Journal of the Air Pollution Control Association

ISSN: 0002-2470 (Print) (Online) Journal homepage: http://www.tandfonline.com/loi/uawm16

The Absorption of Atmospheric Sulfur Dioxide by

Water Solutions

Frank P. Terraglio & Raymond M. Manganelli

To cite this article: Frank P. Terraglio & Raymond M. Manganelli (1967) The Absorption of
Atmospheric Sulfur Dioxide by Water Solutions, Journal of the Air Pollution Control Association,
17:6, 403-406, DOI: 10.1080/00022470.1967.10468999

To link to this article: http://dx.doi.org/10.1080/00022470.1967.10468999

Published online: 16 Mar 2012.

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 FRANK P. TERRAGLIO,
Department of Applied Science,
Portland State College,
Portland, Oregon, The Absorption of Atmospheric
and
RAYMOND M. MANGANELLI,
Department of Environmental Science,
Sulfur Dioxide by Water Solutions
Rutgers, The State University

Results of a laboratory study indicate that the rate of solution of atmospheric sulfur dioxide in distilled water,
over the range of atmospheric concentrations of 0.81-8.73 mg SO 2 /M 3 , is a function of the concentration of
SO2 in the atmosphere, with saturation being reached more rapidly at the higher concentrations. This would
indicate that rain water, with constantly renewed surfaces, can be very effective in the removal of atmos-
pheric SO2. The pH of the exposed water samples reached values of 4.0 or less, comparable to values
observed in fog and cloud water near large industrial areas. Overall solubility of sulfur dioxide in dis-
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tilled water did not follow the law of partial pressure. At the atmospheric concentrations used it was found
that over 98.5% of the sulfite in solution was in the form of the bisulfite ion with, the remainder present as
unionized sulfurous acid. Computations using the concentration of unionized sulfurous acid in the solution
showed that the solubility of this portion of dissolved sulfite did follow the law of partial pressure.

)sorption of sulfur dioxide by
water surfaces, whether the sea, surface
waters, rain water, or fog has been men-
tioned as one of the principle removal
mechanisms that take place and prevent
continued build-up of the concentration
of the gas in the air. Corrosion of
metals by sulfur dioxide has been shown
to require the presence of water. Other
materials such as limestone, mortar, and
paper are subject to attack by atmos-
pheric sulfur dioxide, particularly in the
presence of significant amounts of mois-
ture.
The solubility of sulfur dioxide in air-
borne water droplets is an important
consideration in the effect of the gas on
human health, particularly regarding in-
halation of the water aerosol.
For these reasons a study was under-
taken to obtain information about the
solubility of the sulfur dioxide in water
at concentrations near these normally
found in the atmosphere.
One of the early reports on the solu-
bility of sulfur dioxide was by Sims,11
who found that at pressures of 0.25 at-
mospheres and below 40 C the solubility
in water was much greater than that pre-
dicted by the law of partial pressures.
Sherwood10 extended these findings
down to partial pressures (or concentra-
tions) of 1729 mg/m3 of sulfur dioxide
and found the solubility to be 0.2 g SO2/
1000 g of water at 20C. Johnstone and
Leppla6 reported the solubility of sulfur
dioxide in water as 0.16 g SO2/1000 g of
water when the atmospheric concentra-
tion was 700 mg/m3. Johnstone and
Cowghanowr0 determined the rate of ab-
sorption of sulfur dioxide at atmospheric
concentrations of 53.2 and 532 mg/m3 in
water drops containing catalysts and
found that the solubility was a function
of the concentration of sulfur dioxide
and the nature of the catalyst. Many
studies1 on the solubility or sulfur dioxide
in water deal with the removal of the gas
from stack emissions where it is present,
generally, in concentrations above 1%.
Field studies have been undertaken by
a number of investigators to determine
the extent of the solution of sulfur di-
oxide in water. Junge7 reported that
sulfur dioxide removal is achieved pre-
dominantly by precipitation where the
process is solution of the gas in fog drop-
lets followed by precipitation. Meet-
ham8 has reported that in London some
sulfur dioxide is removed from the air by
solution in cloud droplets, falling rain,
and in surface waters, but less than one
fifth of the sulfur dioxide emitted to the
atmosphere is brought down with the
rain. A similar quantity escapes by
being blown to sea. Much of the re-
mainder is reported as dissolved in the
water on buildings, soil, and vegetation,
both after rain and at other times.
Newall and Eaves9 found no correlation
between rainfall and daily sulfur dioxide
concentrations. Houghton4 found the
pH of fog and cloud water to be as low as
3.0 in parts of New England, and he
ascribed this to the solution of sulfur di-
oxide and sulfuric acid from the air into
the water droplets. Copson2 reported
the pH of rain water samples at Bay-
onne, N. J., have been as low as 4.1.
Procedures
Chamber
The absorption studies were carried
out in the laboratory using a dynamic
test chamber, having a volume of 5.59
m3. A complete description of the phys-
ical construction and operation of the
chamber has been given by Terraglio.12
For all of the studies reported the tem-
perature in the chamber was maintained
between 23 and 27 C and the relative
humidity ranged from 50 to 80%.
Constant levels of sulfur dioxide were
produced in the chamber by preparing
cylinder dilutions of sulfur dioxide in
nitrogen at a 1% concentration. The
diluted sulfur dioxide was mixed at a
constant rate with treated laboratory air
and introduced into the test chamber.
Concentrations in the chamber were
monitored by a Davis electroconduc-
tivity meter (Davis Emergency Equip-
ment Co., Newark, M. J.) which re-
corded the attainment of an equilibrium
concentration of sulfur dioxide.
The sulfur dioxide concentration
within the test chamber was measured
by the colorimetric method described by
West and Gaeke.13 Several samples of
the air in the chamber were taken during
the period of a test by collection in
fritted glass bubblers operated at 3
liters/min. The length of sampling de-

