Introducing Atmospheric Reactions
A Systematic Approach for Students
N. Colin Baird
University of Western Ontario, London, ON, Canada N6A 587
As cmvirnnnicntal srienre incrensei in importanre hoth
to students and to ~ r o f ~ ~ s s i o n athe
l s , topic of ntmi,sphenc
chemistry also grows in relevance-even finding its way
into introductory textbooks for general ( 1 )and for environ-
mental chemistry (2).Unfortunately, air is a complex reac-
tion medium: over 200 reactions occur simultaneously in
polluted urban air (3).Consequently, there is a tendency
among educators either simply to ignore the mechanisms
of atmospheric reactions and simply quote the overall re-
sult or to present a n arbitrarily chosen small numbw of
reactions a s representative.
In what follows, an attempt is made to outline the domi-
nant reactions that occur i n air, to show that the relative
importance of such processes can be rationalized using ele-
.
mentarv urinciules.. and to illustrate a few "rules" usine
~~~~~~~~
which tjle'predominant fate of many pollutants ran be prr-
dieted. In essence. the half-duzen or so reaction t .v.~ c of
greatest importance to the chemistry of the lower atmos-
phere have been deduced from the verv large set of reac-
kons in air discussed by Finlayson-pitti and-~itts(3a) and
are presented here.
Organizing Principles for Air Chemistry
As has been noted many times, the Earth's atmosphere
is a n oxidizing environment owing to the great concentra-
tion of Oz present. Almost all the gases released into air-
whether "natural" substances or pollutants-are eventu-
ally oxidized; e.g.
CH, + 20, + CO, + 2HzO
Intact 0, molecules do not directly react with the origi-
nal gases! The homogeneous oxidation of covalent mole-
cules in air inevitablv occurs bv a seauence of free radical
reactions. The "activation" of the original molecules occurs
either when thev absorb sunlight - and undergo .. photo-
. molecules X-H the process of H atom abstraction by OH'
chemical decomp(~sitim,or in the more t'rrqucnt case when
thev are attackvd hs the hvdroxyl t'rer radical,' OH' lor in
rare cases by ozone).
Examules of ~hotochemicaldecom~ositionmainly in-
volve t i e carbdnyl group; most impokant are the Hlde-
hvdes H?CO and CHaCHO which are released in automo-
bile exhaust and which are produced as intermediates in
the atmospheric oxidation of other pollutants, for example:
sunlight W
H&O H' + HCO'
(A fraction of aldehvdes
" -
eive molecular products such a s
Hz.) Such reactions increase the concentration of free radi-
cals in air. which i n turn a e a t l v increases the rate of the
overall oxidation reaction; and is the driving force in pho-
tochemical smog episodes in Los Angeles, Mexico City, and
many other warm, sunny cities. The feasibility for sunlight
to produce free radicals from other gases can be easily de-
'we adopt here the standard convention that a superscript dot
place after a formula indicates that the species is a free radical;
whereas, one place directly above an elemental symbol indicates
that the unpaired electron is localized on that atom.
termined by cnlcul:~tingthe A l I of the dissociation reaction
and noting that the sunl~ghtcutoft' wavelrnfirh of about
290 nm corresponds to an enwhy of413 k.1 mol ' = 99 kcal
mol-'.
Much more common than photolysis of closed-shell mo-
lecular pollutants is their reaction with OH', a very reac-
tive species whose concentrati~nin air is miniscule (about
5 x lo6 molecules per mLj but without which most pollut-
ants would not be oxidized a t a measurable rate. Reactions
involving the hydroxyl radical readily occur provided that
their activation energies do not exceed a f e a kilocalories
per mole; thus, endothermic reactions involving OH' are
not important because their rates are so slow. The lowest
activation energy-and hence fastest -reaction for a mole-
- cule involves addition of OH' to a n atom which is partici-
pating i n a multiple bond, e.g. a n alkene:
s
HzC=CH2 + OH' + H,CCH,OH
The site of the unpaired electron is, thereby, altered from
the oxygen atom in OH' to the atom of the double bond to
. does not attach. In order for the reaction
which the oxveen
to be exothermic, the newly-formed single bond to oxygen
must be stronger than the oi bond which is destroyed: this
condition is n i t fulfilled if h e atom attached to ;xy;en is
also an oxygen atom (since 0-0 bonds are weak), or if the
pi bond i s that of a carbonyl group (since i t is stronger than
is a CO single sigma bond). Hydroxyl radicals do not add to
any fully-oxidized product, such a s COz, SO3, HNO3, or
N205, since the multiple bonds therein are so strong. Simi-
larly OH' addition does not occur in nitrous oxide, NzO,
because of the high bond strengths in the reactant and the
weak N-0 bond that would result.
