.4tmospherir Encironmenf Vol. 11, pp. 813-817 Sergamon Press1977.

Printed
inGreatBritain.

THE REACTION OF SULFUR DIOXIDE WITH

OZONE IN WATER AND ITS POSSIBLE
ATMOSPHERIC SIGNIFICANCE

RONALD E. ERICKSON, LELAND M. YATES, ROBERT L. CLARK

and DAVID MCEWEN
Department of Chemistry, University of Montana, Missoula, Montana 59801, U.S.A.

(First received 25 February and in &ml farm 27 December 1976)

Abstract-The rate of the reaction between ozone and dissolved sulfur dioxide is strongly pH dependent.
This is so because sulfite ion reacts extremely rapidly (second order rate constant four orders of
magnitude higher than that of bisutite ion). These results suggest that under some conditions, atmos-
pheric oxidation of sulfur dioxide may involve ozone.

INTRODUCTION with bisulfite ion, using a pH of 4.65 and assuming

Sulfur dioxide is known to be converted into sulfate
(sulfuric acid) in the atmosphere by a number of
chemical processes (Urone and Schroeder, 1969;
Bufalini, 1971: Sethi, 1971; Sidebottom, Badcock,
Jackson and Calvert, 1972; Wilson, Levy and Wim-
mer, 1972; Freiberg, 1975). We report here on the
chemical kinetics of the reaction of ozone with
various sulfur (IV) species in aqueous solutions. A
suggestion by R. D. Cadle (1969) that a study of the
ozonation of sulfurous acid in fog droplets might be
appropriate prompted us to undertake this study.
Despite the many kinetic studies carried out since
1969, a recent review by Finieyson and Pitts (1976)
still states, Present un~er~~ties in the rate constants
[referring to SO2 oxidation by OH, HOz, 0(3P), Oj,
NO,, N,O,, ROz and RO] and in many of the prod-
ucts of these reactions preclude a quantitative assess-
ment of their importance, although OH is probably
important.
Sulfur dioxide is readily soluble in water, forming
some hydrated species of sulfur dioxide, which in turn
ionizes to bisulfite and sulfite ions.
SOz(aq) k% H+ + HSO; K1o,Q, = 1.3 x lo-M.
HSO; +> H + SO;2K2(25, = 1.0 x 10-M.
(2)
Each of these species is capable, in principle, of react-
ing with ozone as is shown in equations 3-5, and
the relative rate of these possible reactions determines
the actual overall reaction path.
H,SO,
03 + SO2W) 5 (3)
Hlo
HSO;
03 + wso; F;
2 apparatus
o3 + so; ;5; so;
While this work was ia progress Penkett (1972)
reported on the kinetics of reaction 4, that of ozone
all reaction is due to bisulfite ion, which is the pre-
do~nant species under these conditions. He showed
that the reaction is second order, first order in both
ozone and bisulfite ion. Our results, extrapolated to
his conditions, differ considerably from his in some
respects (although the possible significance of the
reaction to atmospheric conversion was clearly stated
by Penkett at that time), and we will consider those
differences after reporting our methodology and
results.
METHODOLOGY
We determined the rate of ozonation of total sulfur
species present in buffered aqueous solutions of sulfur
dioxide at variable pH by a stopped flow technique.
The stopped flow system used was an Aminco-Mor-
row stopped ilow spectrophotometer with associated
U.V.source and a Biomation transient recorder Model
610 with a Cathode Ray Tube display. The transient
recorder storage was then fed into a Bausch &
Lomb VOM-10 recorder. This enabled the signal col-
lected over a few milliseconds to be recorded on a
10 second virtual time base for a permanent record.
(1) The reaction was followed by observing the de-
crease in ozone concentration (initial concentrations
of ozone = 5 x 10m5 to 5 x 10m4M, total sulfur
(IV) = low5 M, pH range of - 1.30 to 4.02, T = 25C
and 16C). Five traces were recorded with each run
and three runs were made with each pair of reactant
solutions.
The solutions of ozone were prepared by bubbling
+ OZ. ozone into the proper buffered solution with nitrogen
from ozone saturated silica gel at -78C and were
+ OZ. analyzed spectrophotometrically in the stopped flow
(4)
(1 = 276 nm, E = 2150); A = 250 nm,
+ 02. E = 2430). The KI method was used for standardiza-
(5)
tion. The S(IV) solutions were made by dissolving re-
agent grade sodium sulfite in the desired buffer and
adding H,S04 if necessary to give the desired pH.
813
814 R. E. ERICKSoh. L. M. YATES, R. L. CLARK and D. McEwr~

