Journal of the Air Pollution Control Association

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A Study of Sulfur Dioxide in Photochemical Smog

II. Effect of Sulfur Dioxide on Oxidant Formation in Photochemical Smog

Wm. E. Wilson Jr. , Arthur Levy & D.B. Wimmer

To cite this article: Wm. E. Wilson Jr. , Arthur Levy & D.B. Wimmer (1972) A Study of Sulfur
Dioxide in Photochemical Smog, Journal of the Air Pollution Control Association, 22:1, 27-32, DOI:
10.1080/00022470.1972.10469605

To link to this article: https://doi.org/10.1080/00022470.1972.10469605

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 A Study of Sulfur Dioxide in Photochemical Smog
II. Effect of Sulfur Dioxide on Oxidant Formation in
Photochemical Smog

Wm. E. Wilson, Jr., Arthur Levy

Battelle Columbus Laboratories

and

D. B. Wimmer
Phillips Petroleum Company

Sulfur dioxide, a reducing agent found in urban air, might be expected to react 0.1% of the SO2 reacted during 24 hours.
with the oxidizing atmosphere produced by photochemical smog. It does not, The absence of aerosol formation from
mixtures of SO2 and O3 has been taken
however, react directly with either ozone or nitrogen dioxide in air although as evidence that SO2 and O3 do not react
these reactions can occur in solution or on surfaces. However, sulfur dioxide in the dark.5 However, statements
does react with other, less well-identified oxidants which are formed during the have been made to the effect that it is
photochemical smog reaction process. One mechanism involves the reaction of not possible to have photochemical
SO2 with NO3 (or N2O6) formed as a result of the reaction of NO2 with O3. smog in cities with high SO2 levels, such
as Chicago and New York, because the
The interactions of SO2 with photochemical smog were investigated in environ- SO2 in the atmosphere removes the
mental chambers. A regression analysis, carried out on the data from 23 cham- oxidants. It is important, therefore,
ber experiments with 1 -butene, indicated that the effects of SO2 on oxidant to obtain additional information about
production depend on the concentrations of water vapor, initial nitrogen dioxide, the reaction of SO2 with oxidants, both
and sulfur dioxide. The effect also depends on the type of hydrocarbon. Sulfur in photochemical smog and in simpler
systems.
dioxide was found to reduce the maximum oxidant obtained from 1-butene,
1-heptene, and 2,2,4-trimethylpentane, but to increase the oxidant obtained Although the role of SO2 in aerosol
from toluene. In all cases, however, the maximum NO2 concentration was lower
formation has received considerable
study,6-7 little is known about its inter-
when SO2 was present. The reaction mechanisms involved in producing these action with oxidants in photochemical
effects are discussed. smog. Ripperton, el al.,8-9 reported
that oxidant was suppressed by the
addition of SO2. Altshuller, ei al.,10
however, reported no change in oxidant
with the addition of SO2. In the first
This paper reports part of a study under- This reaction is exothermic and on the paper in this series,3 SO2 was found to
taken to determine the nature and ex- basis of thermodynamics the equilibrium suppress oxidant under certain condi-
tent of the interaction of SO2 with the would be expected to be far to the right. tions although there was considerable
photoinduced reactions of hydrocarbons However, the reaction to the ground scatter in the experimental results. In
and nitrogen oxides in air.1"3 state of O2 requires the disruption of an this paper we report a statistical analysis
Since SO2 is a reducing agent and electron pair to form the two unpaired of the data from the l-butene/NO^/SOs
photochemical smog is normally con- electrons of the O2 molecule. This reac- system which was undertaken in an
sidered to be an oxidizing system, an tion would, therefore, be kinetically effort to determine the factors respon-
interaction would be expected. Atten- limited by spin conservation. sible for the varying results from these
tion naturally is directed toward the There is very little published informa- studies. The photochemical smog in-
reaction of SO2 with ozone, the major tion on this reaction. Cadle4 refers to teraction of SO2 with other types of
oxidant in photochemical smog. unpublished work in which experiments hydrocarbons and the reaction of SO2
showed that with 1% ozone, 1-10% with O3, NO3, and several other oxidants
S02 + 0 3 - • S0 3 + 0 2 SO2, and 0-1% water vapor, less than was also investigated.