June 1967 / Volume 17, No. 6 403

 20

. I5
M
O
(/)
i
E
T3 10
o>
^ o > o>
V.
o o
to
OT
(/) E
^0.81
a _ _ _ _-o- -

. ^.025
0 1 2 3
Time - Hours 2 3
Time Hours
Fig. 1 Rate of solution sulfur dioxide in distilled water.
Fig. 3. pH of distilled water samples exposed to an atmosphere containing
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5.54 mg SO 2 /M 3 .
100

peated for several concentrations of air-

c
a>
o
a.
Concentration
0.81 mg. SO2/M3
2.54
0-0-0
x-x-x
0.5 1.0
T i m e - Hou rs
Fig. 2. Rate of solution of sulfur dioxide in distilled water as per cent of
final saturation value.
pended on the concentration within the
test chamber. Results of the analyses
were averaged to determine the concen-
tration of airborne sulfur dioxide that
existed in the chamber during the test.
Analytical
Samples exposed in the chamber were
analyzed by the colorimetric method.
The water solutions after exposure in the
test chamber were transferred to a
sodium tetrachloromercurate solution,
the trapping media used in the colori-
metric method. The absorbed sulfur
dioxide was complexed immediately and
could be held for subsequent analysis.
404
5.5 4
8.7 3
1.5 2.0
The pH of the exposed water solution
was determined before the sample was
transferred to the sodium tetrachloro-
mercurate solution.
Samples
Exactly 20 ml of distilled water were
placed in Petri dishes that were 12 mm
deep and 89 mm in diameter. This re-
sulted in an area of 62.2 sq cm of solution
exposed with a depth of 0.32 cm. The
samples were placed on a shelf that
passed through the test chamber and
left exposed, in the dark, to the atmos-
pheric sulfur dioxide for different peri-
ods of time. The procedure was re-
borne sulfur dioxide.
The exposure of shallow layers of solu-
tion representing essentially surface
films insured rapid approach to equilib-
rium and uniformity of concentration
throughout the entire body of the solu-
tion.
Results
Rate of Solution
The rate of solution of atmospheric
sulfur dioxide in distilled water is shown
in Fig. 1. The amount of sulfur dioxide
found in solution increased at a steadily
decreasing rate at all atmospheric con-
centrations. No further increase in
amount was found after 2 hr exposure,
which indicated that a saturation or
equilibrium condition had been reached.
The solubility of sulfur dioxide at an
atmospheric concentration of 0.81 mg
SCVm3 was 4.53 Mg/ml and this was
proportionately greater than the solu-
bility at an atmospheric concentration
of 8.73 mg SO2/m3 when 16.75 Mg S02/ml
was found. An increase in the atmos-
pheric concentration greater than ten
times resulted in a less than four times
increase in the dissolved sulfur dioxide.
From Fig. 1 it can be seen that the
approach to the saturation value was
more rapid at the higher atmospheric
concentration that at the lower. This
is illustrated more clearly in Fig. 2,
which shows the per cent of final satura-
tion reached in each time increment
calculated for each dissolved sulfur
dioxide concentration. It can be seen
that, although all of the samples reached
a saturation value in less than 2 hr, those
samples exposed to higher atmospheric
concentrations reached saturation
sooner.
Journal of the Air Pollution Control Association
 While the general shape of the curve
suggested a first-order reaction, a
single rate constant did not describe the
solution of gaseous sulfur dioxide in
distilled water. If the solution of
atmospheric sulfur dioxide followed a
first-order reaction, then a single con-
stant would have been obtained re-
gardless of the concentration. There-
fore, the atmospheric concentration
of sulfur dioxide is not the only factor
influencing the rate of solution of the
gas in distilled water.
It was observed that the pH values
of the water samples decreased rapidly
upon exposure to atmospheric sulfur
dioxide. An example is given in Fig.
3 which shows the pH of the distilled
water samples exposed to 5.54 mg
SO2/M3.
The rate of solution of the gas was
rapid for the first V2 hr during which
time the pH decreased from 6.1 to
approximately 4.0. As the rate of
solution of atmospheric sulfur dioxide
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The partial pressure of SO2 above the
solution times a constant H is in equilib-
rium with the uncombined gas in the
solution. The constant H is Henry's
constant for the solution of gases.
Rewriting eq (1):
[S02]Sola. ^ HP
The reactions in solution are:
H2O + SO2 ^ H2SO3
H2SO3 ^ H+ + H SO3-
The values for K\ and Ki are as
follows:
Ki = 1.7 x 10- 2
K2 = 5 x 10- 6
With the great difference in the ioniza-
tion constants, it can be assumed that
the hydrogen ion from the second ioniza-
tion does not contribute appreciably
for the hydrogen ion concentration in
solution that could be used to compute
the pH which was compared to the
observed value. The results are pre-
sented in Table I, and it can be seen
that very close agreement was obtained
between calculated and observed values.
From eq. (7), the amount of bisulfite
in solution was equal to the amount of
hydrogen ion in the solution, and from
(2) eq. (5), the amount of un-ionized sul-
furous acid was equal to the total sulfite
(3) in solution minus the amount of bi-
sulfite.
(4) Equation (1) states that, if the
amount of un-ionized gas in solution
is divided by the partial pressure (the
air concentration), the result should be
a constant if the gas follows the law of
partial pressure. The column headed
"H" in Table I shows the result of this
calculation for air concentrations rang-
ing from 0.81 to 8.73 mg SO2/m3. It
can be seen that the solubility of un-
ionized sulfurous acid does follow the