20
Concentrations were determined spectrophotometri-
tally at 270 (6 = 461) 276nm (E = 500). This yielded 18- .
the concentration of sulfur dioxide directly (two wave-
lengths gave results within 34:; of one another) and 16-
allowed equilibrium calculations for other S(W) spe-
cies. Some of the more acidic solutions were prepared 14-
by passing SO, into the solution of sulfuric acid used o
IZ-
for the buffer (cn. 2 M HzS04 for pH -0.30).
At extremely high acidities both ozone and sulfur Xi ,o_m
. /!
dioxide absorb at 276 nm and proper corrections were $
made in calculating ozone concentration. At most pH 8-
values (pH > 2) the (cont. x E) factor for aqueous sul-
6-- ./
fur dioxide become less significant.
A possible source of experimental error would be .
4 .--
the decomposition of ozone caused by water, trace l
/
impurities or the buffer. Normal buffer solutions 2-
.
using phthalates or ammonium compounds react _/
. I I
rapidly with ozone and were completely unacceptable. 0 I 2 3 4
However acid phosphate buffer systems did not des- PH
troy ozone at an appreciable rate (t1/2 z 3 h) and
Fig. 1. Dependence of rate on pH for 75 C runs li is in
no ozone loss corrections were necessary for the very (M/l s)- I.
fast reactions measured in these experiments.
(aqueous SO,, bisulfite ion and sulfite ion). For
RESULTS AND DISCUSSION example, using the values of the equilibrium constants
shown in Equations 1 and 2 at a pH of -0.30
The reaction between ozone and sulfur (IV) species ([H+] = 2M)
follows second order kinetics. first order in ozone and
in sulfur (IV), at every pH which we employed. CH+ICHSO,j= 1,5 x ,. 2

Rate constants were determined using the following

SO2W
equation obtained by integration of the rate equation
(- d[O,]/dt = k[O,] [S(W)] assuming the observed then
stoichiometry of the reaction :
k = [l/a - b][ln(b(a - x)/a(b - x))]/t
k = rate constant
where and
a = initial ozone concentration
h = initial sulfur concentration
.Y = change in concentration of 0, at
1 = time of measurement. or the S(IV) species present are in the approximate
Table I shows typical rate data. Similar constancy ratio of 133:1:5 x 10e8 while at a pH of 3([H+] =
of data results was found at all pH values. The con- tom3 M).
stancy obtained using the equation for a second order
HSO; 1.5 x 10.
reaction, first order in each reactant. is interpreted -~~ = 15
to show that the reaction, overall. of ozone with S(IV) SO2 (aq) 1o-J
obeys this rate law at all pH values studied. so; 1.0 x lo--
Our original supposition was that although all sul- =lxlO~
HSO, 10 3
fur species might undergo oxidation by ozone in
aqueous solution, manipulation of the pH of the reac- and the ratio of the species present becomes
tion could isolate reactions of the individual species 0.07: 1: lo-.

Table 1. Typical kinetic data (pH = 3.12)

[%I Total S(W)

(0 - XI (b - XI b(a - x) In& - .x) &w,
t (sl M/l M/l a(b - x) a(b - x) (M/l s)-

0 5.89 x 1O-4 8.84 x IO-

0.0004 4.85 7.80 1.07 0.069 5.86 x IO5
0.0008 4.08 7.03 1.15 0.138 5.85
0.0002 3.49 6.44 1.23 0.207 5.84
0.0016 3.03 5.98 1.31 0.274 5.80
o.cQ20 2.65 5.60 1.41 0.342 5.80
 Reaction of sulfur dioxide with ozone in water 815

Figure 1 shows a plot of pH vs k,o,a,s(IM,where in Table 2.