January 1972 Volume 22, No. 1 27

Experimental Table I. System parameters and effects of SO2 on oxidant and NO2.
Dynamic experiments were performed Oxidante
in a 200-liter environmental chamber
Hydrocarbon Rate, NO 2
made from two Pyrex bell jars connected NO NO 2 Max ppb
so S-S, Peak
by a central ring of anodized aluminum. Composition ppm ppm ppm p p m2 ppm ppm min ppm
The 800-cm3/sec throughput used gave a b
l-butene - 4 1.0 <0.05 0 0.56 0.12 21 0.77
adequate flow for the analytical system 4 1.0 <0.05 0.75 0.29 0.16 8 0.70
and resulted in a time constant (volume/ l-butene b
4 1.0 <0.05 0 0.42 0.13 10 0.87
flow) of about 4 hr. Illumination, 0
4 1.0 <0.05 0.75 0.17 0.06 5 0.67
provided by 34, 4-ft long black fluores- 1-heptene 3 0.75 0.75 0 0.53 — 21 1.01
3 0.75 0.75 0.75 0.30 — 7 0.80
cent lights (GE F40BL), gave an in- 2,2,4-trimethyl-
tensity, measured by NO2 photolysis, of pentaneb 6 0.5 0.5 0 0.44 — 16 0.71
ko = 0.5 min"1, which is slightly greater b
6 0.5 0.5 0.75 0.27 — 6 0.61
than noonday sunlight. Batch experi- Toluene 4 0.5 0.5 0 0.26 0.16 3.9 0.57
ments were made in a 610-ft3 environ- 4 0.5 0.5 0.75 0.39 0.26 4.7 0.60
c d
Mixture > 2 2.5 0.1 0 0.38 — 5.7 1.47
mental chamber constructed of polished 2 2.5 0.1 0.3 0.30 — 4.3 1.35
aluminum with "Teflon FEP" windows. a
Illumination in this chamber is equiva- With stirring at 65% RH and 82°F: all other experiments were without stirring; 200-liter cham-
ber runs—50% RH at 82°F, 610-ft3 chamber run - 40% RH at 95°F.
lent to 0.8 of noonday sunlight. b
200-liter chamber, dynamic operation, flow rate/volume = 4 hr.
c
Oxidant measurements were made 610-ft3 chamber, batch operation.
d
with a Mast meter. A OO3 scrubber Composition of hydrocarbon mixture: 45% 1-butene, 7% 2-methyl-2-butene, 8% 1-heptene,
23% toluene, 7% 1,3,5-trimethylbenzene, 10% methylbutylbenzene.
was used to oxidize SO2 and thus prevent e
Concentrations given are for maximum (Max) and steady-state (S-S), rate is maximum rate
its interference with the oxidant analy- of formation.
sis.11 Numerous experiments and fre-
quent checks were made to ascertain
that the CrO3 scrubber did indeed com-
pletely remove the SO2 but did not re- stirring, Figure 16, no stirring) indicate reach the oxidant maximum. The
move any of the oxidant produced in that the effect of SO2 on oxidant is oxidant profiles, shown in Figure 2, in-
runs without SO2.12 The Mast reading greater in the nonstirred system which dicate that 0.75 ppm SO2 reduced the
was corrected for contributions due to contained aerosol (~100 /*g/m3). This maximum oxidant by 45%. The rate
NO2 and NO (oxidized to NO2 by the suggests that the aerosol may play a role of formation of oxidant was also reduced.
scrubber). The oxidant is largely ozone in the reduction of oxidant by SO2. An effect can also be observed on the
but includes contributions from per- The presence of SO2 does not seem to NO2 profiles (Figure 2), the peak NO2
oxyacylnitrates and possibly other oxi- affect the NO2 formation rate. The concentration and the rate of removal of
dants.13 SO2 was monitored by a Beck- maximum NO2 concentration reached NO2 being lower when 0.75 ppm SO»
man coulometric instrument which used and the rate of removal are affected was added to the system.
a proprietary scrubber to remove however. In the 1-butene runs the
oxidants. differences between the NO2 profile with Toluene System
The environmental chambers and the 0.75 and 0.25 ppm SO2 indicated that