decreased the pH of the water decreased
to a final value of 3.8.
All of the distilled water solutions
showed the same pattern of pH changes
with changes in the rate of solution of
the gas. Slightly lower pH values
were noted with increasingly higher
atmospheric sulfur dioxide concentra-
tions. The observed pH values found
when the solution of atmospheric sulfur
dioxide had reached equilibrium are
shown in Table I. It can be seen that
within the range of atmospheric con-
centration tested, the pH of the exposed
water samples decreased to approxi-
mately 4.0 when solution of the gas
ceased.
It should be pointed out that the
distilled water samples were exposed
essentially as surface films with only
slight depth. The rate of solution of
atmospheric sulfur dioxide in deeper
samples of water cannot be determined
from this study.
Discussion
The absorption of atmospheric sulfur
dioxide by water results in the forma-
tion of sulfurous acid which in turn is
ionized in the solution. The equilib-
rium conditions that exist are given by
the following equation:
[S02]som. ;= H [SO2]ga3 (1)
to the pH of aqueous solutions of sulfur
dioxide and that eq (3) represents the
conditions that exist in the solution.
If the amount of bisulfite can be de-
termined for (3), then the amount of
unionized sulfurous acid can be de-
termined, and from this the value of H
computed for eq. (1), which would show
whether the solution of atmospheric
sulfur dioxide at low concentrations
followed the low of partial pressures.
The information available is the
total amount of sulfur dioxide in solu-
tion shown in Table I, and the value for
the ionization constants of sulfurous
acid.
The relationships that are known are
as follows:
[H2SO3] + [H SO8-] =
T (total sulfite in solution) (5)
[H+j [H SO3-]
=
1 W
[H2 SO3]
[H+] = [H SO,"] (7)
Solving the simultaneous equations
gives:
[H+]2 + Ki [H+] - KxT = 0 (8)
Solution of the quadratic equation,
using the amount of sulfite found in
solutions listed on Table I, gave values
law of partial pressure.
It also can be seen from this table
that the un-ionized sulfurous acid in
the solution represented only a small
fraction of the total sulfite in solution.
Most of the sulfite was present in the
form of bisulfite. The concentration of
bisulfite, which was equal to the hydro-
gen ion concentration shown on Table
I, was 100 times the concentration of the
un-ionized sulfurous acid.
Summary
A laboratory study was conducted to
determine the rate and extent of ab-
sorption of atmospheric sulfur dioxide
by distilled water surfaces. The infor-
mation was desired to aid in the assess-
ment of damage to materials by solu-
tions of acid gases and to provide infor-
mation that would be useful for the de-
termination of possible health effects.
The rate of solution of atmospheric
sulfur dioxide in distilled water films was
found to be a function of the concentra-
tion of sulfur dioxide in the atmosphere.
The higher the concentration in the air,
the more rapidly the solution reached a
saturation value. It was found that
over the range of atmospheric concen-
trations of 0.81-8.73 mg SO2/m3 distilled
water samples reached saturation in less
than 2 hr. Even during the 2-hr period
of exposure the rate of solution during

Table IComparison of Calculated and Observed pH Values in Aqueous Solutions Exposed to

Atmospheric SO2 and Computation of Henry's Law Constant

M un-ionized
Air Cone, Soln. Cone, m SO2/I, m H+/1, Ha SO,/1 -pH-
m g SO2/1113 jug SC>2/ml X 104 4
10 x 104 Cal Obs H
0.81 4.53 0.7031 0.7002 0.288 4.15 4.1 0.023
2.54 8.88 1.3880 1.3768 1.12 3.86 4.0 0.028
5.54 12.83 2.005 1.9815 2.31 3.72 3.8 0.026
8.73 16.75 2.617 2.5779 3.91 3.59 3.7 0.028
H = pgSO2/mlsoln./mgSO2/m3air.

