Chemistry of Atmospheric Reactions of VOCs Leading to Smog

B1

Appendix

Figure B1-12 Interaction of VOCs with combustion products produces photochemical smog

H.

REACTIVITY METRICS (KOH)

As Equation 6.1 allows the kinetics of the reversible reaction

Equation B1-11 to be quantied, so does it allow signicant
kinetics of the non-reversible Equation B1-8 to be quantied.
R  H HO /H2 O R 

B1  8

The reaction rate constant for this bimolecular secondorder (usually) oxidation reaction, kOH, can be determined
in an apparatus considerably smaller, simpler,17 and
cheaper than a smog chamber. This is because only two
chemical species are requireddthe organic chemical and
a source of hydroxyl radicals18 as oxidizing agents. So, to

determine kOH it is not necessary to simulate all the

elements of the pathway by which ozone is produced, only
the single reaction of Equation B1-8.
Consequently, kOH data (Table 6.1) to reliably evaluate
the reaction of a single hydrocarbon chemical were
available to policymakers decades before reliable MIR
data were available to evaluate the outcome of a series of
atmospheric events. So the basis for judgments19 about
VOC exemptions for hydrocarbons was this key
assumption:

The reaction of Equation B1-8 was the limiting step in

the formation of ozone from organic chemicals,
although no ozone was produced in that specic
reaction.

17

However, this apparatus is not simple. All concentrations are low and
the involved species have short half lives. For example, the HO* radical
concentrations are perhaps 0.1 pptv (parts per trillion) on a volumetric
basis), and their half life is perhaps 1 second. While a smog chamber will
hold dozens of cubic meters (Box 6.4), the apparatus for measuring kOH
will hold only a few milliliters.
The procedure for determining kOH is to hold the concentration of
the specie being tested constant during a period when the HO*
concentration is measured in an inert gas atmosphere (nitrogen, argon,
helium) at reduced pressure. The value of kOH is determined from a linear
plot of the logarithm of HO* concentration vs. time.
A useful reference is Klopffer W. Wagner B. Atmospheric
Degradation of Organic Substances. Wiley-VCH, 2007. Another with
useful experimental data is Schmidt S, Jecklin MC, Zenobi R.
Degradation of Volatile Organic Compounds in a Non-thermal Plasma
Air Purier. Chemosphere 79(2):124e130.
18
The HO* radicals are produced by the photolysis of hydrogen
peroxide or water. Essentially, in these experiments, the entire ozone
formation scheme does not have to be simulated.

19

It is the complete environment (composition of all reactive

components, frequency distribution of incident radiation, composition of
auxiliary components such as water, aerosol, and particulate surface,
and temperature) which affects smog generation.
It is this complexity which makes reliable and informative
atmospheric computer modeling of smog or ozone production a task
reminiscent of the Greek mythological king Sisyphusdor expressed in
more modern terms, two steps forward, and one step back.
This is one reason that the concept of VOC reactivity is not simply
a property of a specic chemical. Yet those who desire VOC regulations
based on a reactivity scale (such as this author), often oversimplify this
complexity.

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