instruments and techniques used have Toluene was chosen as a representa-
the interaction is not a simple one and tive of the aromatic compounds found
been described previously.1-14 probably involves several competing in urban atmospheres. As with 2,2,4-
Results reactions. trimethylpentane a mixture of 0.5 ppm
Systems Studied NO and 0.5 ppm NO2 was chosen to in-
1-Heptene
The influence of SO2 on the photo- crease the reaction rates. The effect
chemical smog reaction sequence has 1-heptene is less reactive than 1-bu- of SO2 in this system was completely
been studied in several diverse systems. tene but produces appreciable amounts different. Both the maximum and the
Some system parameters and the effects of aerosol even in the absence of SO2. steady-state concentrations of ozone
on oxidant and NO2 formation are sum- Several batch reactions with 1-heptene, increased with added SO2. The oxidant
marized in Table I. The hydrocarbon NOX, and SO2 were made in the 610-ft3 profiles, shown in Figure 3 indicate
species studied include two olefins chamber to determine if differences in that the rate of formation of oxidant is
(1-butene and 1-heptene), a paraffin surface materials or surface-to-volume about the same for the first 100 min.
(2,2,4-trimethylpentane), an aromatic ratio or differences between static and After this time, however, the effect of
(toluene), and an olefin-aromatic mix- dynamic operation would change the SO2 can be seen. When SO2 was pres-
ture. No effort was made to duplicate influence of SO2. The results, shown ent the oxidant continued to increase
the hydrocarbon concentration or the in Table I, indicate that in this system and for 0.75 ppm SO2 reached 155% of
hydrocarbon-nitrogen oxides ratio. In- also the addition of SO2 causes a reduc- the maximum oxidant concentration ob-
stead the concentrations were chosen tion in rate of formation of oxidant, in tained without SO2; the steady-state oxi-
to give convenient reaction rates. the peak oxidant concentration, and in dant concentration increased by 175%.
the peak NO2 concentration. The NO2 profile, shown in Figure 3,
1-Butene System is also influenced by the presence of SO2.
2,2,4-Trimethylpentane System The peak NO2 concentration was low-
The first series of 1-butene runs was
made with rapid stirring which prevents Although 2,2,4-trimethylpentane is ered by adding SO2 although, as in the
observation of aerosol.15 It is not yet quite reactive for a paraffin, it is much case of 1-butene, 0.25 ppm SO2 caused
certain whether aerosol formation is in- less reactive than most olefins and sub- a greater reduction in the maximum
hibited or whether the aerosol is coated stituted aromatic compounds. In order concentration of NO2 than 0.75 ppm
on the fan blades and chamber surfaces. to speed up the reaction, a higher hydro- SO2. The maximum rate of disappear-
The subsequent series of runs were made carbon-nitrogen oxides ratio was used ance of NO2 did not appear to be af-
without stirring and appreciable (6 to 1) and the nitrogen oxides input fected but the steady-state concentra-
amounts of aerosol were formed when was set at 0.5 ppm NO and 0.5 ppm tion of NO2 was much lower when SO2
SO2 was present. The oxidant profiles NO2. Even so the reaction was slow was present. The peak NO2 concentra-
for the 1-butene system (Figure la, with and 8-hr reaction time was required to tion was also reduced.