If addition of OH' is not feasible due to lack of a pi bond
or for energetic reasons, then i n hydrogen-containing
usually occurs because its activation energy is usually only
slightly greater than that typical of addition:
X-H + OH' + X'+ H,O
The strength of the H-OH hond thereby formed exceeds
that of almost all X-H bonds (a notable exception being the
H-F linkage) and so no large harrier to the reaction is im-
posed by its energetics.
According to the reasoning above, t h e first products
formed by the activation of a molecular gas in air are free
radicals. In most cases, the next reaction incorporates dia-
tomic oxygen into the system a s a whole. One common
mechanism by which this occurs is the abstraction by 0 2 of
a hydrogen atom from the free radical to form the hydro-
peroxv radical, HOW. Since the H - 0 0 bond is not strong,
?),can nl,itract hydrogen from radicals only if this procris
i~llowjthe simultaneous formation of a nea. pi bond within
the original radical, thus compensating energetically for
the loss of the bond to hydrogen. Usually the new bond
forms bv combinine the electron that had been bonded to
H with the unpairLd electron i n the free radical; thus, the
hydrogen to be abstracted must be originally bonded to a n
Volume 72 Number 2 February 1995 153
 transfer of a n oxygen atom to NO'; thus the peroxy radi-
cal oxidizes nitric oxide to nitrogen dioxide:
Does radical NO; + O-centered
have a peroxy HOO' + NO' + OH' + NO;
radical
bond? XOO' + NO' + XO' + NO;

1 F ~
,
Is it of type
-C
No
H ?~ C-csplits
Rfstabilizing)
(i
aldehyde +radical
By this process, most of the NO' in urban atmospheres is
oxidized to NO;, and most hydroperoxy radicals are con-
verted to hydroxyl radicals.
Many oxygen-centered free radicals XO' of interest con-
tain a hydrogen atom that can be abstracted by 0% to form
HOO' and a molecule which contains a double bond to the
oxygen. In other XO' radicals, there is a chain of carbon
atoms attached to the oxygen; scission ofthe carbon-carb-
on bond nearest the oxygen produces an aldehyde and a
carbon-centered free radical. Because this process is only
mildly endothermic (about +12 kcal mole-') when the carb-
on chain is unbranched, substitution a t the radical site in
Can H removal the product by an oxygen group or several alkyl groups low-
from H-X convert ers the activation to almost zero; in such circumstances, the
X-0' (or X=O) to HOCI '+ non-radical bond scission process occurs spontaneously and is faster
Olgb&d
X=O (or XEO)? than hydrogen abstraction by 0 % .Specific examples of
these XO' reactions are discussed in the next sections.
The organizing principles developed above are sum-
marized as "decision trees" in Figures 1and 2.
Applications
0, ad& to radical
site to produce The reaction principles developed above can be applied
perom radical readily to deduce the fate of many atmospheric pollut-
ants. Consider for example the reactions of sulfur diox-
Figure 1. The fate of airborne free radicals, under conditions with significant ide gas emitted into the atmosphere if it is oxidized by
nitric oxide present and beforeradical + radical reactions become important. homogeneous processes.2 Since so2does not absorb sun-
light and contains no hydrogen, it is stable until acti-
atom bonded to the radical site. For example, if a gaseous vated by addition of O R to the sulfur atom:
methanol molecule is activated by abstraction of a
methyl group hydrogen to yield the radical CHzOH',
then abstraction of the hydroxyl H by 0% results in the yes Gas eventually returned
conversion of the CO single bond to a double bond: soluble or fully ) to Earth's Burface
H2CO-H + 0%+ H2C=0 + HOO'
Similarly, the HCO' free radical produced by photolysis
of formaldehyde is converted to carbon monoxide by ab-
straction of its hydrogen:
D o e s gas

'PI1:
H-&O + 0%+ ce=o@+ HOO' photodecompose
If hydrogen abstraction is not feasible because a pi
in sunlight?