ktota,s,,v, represents the total second order rate con-
stant for reactions 3, 4, and 5. The figure shows a
stronger dependence of the rate constant on pH than
we had anticipated. Even if aqueous SOZ itself has
a very low reaction rate, at all pH > 2 and < 6
HSO; is the predominant species present; therefore,
if all reactions were with this species, the rate depen-
dence on pH in this range would be small, contrary
to our observations. Likewise, if the reaction were
due entirely to sulfite ion, the dependence on pH
would have been larger than that which was observed.
We are left with two alternatives: either [H+] has
a strong inhibitive effect on the rate or the concen-
tration of the species reacting is dependent on the
reciprocal of the [H+]. We have chosen the latter
as the most logical explanation of our observations.
Using a series of simultaneous equations including
the fractions of the different species present and the
observed rate constant at various pH values, we can
test our assumption.
As noted we observed first order kinetics for both
S(IV) and [0,] or second order overall at ail pH
values studied. If this observation is valid over a
range of pH values, then if our assumption of species
reaction rates is correct, we arrive at the conclusion
that each species reacts with the same order kinetics,
but different rate constants. The following relation-
ship then would hold:
k,,,,,,,Cs(Wl~O,l
= $o,CS%J?h~
+ biso;WO;lP,I + k&WX21tW
but CSOziasJ= WVT x.&ox
CHSW= WV), x.&o;
[so;21 = S(Ivh_x&o,2
where f; = fraction of the total S(IV) present as that
species. From this we arrive at the relationship shown
Table 2. Equations for calculations of specific rate constants
ksc,v~,CWhl = ko,ho,CWVIl~
+ km;h&JS(IV)I, + ho,4o;dXVI~
or dividing by [S(IV)],
k,,,, = kso,.fso, + ho, f bo;&cp
All of the ks being second order rate constants would
have the units of 1 mole- set- or [MS]-. The
only real assumption in this treatment is that reac-
tions 1 and 2 are rapid enough under the stated con-
ditions so that equilibrium is reached. Equilibrium
constants are temperature dependent and to calculate
the fractions of the species present, we used the equa-
tions of Johnstone and Leppla for values of K1 at
16C. No temperature dependence data were found
for K2 so we used the same value at 16C as at 25C.
At the pH of interest, this is justifiable because the
effect of a few percent difference in this value would
have virtually no effect on the calculated concen-
tration of SO; and its fraction of the total S(IV).
Using the equations in Table 2 in all combinations,
it is possible to calculate specific rate constants as
follows:
k,,;(25C) = 3.1 T 0.24 x lo5 (M/l s)- (6)
kso, = (25C) = 2.2 T 0.35 x 109 (M/l sj- (7)
k,so,(l6C) = 1.7 T 0.17 x lo5 (M/l s)-1 (8)
ho, = (16C) = 1.3 T 0.4 x lo9 (M/l s)-. (9)
The rate constant for the reaction between ozone
and sulfurous acid (or sulfur dioxide dissolved in
water) was at least two orders of ma~itude less than
that of bisulfite ion and became a si~ificant contribu-
tion to the overall rate only at pH < 2. To determine
the rate constant exactly would require extensive
kinetic runs in highly acidic (negative pH) media. The
reaction is obviously of no environmental importance
and was not studied.

25.0 Runs
[Fraction HSO,] + [Fraction SO,] + [Fraction SOJ
pH ho; ks0;L 4%
1. -0.30 2.24 x lo3 = 0.0065&J; + 3.8 x lo-Ok -2 + 0.993 kso,
2. 0.62 9.82 x IO3 = 0.051 kmc; + 2.48 x U+k:;z + 0.948 kw,
3. 1.20 4.31 x to4 = 0.171 k=c,; + 3.14 x IO-ksO; + 0.829 kso,
4. 1.71 1.02 x IO5 = 0.402 kHSO; -I- 2.39 x W6k,;2 + 0.60 ks,,
5. 2.11 1.63 x IO* = 0.627 km,,; + 9.38 x 106k,,~ + 0.375 ko,
6. 2.50 3.03 x lo5 = 0.805kmo; + 2.95 x IO-Sk,,l + 0.196 &,
7. 2.80 4.51 x to5 = 0.891kmo; + 6.54 x lo-k,;~ + 0.110 k,*
8. 3.12 5.97 x lo5 = 0.946k,; + 1.44 x 10-4k,,* + 0.055&,
9. 3.55 9.47 x lo5 = 0.979 kmo; + 4.03 x 10-4k,;I + 0.021 kwl
10. 4.02 1.74 x lo6 = 0.994 km,,; + 1.20 x 1O-3 kso;z + 0.007 ksO,

16.0 Runs (K, = 1.6 x lo-*, K, = 1.0 x lo-)

11. 0.59 8.6 x lo3 = 0.058 k=t,; + 3.15 x 1O-8 kso;z + 0.94 bcIio,
I 2. 2.13 1.42 x lo5 = 0.683 kmo; + 2.76 x 10-5~o;z + 0.32 ho,
13. 3.09 2.13 x 10 = 0.951 k,; + 1.64 x W4k,;z + 0.048 kw2
14. 3.74 1.43 x i06 = 0.989 km; + 7.61 x 10-4!+z + 0.0 kso>
816 R. E. ERICKSON,L. M. YATES, R. L. CLARK and D. McEw~.x

Substituting the rate constants of the major species droplets of water, pH = 5.0, and a temperature of
into the Arrhenius equation leads to the following 10C. Using the activation energies obtained in this
formulas: work, we can extrapolate values for kHSOTand /zso, i
d(HS0;) of I.1 x IO (M/l)Is- and 7.4 x IO8 (M/l)-s-
- ---iF-- = 1Ol4 exp - 1 l,OOO/RT(HSO;)(O,) respectively.
(10) Using the values of

- F = 10 exp - 10,.5OO/RT (SO;)(O, ).