28 Journal of the Air Pollution Control Association

 U.DU
, 0.0 ppm S0 2
- y WITH STIRRING
0.40 - U 0 . 2 5 ppm SO2
\ \
\V0.75 ppm SO2
i level. In humid air, a very slow reac-
0.20
viN^
0 7
0 40
i i
120 160
i
0.40 - NO STIRRING
0.0 ppm
SO2
£ 0.20
160
Figure 1. Effect of SO2 on oxidant formation
and reaction in the l-butene-NOx system (4
ppm 1-butene, 1 ppm NO, 0.0-0.04 ppm NO2),
with stirring, 65% relative humidity, and no
stirring, 50% relative humidity.
Interaction Mechanism
Possible Reactions
There are a number of oxidant species
with which SO2 might possibly react.
Several obvious oxidants have been
found unreactive at atmospheric con-
centrations and temperatures. Some
additional oxidants have been dis-
covered which do react with SO2 under
conditions simulating those found in the
environment.
Ozone. As indicated in the introduc-
tion the reaction of sulfur dioxide and
ozone is exothermic. However, the
activation energy must be high, possibly
due to steric or spin considerations.
No reaction could be observed when O3
and SO2 were mixed in dry air at the
ppm concentration level. This experi-
ment was performed in two ways. The
chamber was filled with ozone and the
dynamic flow through the ozone genera-
tor was adjusted to maintain one ppm
ozone. Then 1.0 ppm of SO2 was
added. There was no change in the
ozone concentration. The experiment
was repeated by first adjusting the SO2
to 1.0 ppm and adding O3. Again there
was no change in concentration.
In humid air a slight decrease in O3
and SO2 could be observed which prob-
ably indicates a surface reaction. When
liquid water was sprayed into a mixture
of ozone and SO2 there was an im-
mediate drop in the concentration of
both, indicating a rapid reaction be-
tween these two species in solution.
January 1972 Volume 22, No. 1
Nitrogen Dioxide. The reaction of
SO2 and NO2 is exothermic (AH = —10
kcal/mole).
NO2 + SO2 -> SO3 + NO.
However, the reaction is very slow in the
gas phase. In dry air no reaction of SO2
and NO2 could be observed at the ppm
tion can be observed which suggests that
this reaction may take place on surfaces
or in droplets.
NOS or (N2O5). A reaction of SO2
200
with NO3 (or N2O5) was discovered
during a study of the dark reaction of
SO2 with O3 and NO2 at the ppm con-
centration level. Although SO2 does
not react with either O3 or NO2, reac-
tions do occur when all three are mixed
together. The reactions result in the
disappearance of all three components
and the formation of materials which
give no response on the Mast oxidant
meter or with Saltzman reagent.
The Ozone Plus Nitrogen Dioxide Re-
action. When the system contains ap-
preciable amounts of both O3 and NO2
200 the following reaction sequence becomes
important.
NO2 + O3 -> NO3 + O2 (1)
NO3 + NO -»- 2NO2 (2)
NO3 + H2O - * HNO3 + OH (3)
NO3 + NO2 - * N2O5 (4)
N2O5 + H2O -> 2HNO3 • (5)
In most photochemical smog studies
the initial nitrogen oxide is primarily
NO with varying amounts of NO2. As
the reaction proceeds the NO decays
and the NO2 increases, goes through a
peak, and then decays. At the NO2
peak the concentration of NO + NO2
is still approximately equal to the initial