bond cannot be formed, then 0% generally adds to the
free radical a t the site of the unpaired electron, creating
a peroxy free radical X 0 0 ' analogous to the hydroperoxy
radical HOW. An example is the reaction with 0% of the
methyl free radical (created by the abstraction of a H by Do gea moledes
OH' from methane):
CHj + 0%+ CH,OO'
, that OH'
have multiple
can add
bonds OH'addition
occurs
> Freer!Asare
prcdueed

Atrivial example is the reaction of Ozwith atomichydrogen.

Compared to the free radicals produced initially by
photolysis or OH' attack, the peroxy free radicals are
relatively long-lived. They generally cannot abstract hy-
drogen because the OO-H bond is a weak one and thus
such reactions are endothermic and would have large ac-
tivation energy barriers. I n urban atmospheres and
other air masses containing the stable free radical nitric
oxide, NO', the usual reaction of peroxy radicals is the

2~uch of the SO, is actually oxidized by heterogeneous proc- Gm i. inert in

esses involving water droplets; the mechanism, which involves troposphere; will rise
ozone and hydrogen peroxide as the oxidizing agents, is beyond to stratosphere
the scope of the present discussion of homogeneous reactions. Figure 2,The fate of gases emitted intoair,

154 Journal of Chemical Education


This free radical then reacts with diatomic oxygen by ab-
straction of the hydrogen, since this allows conversion of
S-0 to S=O:
The sulfur trioxide so formed is fully oxidized; it quickly
combines with water vapor to form droplets of sulfuric acid
aerosol, HzSO,(aq).
A second example is the oxidation of methane, CHI,
which is emitted in vast quantities into the atmosphere as
a result of both "natural" and anthropogenic activities.
Since methane does not absorb sunlight and contains no pi
bonds, OH' abstracts a hydrogen atom from it:
CH, + OH' + CH; + H20
(Since the activation energy here is several kilojoules,
this reaction is relatively slow; on average a methane
molecules exists in air for a decade before it is activated.
Other alkanes react more quickly since the activation en-
ergies for abstraction are near zero.)
As predicted from our principles, the methyl radical re-
acts with diatomic oxygen; since no pi bond can form, the
oxygen adds to the carbon atom since it is the radical site:
The methyl peroxy rndlcal then oxidizes nitricoxide, pnl-
ducing the methoxy free radical and nitrogen dioxide:
CH300' + NO' + CH30' + NO;
In the electronic structure of the methoxy radical, the
unpaired electron is sited a t the oxygen atom, and there
are hydrogen atoms bonded to the carbon atom; thus, the
next reaction is abstraction by 0, of a hydrogen and the
simultaneous creation of a carbon-oxygen pi bond, i.e. for-
maldehyde:
CH30' + 0, 'HzC=O + HOO'
Formaldehyde is a natural constituent of air because it
is an intermediate in the oxidation of methane. As pre-
viously discussed, in air it photodissociates in sunlight to
produce free radicals
HzCO + sunlight + H' + HCO'
As discussed above, both these radicals react with dia-
tomic oxygen to produce the hydroperoxy free radical.
H' + OZ -t HOO'
H-&O + Oz -t Ce 'o@ + HOO'
The carbon monoxide obtained here is also a natural inter-
mediate of methane oxidation; since the second pi bond in
it is weak and since CO does not absorb sunlight, OH' adds
to the carbon atom:
Ce-O@ + OH' + H-O-C=O
Clearly, diatomic oxygen will abstract the hydrogen from
this free radical since a n additional CO pi bond is thereby
formed; in this way, the fully-oxidized gas carbon dioxide is
finally obtained:
HOCO' + OZ -, O=C=O + HOO'
Finally, the four HOO' free radicals produced in the above
reactions eventually oxidize the same number of nitric ox-
ide molecules:
4(HOO' + NO' + OH' + NO;)
If all 10 reaction steps above in the methane oxidation
sequence are added together, the overall reaction is seen to
be
CH, + 5 NO' + SO2 -
sunlight
CO, + HzO + 5NO; + 2 OH'
In a sense, nitric oxide is co-oxidized with methane-and
with many other substances-in atmospheric reactions.