All of our rate constants {Equations 6-9). but par-

ticularly those involving sulfite ion, have large vari-
ances. Two major factors account for the relatively (H )(HSO;)
K, = .-..___I = 0.0184
large uncertainty. First, the equilibrium constants 602iaql)
(Equations 1 and 2) are of great importance in the
from the work of Johnstone and Leppla (1934) we
calculations and literature values vary widely. Second,
arrive at an HSO; concentration of 4 x 10es M, an
the basic assumption behind using those constants
SOT concentration of about 4 x lo- M and an
is that ionic equilibria are indeed achieved. However,
the rate constant of the ozone-sulfite ion reaction is ozone cont. of lo- M. So the rate is:
so large that under some of our conditions (those
dS(IV)
of reasonably high total S(IV) and high pH), it is ~-- = (1.1 x 105 X 4 x 10-5 + 7.4 X 108
dt
questionable whether equilibrium was achieved. Since
the rate constants for the second ionization con- x 4 x lo- ?1 x 10 )
stant of sulfurous acid are apparently unknown, it
= 3 x Ill-(M:l)s- .
is impossible to calculate the exact magnitude of the
problem. For each m3 we have I x 10. 1 of solution so we
Qualitatively, the result of failure of the main- now obtain 3 x 10- moles/mJisec reacted 01
tenance of the equilibrium concentration of SO; I x 10~mo1es/m3~1~ or 6.4 x 10mhg/m!h.
would be a lower concentration than that assumed. The starting concentration of 0.007 ppm gives
Thus, the true &ojZ would be larger than the calcu- 30pg/m3 so (6.4/X)) = 0.32 or 33,, per h is reacted.
lated value. As a result, we can conclude that our Penkett arrived at a figure of 12.6,, per h. This diffcr-
value of k r lo9 is a lower limit for the true value. ence is partially due to the apparently different values
Thus, at any pH above 3 (i.e. any naturally occur- used for K,, and K, (he calculated a concentration
ring atmospheric water) mosr of the ozone caused oxi- of HSOJ = 1 x 10. ). Another possible contributing
dation of sulfur species occurs through sulfite ion factor may lie in the precision of our activation
even though over 99% of the sulfur (IV) in solution energy and the consequent uncertainty of the extrapo-
is in the form of bisulfite ion or sulfur dioxide. lated values for the specific rate constants. All of the
Q~ii~tively, the im~rtance of the ozone-oxida- above c~~lculations assume that solution is rapid
tion of sulfur (IV) in the atmosphere is paradoxical. enough that equilibrium between the various phases
In areas of very low sulfur dioxide concentration the and species is maintained.
acidity of any atmospheric water could be low (high Reaction of ozone with low valent metallic ions
pH), but the relative concentration of sulfite ion in solution would decrease its concentration and il
would be high. On the other hand, highly polluted such reactions have very high rate constants, then
(SO,) air would have atmospheric water of relatively the significance of S(N) reaction is lessened. We do
low pH and high sulfur (IV) concentration. However. not have the necessary data to test this alternative
equilibrium at such acidities would demand propor- hypothesis.
tionately less sulfite ion. The first approximation is Comparing the above rate with rates published fat
that the rate of ozone caused disappearance of sulfur other oxidation modes. it must he concluded that.
(IV) is independent of the concentration of sulfur for the cited conditions (liquid droplets. presence of
dioxide in the air. ozone at a constant ~0Ilcentrat~onj ozone caused oxi-
For q~ntitative calculations, it is necessary to dation may be an jmpor~nt contribution to the oxi-
make some assumptions about the quality and mois- dation of S(N) in the atmosphere. For oxamplc,
ture content of a specific air mass in order to assess Brimblecombe and Spedding (1974) using approxi-
the importance of the ozone reaction. The most mately the same total S(N) and H,O(l) values that
obvious point is that the air must contain liquid water we assume. calculate the removal of about 3!,, per
in arder for the ozone reaction to be important as day by the Fe(N) catalyzed oxidation by atmospheric
it has been shown that ozone does not react rapidly oxygen, Cheng et uI. (1971) calculate a 2);;ihdecrcasc
with sulfur dioxide in the vapor phase. in sulfur dioxide in natural fog in the presence of
For purposes of comparison, let us assume approxi- manganese salts and Sidebottom clt ul. (1972) show
mately the same concentrations as Penkett did: SOZ a 1.9x,/h loss of sulfur dioxide photochemically at
at 0.007 ppm, ozone at 0.05 ppm, 0.1 g per m3 liquid high humidity.
 Reaction of sulfur dioxide with ozone in water
Obviously the rates we have determined (as well
as the lesser rates found by Penkett (1972)) are large
compared to those of other oxidation modes and to
actual conversion rates in the atmosphere. Finlayson
and Pitts (1976) note that actual conversion takes
place at between 5 and 10%/h (Los Angeles) to
<0.25%/h (Europe). Again, we must emphasize that
ozonation as a mode of conversion may be significant
only under conditions in which droplets of water are
present.
Acknowledgement-The authors thank the Environmental
Protection Agency for a grant which supported this
research.
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