nitrogen oxides concentration. How-
ever, after the peak has been reached,
the nitrogen oxides in the system, that
can be measured as NO and NO2, de-
crease rapidly. Alkyl nitrate and per-
oxyacylnitrate compounds account for
only a small part of the nitrogen oxides
disappearing. Reaction (1), followed
by Reaction (3) or by Reactions (4) and
(5), accounts for the rapid disappearance
of NO2 after it reaches its peak concen-
tration. This sequence results in the
removal of NO2 from the system as
nitric acid:
When SO2, NO2, and O3 are present
the following reactions become possible
NO2 + O3 - * NO3 + O2 (1)
NO3 + SO2 •-*• NO2 + SO3 (6)
N2O5 + "SO2 -* SO3 -f 2NO2 (7)
SO3 + H2O -> H2SO4 (8)
SO2 + NOX - * (SO3)(NOx)n
•:'. p (solid) (9)
The experimental observation is that
SO2 is removed by a product of Reaction
(1). It is not certain whether NO3 or
N2O5 is the more important species. At
present, the evidence suggests that the
reaction of NO3(N2O5) with SO2 is fast
and that two molecules of NO* disappear
for every molecule of SO2.
Reaction (6) has also been postulated
by Tipper and Williams to explain their
observations of the NO + SO2 system
studied at much higher concentrations
and temperatures.16 Their mechanism
included the following steps:
NO + O2 - > N O 3
NO 3 - f SO2 — NO 2 + SO3
SO2 4- NO 2 -* SO3NO
SO3NO + NO2 + S O 3 ^
(SO3)2N2O3 (solid).
The first stage of the reaction involved
only NO (second-order) and O2 (first-
order). A second-stage reaction was
also observed which was first order in O2,
NO, and SO2; had an activation energy
of 7 kcal/mole; and formed a white
solid which was thought to be a mixture
of SO3 and (SO3)2N2O3. Reaction (6)
has also been postulated by Cullis, et al.,
to explain NO catalyzed oxidation of
SO2 at higher concentrations and tem-
peratures.17
Effects of SO2 Interaction
Removal of NOX. The NO2 profiles
(Figures 2 and 3) and the NOX concen-
trations given in Table I indicate that
lower NO2 peaks were observed in all the
reaction systems to which SO2 was
added. This may be related to the
reaction of SO3 with the O3 + NO2 reac-
tion product.
Effect on Ozone. The chemical inter-
action of SO2 may contribute to lower
ozone in two ways. The reaction with
NO3 slows down the formation of ozone;
the removal of NOX from the system
reduces ozone formation by lowering the
NO2 concentration. These considera-
tions could be used to explain the oxi-
dant reduction in olefin and paraffin
reaction systems. However, the obser-
vation that oxidant actually increases
with SO2 in the irradiated toluene/NOx
system requires a further consideration
of this interaction.
Some insight into this situation may
be gained by examining the NO2 and
oxidant profiles from the toluene/NO x /
SO2 study. (Figure 3). The ozone
profiles increase at the same rate until
about 100 mins. Then in the systems
containing SO2, the ozone profile con-
tinue^ to increase but, in the system
withoutjSOv, the ozone profile begins to
decrease. It is just at this time that the
NO2 profiles start to diverge. The NO2
concentration remains higher in the run
without SO2.
29
 0.0 ppm S0 2 -0.0 ppm S0 2