This mechanism corresponds to the ambient temoerature
"burning" of hydrocarh&s in air.
Further Reactions of Free Radicals
The "rules" quoted above are appropriate to the back-
ground concentrations of free radicals found in most air
masses-in particular to those which are neither particu-
larly "clean" nor particularly "dirty". In episodes of high
~ollutionin manv urban areas. the concentration of the
tree radicals becomes so great that other processes, espe-
cially radical-radical reactions, achieve importance.
Wjlen two species with unpaired electrons combine, gen-
erally a closed-shell molecule is produced. For example,
when late in the day of an episode of urban smog the con-
centrations of both the hydroxyl radical and nitrogen diox-
ide become relatively high, they combine with each other
to produce one of the final products of the process, nitric
acid:
OH' + NO; -, HNO,
If the combination of the two radicals yields a species
with a chain of three or more oxygen atoms, then one or
two O2 molecules split out since 00 single bonds are rela-
tively weak and unstable; for example two hydroperoxy
radicals combine to yield hydrogen peroxide and diatomic
oxygen:
2 H00' + [HOOOOH] + H,Oz + OZ
Nitrogen dioxide, NO; , although a free radical is rela-
tively stable in air. As illustrated above, it can participate
in radical-radical reactions. Alternatively, when exposed
to sunlight it can photodissociate by detaching a n oxygen
atom:
sunlight
NO; A NO' + 0
Since the O-NO bond energy is 306 kJ mol-', the maxi-
mum wavelength for this process is about 391 nm, i.e. in
the UV-A region. The oxygen atoms produced here quickly
combine with diatomic oxygen to produce ozone:
0 + 0, " o3
This sequence is the principal route by which ozone is pro-
duced in both clean and polluted air.
Photochemical Smog: The Problem of "Urban Ozone"
In relatively "clean" air, the reactions described above do
not produce pollutants in sufficient concentration to be
troublesome to the health of living matter. In contempo-
rary civilization, though, huge volumes of very reactive hy-
drocarbons and aldehydes, and huge volumes of nitric ox-
ide, NO', are emitted each day into the air of urban areas.
As a consequence, the oxidation reactions proceed much
more rapidly and produce much greater quantities of nox-
ious products than in "clean" air. This is particularly true
in cities that are especially sunny and warm, and whose
Volume 72 Number 2 February 1995 155
 into u r b a n a i r from vehicle ex-
STEP haust, particularly if the fuel con-
RHC = CHR tains a n alcohol. I n a sunlit atmos-
phere, t h e aldehydes decom ose
photochemically (reaction 6) t o B
produce two new free radicals R'
and HCO'. This step i s a critical
one i n t h e photochemical smog
process, since i t increases t h e free
radical concentration i n air and
makes the atmosphere much
more reactive than i s "clean" air.
Although the same sort of process
occurs with methane, i t s effect
there i s much less since methane
m o l e c u l e s on a v e r a g e r e q u i r e
RHC = 0 + RH~oH years before undergoing success-
ful OH' attack, whereas alkenes
1
Oz
RHC = 0 + HOO'
react with i t i n a matter of min-
utes.
Inclusion of t h e conversion of
HCO' to carbon monoxide (reaction
7b) and the addition of 0 2 to R' (re-
action 7a) and the subsequent oxi-
+ HCO dation of NO' by the peroxy radical
7 a.b
ROO' HOW
4%
+ CO
(reaction 8 a ) a n d by t h e HOW
radicals produced i n reactions 5
and 7b yields the following overall

N 4
A+ NO'
RO' OH'
4 NO'
+ NO;
reaction:
RHC=CHR + 6NO' + 6 0 2 +sunlight

Figure 3. The reaction sequence for a prototypical alkene, RHC=CHR,where R is a short alwl chain,
T h e alkoxy r a d i c a l s RO' s u b -
sequently react with O2 t o pro-
duce additional aldehyde
air masses can be immobilized temporarily by geographic molecules by loss of hydrogen attached to t h e alpha carb-
constraints such a s mountains. on; their photochemical decomposition yields a carbon
The greatest mass of reactive hydrocarbons are gener- chain with one less member t h a n was present i n R. The
ally those emitted by motor vehicles-either by evaporation degradationofthe alkylchaincontinuesuntilitis all con-
of their fuel or by emissions of incompletely-burned fuel verted to carbon monoxide, with a corresponding increase
through their tailpipes. The most reactive class of hydmcar- i n the number of free radicals i n the air each time t h a t a
bons are the alkenes, followed by aromatics and alkanes. carboniseliminated.
