrown color and pungent odor.

Hundreds of ppb

Ozone (O3)

Active oxidant

Harmful to respiration, especially for

sensitive people such as asthmatics or
people who do strenuous exercise
outdoorsD.
Is very destructive to plants.

Hundreds of ppb, or less

Inammation of air passages reducing

lung capacity. Long-term damage to
lungs and ability to resist other lung and
throat problems. Cause a plant disorder
known as silver leaf.

10 to 20 ppb

Peroxyacetyl Nitrates
(PAN)

I. SUMMARY
The concern about these reactants, intermediates, and
products is deadly serious.
Hydrocarbon chemicals (VOCs) are not the prime cause of
contamination of the earth's air. There would be no formation of ozone-derived smog if hydrocarbon solvent emissions20 were not combined with the emissions from
combustion processes.
The equations and structures in this appendix may
appear complicated to a manager trying to remove oil and
metal particles from machined injection valves. A simplied viewpoint is shown in Figure B1-12. The identity of the
principal compounds, characteristics, and concentration
ranges is tabulated in Table B1-1.

20

Hydrocarbon emissions also come naturally from tree leaves. Trees

emit VOCs in the form of isoprene and monoterpenes (analogs of
D-limonene; Ref. 3, Chapter 7). In fact, the sharp scent of white spruce
trees comes from monoterpenes emitted from their needles.
Sesquiterpene is a particular kind of VOC that may be especially
important in atmospheric chemistry. Sesquiterpenes are suspected to be
the main ingredients in the blue haze that gives the Smoky Mountains
and Blue Ridge Mountains of Appalachia, USA, and the Blue Mountains
of New South Wales, Australia, their names.
One of the ironies of modern forest management is that increased
planting of rapidly growing trees to replace those cut for commercial
purposes has increased the ozone content of the troposphere. It seems
that more rapidly growing trees release more VOCs. In some areas,
ozone levels are increasing after all reasonable steps have been taken to
reduce VOC emissions from commercial and home sources.
The NOx needed for reaction with tree-released VOCs is provided by
automotive emissions emitted elsewhere and borne by wind currents to
where trees or machines have emitted VOCs.

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Levels of Concern

However, these equations and structures are important.

They are the scientic basis for regulations dening which
solvents can be used to remove that grease, how the solvent
cleaning equipment must be designed, and how employees
using that equipment must be protected.

Endnotes
A. In scientic literature,VOCs are often noted as ROGs (reactive organic
gases).
B. A circular process is one which could be completed within a closed
volume e a sealed bag such as a smog chamber. When the products
of one reaction appear, another can start. The following reaction will
be quenched when it the ingredients which it consumes are no
longer available. The initiating reaction of a circular process, like all
other reactions within it, is only active when its starting ingredients
are available. So, the chemical equations of a circular process dont
balance numerically, they are just periodically active.
C. More information can be found at http://www.atmos.anl.gov/ACP/
Gaffney.pdf.
D. The information upon which Figure B1-10 is based is Professor
Carters MIR dataset as noted in Chapter 6, Endnote S, and
Finlayson-Pitts B.J. & Pitts J.N. Atmospheric Chemistry of
Tropospheric Ozone Formation: Scientic and Regulatory
Implications. Air and Waste. 1993;43:1091e1100. Table II.
E. Its toxicity level determines the O3 standards that drive the VOC
regulations.