-0.75, ppm S0 2
u.ou -0.25 ppm S0 2
0.74 ppm
0.50 SO2
0.0 ppm S02 / -
0.40 \y
E /
a.
o.

:
0.30 /
"c / ^*"

A'
Oxida

0.20

0.10
/ 0.74 ppm S02
0 —^^r , i i
100 200 240 0 50 100 150 200 240
0 100 200 300 400 480 0 100 200 300 400 480
Minutes Minutes Minutes Minutes

Figure 2. Effect of SO2 on oxidant and NO2 in the 2,2,4-trimethyl- Figure 3. Effect of SO2 on oxidant and NO2 in the toluene-NO x system
pentane (6 ppm 2,2,4-trimethylpentane, 0.5 ppm NO, 0.5 ppm NO2, (4 ppm toluene, 0.5 ppm NO, 0.5 ppm NO2, 50% RH).
50% RH).

If each NO3 + SO2 reaction actually Method of Analysis a regression model containing 20 con-
results in the removal of two NO* mole- Since the data in Table II frequently stants. However, not all terms were
cules, as seems likely, the more rapid involve the simultaneous variation of retained in the final regression equation.
removal of NO2 in the presence of SO2 more than one independent variable, the In spite of the variable scaling meth-
means that there is less NO2 to react assessment of effects attributable to ods used, the coefficients an, an, and ais
with O3 and the O3 concentration can individual variables was carried out via could not be accurately computed be-
increase to a higher concentration. The regression analysis. The independent cause of relatively high degrees of linear
situation would be more obvious in the variables of the regression were taken to correlation with other variables. These
toluene runs because the reaction of be: terms were deleted, resulting in a model
ozone with toluene is slow and O3 + NO2 that contained no third order NO2-SO2
would be the major means of removing Xi = percent relative humidity interactions and no third order NO2
ozone. The reaction of ozone with term. In view of the high qualitj' of the
olefins is in general faster than with X2 = initial NO2 concentration, correlation finally obtained, this restric-
aromatics. Therefore in experiments ppm tion is not considered serious.
with olefins the reaction of ozone with the Xz = SO2 concentration, ppm Additional deletion of terms was
hydrocarbon would tend to reduce the carried out via a regression analysis
ozone concentration. A complete third order polynomial was program which included a statistical test
Simultaneous Effects of S02, NO2, and chosen as the regression model in the of significance for each coefficient. The
Water Vapor on Oxidant. The fore- absence of a theoretical description of term having the coefficient of least
going sections have shown that the effect independent variable effects. In order
of SO2 on oxidant can vary markedly to minimize the degree of linear correla-
among radically different reactant sys- tion among independent variables, the
tems. It seemed possible that more first-order variables were scaled accord-
subtle variations in the reactant system to their means and standard deviations
might also influence both oxidant and to generate a new set of variables:
SCVoxidant effects. For example, one Table II. Observations of maximum
A = (Xi - X1)/a1; oxidant with 3.95 ppm 1-butene
might reasonably expect that relative and 1.00 ppm NO2.
humidity would play a role in a chemical scaled relative humidity
system involving SO2 and oxidant. Initial Initial Maximum
B = (X2- X2)/a2; Relative NO2 SO2 oxidant
Since NO2 is the primary photosensitive scaled initial NO2 concentration humidity, cone, cone, concn.,
reactant in hydrocarbon-NOx-air sys- % ppm ppm ppm
tems, the initial concentration of this C = (Xz- X3)/<TZ;
material might also be important. A scaled SO2 concentration. 0 0.04 0.75 0.93
0 0.06 0.35 0.90
quantitative assessment of the roles of 0 0.03 0.25 0.92
relative humidity and initial NO2 con- Hence the general regression model may 0 0.03 0 0.84
centration was carried out using obser- be expressed as: 55 0.13 0 0.74
22 0.11 0 0.74
vations of oxidant formation from 23 F = ao + aiA + a2B -f azC 80 0.10 0 0.76
irradiation chamber runs with a base 22 0.05 0 0.65
reactant system of 3.94 ppm 1-butene + a^2 + a5B2 + a6C2 22 0.06 0.75 0.72
and 1.00 ppm nitric oxide in air. Rela- 55 0.20 0.75 0.54
tive humidity, initial NO2 concentration, + a8AC + agBC + aw 0 0.01 0.05 0.80
0 0.05 0.53 0.85
and SO2 concentration were varied from + aiiB8 + a12C3 + 0 0.10 0 1.09
0 to 80%, 0-0.20, and 0-0.75 ppm, 65 0.05 0 0.39
respectively. The 200-liter chamber, + auAC2 + auBA2 + a^BC2 65 0.06 0.06 0.46
operated in the dynamic mode as de- 65 0.02 0.25 0.39
+ anCA2 + amCB2 + a19ABC 65 0.02 0.52 0.36
scribed previously,1 constituted the 65 0 0.75 0.29
reactor system. The resulting values of where Y = maximum oxidant concen- 65 0.07 0.06 0.53
maximum oxidant, relative humidity, tration, ppm. 65 0.04 0 0.55
SO2 concentration, and initial NO2 con- 0 0 0 0.82
Obviously 23 observations of Y are 0 0.12 0 0.93
centration are summarized in Table II. not sufficient to establish the validity of 0 0.07 0 0.92

30 Journal of the Air Pollution Control Association

 1.20 1.20
0.10 ppm NO2 demonstrated. (Since the degrees of
E 22 percent relative freedom are the same for all values of Y
Si.oo humidity
calculated within the data space, the
1.00
00.8O - 0.0 ppm least significant difference between two
values of Y can be written as H VC12 +
C22 where C\ is the 95% confidence
J — — •