June 1967 / Volume 17, No. 6 405

 the first portion was more rapid than in
the later portions of the exposure period.
These findings indicate that removal
of atmospheric sulfur dioxide by rain
water can be very effective as far as the
rate of solution of the gas is concerned.
Rain water passes through the air
which contains the gas and removes the
sulfur dioxide by solution of the gas.
By exposing new water surfaces con-
tinually, the rate of absorption of the
gas into the water remains at a relatively
high level.
In addition, the findings indicated
that surfacefilmsof water are essentially
saturated in 2 hr so that long-term
exposure to the same atmospheric
concentration of sulfur dioxide would
not result in further removals of the gas
from the air. Thus a film of water cov-
ering nonviable objects would absorb
a fixed amount of gas and no further
sulfur dioxide would be removed unless
the gas in solution reacted with mate-
rials dissolved from the supporting ob-
jects.
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The pH of distilled water samples
exposed in the test chamber decreased
very rapidly and reached value of 4.0 or
less and remained at that level for the
period of the exposure. These findings
can be compared to the report by Cop-
son2 who found the pH of fog and cloud
water at Bayonne, N. J. to be as low as
4.5 and to the findings of Houghton4
who reported the pH of fog and cloud
water occasionally dropped to a value
of 3.0 but most often was near 4.0.
Both of these investigations credit the
solution of acid gases emitted by indus-
trial operations as the cause for the low
pH values.
The over-all solubility of sulfur di-
oxide in distilled water did not follow
the law of partial pressure. Computa-
tion of the amount of un-ionized sul-
furous acid in the solution showed that
the solubility of this portion of the dis-
solved sulfite did follow the law of partial
pressure. It was found that over 98.5%
of the sulfite in solution was in the form
of the bisulfite ion, the remainder was
present as un-ionized sulfurous acid.
This can be compared to the value re-
ported by Falk and Giguere3 of only 10%
of the sulfite in a \M sulfurous acid so-
lution being ionized. The very dilute
solutions formed upon exposure of dis-
tilled water to atmospheric sulfur
dioxide contain mostly bisulfite ion.
REFERENCES
1. D. Bienstock, L. W. Brunn, E. M.
Murphey, and H. E. Benson, "Sul-
fur DioxideIts Chemistry and Re-
moval from Industrial Waste Gases,"
Burea of Mines Information Circular
7836, U. S. Dept. of Interior (1958).
2. H. R. Copson, "A Theory on the
Mechanism of Rusting of Low Alloy
Steels in the Atmosphere," Proc.
A.S.T.M., 45, 554 (1945).
3. M. Falk, and P. A. Giguere, "On the
Nature of Sulfurous Acid," Can. J.
Chem., 36 : 1121 (1958).
406
4. H. G. Hqughston, "On the Chemical
Composition of Fog and Cloud Water,"
/ . Meteorol, 12: 355 (1955).
5. H. F. Johnstone, and D. R. Cough-
anowr, "Absorption of Sulfur Dioxide