As a n illustration of the photochemical smog which can be As noted previously, the increase i n the free radical con-
generated in urban air, the reaction sequence for a pmtotypi- centration does not continue unabated in air, because
cal alkene RHC=CHR, where R is a short alkyl chain, is illus- other reactions become important when radicals abound.
trated in Figure 3. As anticipated from the reaction principles For example, when [OH'] becomes high, some of the alde-
discussed above, the reaction sequence is: hyde is degraded by OH' abstraction of the carbonyl hydro-
gen rather than by photolysis:
1. Addition of OH' to a carbon of the douhle bond
2. Addition of O2 to theother carbon of the original double
bond (since it is the site of the unpaired electron)
3. Oxidation afNO' by 0 atom transfer from the peroxy radi- The R-C=O radicals, as anticipated, add Oz to produce
cal peroxy free radicals which then oxidize NO' if the latter is
Instead of hydrogen abstraction by 0 2 from the alkoxy abundant:
radical A, spontaneous decomposition occurs by scission of
the C-C bond to produce the aldehyde RHC=O and the
radical RHCOH'; this process is almost thermoneutral and
thus i s of low activation energy since a carbonyl CO pi
bond is not much weaker than a CC single bond and be-
cause the product radical is stabilized by the -OH group.
In the subsequent reaction of the new radical, O2 abstracts
the hydroxyl hydrogen to produce a second RHC=O alde-
hyde molecule (reaction 5). The RCOp radicals decompose spontaneously by R-C bond
Thus, the original alkene RHC=CHR produces two al- scission to yield COz; this process is exothermic and there-
dehyde molecules RHC=O, each half the size of the origi- fore fast since the pi bond in O=C=O is much stronger than
nal hydrocarbon. Aldehydes also a r e emitted directly
is a C-C single bond.
3These products occur more abundantly than do the alternatives
He and RCO'; for simplicity, the alternative products are ignored
herein.

156 Journal of Chemical Education

 Once most of the nitric oxide has been oxidized to NO; . .
actions ignored in t h i s sch(:mi, ;in!
ic .. the manv re-
sential orocesses in t r o ~ o s ~ h e rchemistw:
thwc that are rever.;ible
and the radicals concentrations have vastly increased, that
is, the situation typically found during afternoons in pol- and. rhu>., "~ i r l dno net uroducts. or [hose whirh .
~ l "a vlittle
part in the overall reactions and lead only to products of
luted urban atmospheres-radicals such as R-C=O react minor importance.
instead by addition to other radicals such as NO; These principles have been used for several years by the
author in an introductory environmental chemistry course
for science majors, all of whom have had a t least a rudi-
mentarv introduction to oreanic " chemistw and es~eciallv
to Lewis structures. Students seem capable of successfully
usine the ~ r i n c i ~ lto
" A
e sdeduce reaction mechanisms for the
The prototypical radical product of this type corresponds oxidation of gaseous trace substances such a s HzS, ethene,
to R=CHz, and is known a s PAN = peroxyacetylnitrate; it simple alkanes, etc.
is a powerful eye irritant:
Literature Cited

PAN

Conclusions 3. 1s) Finlayson-PiftP, B. J.;Pitts,J. N.,Jr.Afmofpheheii Chemistry: WiIey-Intefefefeience,

John Wiley and Sons: New York, 1986. ibl Heicklen, J.Atmospheric C h ~ m k l r y ;
The organizing principles for homogeneous reactions in Academic Press: New York. 1976. (el Seinfeld, J. H. Atmospheric Chemistry and
atmospheric chemistry are successful in isolating the es- Phyricr ofAir Pnllulion; John Wiley and Sons: New York, 1986.

Volume 72 Number 2 February 1995 157