^0.60 0.0 ppm SO,

X
O interval for Yi and Gi is the 95%
E0.40
13
-. 0.75 confidence interval for F2.) At 0.75
^ ppm ppm SO2 the relative humidity range
E
"jgO.20 was limited to the interval from 20 to
0 \ x 0 . 7 5 ppm S0 2 60%, and no significant effect on maxi-
10 20 30 40 50 60 70 \ mum oxidant was found. The effect of
\
Relative humidity, percent 0.20 SO2 to suppress maximum oxidant is
Figure 4. Effect of relative humidity on maxi-
apparent in Figure 4.
mum oxidant at two SO2 levels (3.95 ppm Effects of initial NO2 concentration on
1-butene, 1.00 ppm NO, Y calc, 95%
confidence limit).
0.05 0.10 0.15 0.20 maximum oxidant are presented in
Initial N0 2 cone, ppm Figure 5. Both at 0 and 0.75 ppm SO2
Figure 7. Effect of initial NO2 concentration the maximum oxidant concentration
on maximum oxidant at two SO2 levels (3.95 increased markedly as initial NO2 in-
ppm 1-butene, 1.00 ppm NO, Y calc,
95% confidence limit). creased. At 0.0 ppm SO2, the con-
fidence interval was sufficiently small
and the oxidant-vs.-NCX slope suffi-
significance was deleted, and the remain- ciently steep that an increment of 0.03
65 percent relative ing coefficients recomputed. This pro- ppm in initial NO2 produced a sta-
humidity
1.00 - cess was repeated until all remaining tistically significant increase in the
/
coefficients were significantly different maximum oxidant concentration. Such
/ from zero at a confidence level nomi- a result is particularly important in view
0.80 - /
/ 0.0 ppm / . nally greater than 95%, i.e., a "lvalue" of the usual practice of designating
greater than two. The final regression reactant mixtures of NO and NO2 as
•S 0.60 - equation was: NO* without defining the NO and NO2
o content. In addition, this effect of
E / / / Y = 0.600 - 0.226A initial NO2 concentration suggests that
| 0.40
+ 0.0698A2 + 0.0786,45 NO2 holdover from the previous day
^ / // could be a previously unsuspected
0.20 - y ' 0.75 ppm - 0.1275D + 0.0503AB2 factor in actual oxidant formation in
^ S02
real atmospheres. Again, the effect of
- 0.0910CA2 + 0.827ABC SO2 was to suppress oxidant.
I i i

0.05 0.10 0.15 0.20 (II)

The suppression of maximum oxidant
Initial N0 2 cone, ppm The eight constants in Equation (II) by SO2 is demonstrated at two levels of
Figure 5. Effect of initial NO2 concentration
coupled with 23 observations, yields relative humidity in Figure 6. In dry
on maximum oxidant at two SO2 levels (3.95 15 degrees of freedom for the regression. air an increment of 0.09 ppm in SO2
ppm 1-butene, 1.00 ppm NO, Y calc, The coefficient of determination was concentration was sufficient to produce a
95% confidence limit).
computed to be 0.958, i.e., 95.8% of the statistically significant decrease in max-
variance in maximum oxidant concen- imum oxidant concentration. In humid
tration as accounted for by the re- air (65% RH) the effect of SO2 was less
gression equation. marked but real. In this case, an in-
Partitioned Effects crement of about 0.18 ppm SO2 was re-
quired to yield a statistically significant
Equation (II) can be used to compute decrease in maximum oxidant at low
the maximum oxidant resulting from values of SO2 where the confidence inter-
0.10 ppm N0 2
any combination of relative humidity, val was comparable to the one in dry
1.00 initial NO2, and SO2 values that lie with air.
the data space occupied by the original
observations. The results of such com-
Interactions
0.80 —
N
\ N ^ 0%.relative putations can be presented graphically,
"»N humidity as in Figures 4-7. The reliability of Equation (II) contains the terms BC,
each computation was assessed in terms CA2, and ABC. This means that the
0.60
^?^--.. of the 95% confidence interval of the
population mean, i.e., the interval which
has a 95% chance of containing the
effect of C (SO2) on maximum oxidant
will depend on the values of A (relative
humidity) and B (initial NO2), i.e.,
0.40 mean of the population of maximum dY/dC = f(A,B). Similarly, the effect
oxidant values associated with the of initial NO2 concentration will de-
65% relativeN N assigned values of the independent pend on the values of SO2 concentration,
N
_ humidity x
0.20 variables. The limits of the 95% con- relative humidity, and the initial NO2
fidence intervals are shown as dashed concentration itself. An analogous
lines in Figure 4. At zero SO2, the statement can be made concerning rela-
0 1 1 1 maximum oxidant concentration de-
0.20 0.40 0.60
tive humidity effects. One interesting
0.80 creased with increasing relative humid-
S0 2 cone, ppm
consequence of these variable inter-
ity over the range from 0 to about 25%. actions is depicted in Figure 7 and in its
Figure 6. Effect of SO2 on maximum oxidant For relative humidities higher than comparison with Figure 5. Figure 7
at two relative humidity levels (3.95 ppm 1- 26%, no statistically significant in- shows that at 22% RH, maximum
butene, 1.00 ppm NO, Y calc, 95%
confidence limit). fluence of relative humidity could be oxidant was increased by increasing

January 1972 Volume 22, No. 1 31

initial N0 2 in the absence of S02. But,
with 0.75 ppm S02, maximum oxidant
was actually suppressed by an increase
in initial N0 2 . This latter effect, at 0.75
ppm SO2 and 22% RH, is in the opposite
direction of the effects of initial N0 2 con-
centration at 65% RH and the same SO2
level. Moreover, the direction of the
SO2 effect was reversed at low initial NO2
and relative humidity. Instead of the
usual suppression of maximum oxidant
found in this series of experiments,
SO2 was found to promote oxidant
at 22% RH and initial NO2 concentra-
tions less than 0.05 ppm (see Figure 7).
However, the low humidity and low NO2
values leading to the promotion of oxi-
dant by SO2 are not normally associated
with polluted atmospheres and prob-
ably have little practical significance.
Nevertheless, the existence of such inter-
actions point up the extreme care that
must be exercised in controlling reactant
variables in irradiation chamber experi-
ments.
Conclusion
The results of this study confirm the
interaction of SO2 with photochemical
smog suggested in previous reports and
explain the lack of an SO2 interaction
observed in other studies. The interac-
tion of SO2 is complex and depends on
several factors including the type of
hydrocarbon, the water-vapor concen-
tration, and the initial NO2 concentra-
tion. Therefore, it is possible that under
certain experimental conditions the
effect of SO2 might be small and partic-
ularly if the above factors were not
carefully controlled the influence of SO2
would not be evident. However, the
interaction of SO2 with photochemical
smog can be significant and this inter-
action should be considered in predicting
the effects of various control measures
on air quality.
Acknowledgments
The work reported was supported in
part by the American Petroleum In-
stitute through The Committee for Air
and Water Conservation and in part by
the Department of Health, Education,
and Welfare through Grant AP00828
from the National Air Pollution Control
Administration, Enviromental Health
Service, Public Health Service. A more
detailed account is contained in "A
32
Study of Sulfur Dioxide in Photochem-
ical Smog. II." American Petroleum
Institute, Project S-ll, which may be
obtained from the American Petroleum
Institute, 1801 K Street, Northwest,
Washington, D. C. 20006.
The authors greatly appreciate the
interest, assistance, and encouragement
of the S-ll Task Force members: J. H.
Weiland, Chairman, Texaco, Inc. and
H. McDonald, Continental Oil Com-
pany, and A. R. Rescorla, Assistant
Director, American Petroleum In-
stitute. The authors wish to acknowl-
edge the capable assistance of D. R.
Hopper and D. F. Miller in the experi-
mental program.
References
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Dr. Wilson is presently Chief,
Aerosol Research Section, Dept. of
Chemistry and Physics, Environ-
mental Protection Agency, Re-
search Triangle Park, N. C. 27709.
Mr. Levy is Fellow, Atmospheric
Chemistry and Combustion Sys-
tems Div., Battelle Columbus Labs,
505 King Avenue, Columbus, Ohio
43201. Mr. Wimmer is Group
Leader, Fundamental Combustion
Research Group, Research Div.,
Phillips Petroleum Company,
Bartlesville, Okla. 74003. This
paper was presented as Paper No.
70-115 at the 63rd Annual Meeting
of the Air Pollution Control Assoc.
at St. Louis in June 1970.