from Air," Ind. Eng. Chem., 50: 1169
(1958).
6. H. F. Johnstone, and P. W. Leppla,
"The Solubility of Sulfur Dioxide at
Low Partial Pressures. The Ioniza-
tion Constant and Heat of Ionization
of Sulfurous Acid," / . Amer. Chem.
Soc., 56: 2233 (1934).
7. C. E. Junge, "Sulfur in the Atmos-
phere," J. Geophys. Res., 65: 227
(1960).
8. A. R. Meetham, Atmospheric Pollu-
tionIts Origins and Prevention, Per-
gamon Press Ltd., London (1952).
9. H. E. Newall, and A. Eaves, "The
FIRMS SEEK POLLUTION-FREE CAR
Ford Motor Co. and the Mobil Oil
Corp. are beginning a $7-million re-
search program designed to develop
fume-free gasoline-powered automobiles,
according to The New York Times.
These auto emissions, including un-
burned hydrocarbon or gasoline fumes,
oxides of nitrogen, and carbon monoxide
are considered major air pollutants, and
in some areas, a heavy contributor to
smog.
A Ford statement said, "It is ex-
pected the study will lead to develop-
ment of a fuel-engine system that will
virtually eliminate automobile emissions,
with minimum cost to the consumer and
minimal effect on car performance."
The Ford-Mobil study will concen-
trate on all elements of the engine, fuel
and lubricant composition, catalysts and
after-burners that could help oxidize
unburned gasoline; methods of control-
ling evaporation from the fuel tank and
carburetor.
If Ford and Mobil could develop
fume-free gasoline engines, it could elim-
inate the need for an electric-powered
automobile, which Ford also has been
promoting as a possible cure for auto-
fume pollution.
The company continues to see a pos-
sible market in the United States and
elsewhere for a special-purpose electric
vehicle designed initially for use in cities
and suburbs. Both Ford and Mobil
expect that emissions from gasoline-
powered vehicles can significantly be
reduced before a really practical electric
car can be developed.
Last fall, Ford's president, Arjay
Miller, announced that Ford was work-
ing on an electric car and he predicted
then that a practical model would be
available withinfiveto 10 years.
Others, however, did not share Mr.
Miller's faith in the electric car and
said they did not think a practical elec-
tric automobile could be developed in
the near future:
Samuel E. Charlton, vice president
Effect of Wind Speed and Rainfall
on the Concentration of Sulfur Diox-
ide in the Atmosphere," Int. J. Air
Water Poll, 6: 173(1962).
10. T. K. Sherwood, "Solubilities of Sul-
fur Dioxide and Ammonia in Water,"
Ind. Eng. Chem., 17: 745(1925).
11. T. H. Sims, "Contributions to the
Knowledge of the Laws of Gas Ab-
sorption," / . Chem. Soc, 14: 1
(1862).
12. F. P. Terraglio, "Laboratory Evalua-
tion of Methods for Sulfur Dioxide,"
M.S. thesis, RutgersThe State Uni-
versity, New Brunswick, N. J. (1962).
13. P. W. West, and G. C. Gaeke, "Fixa-
tion of Sulfur Dioxide as Disulfito-
mercurate (II) and Subsequent Colori-
metric Estimation," Anal. Chem.,
18: 1816 (1956).
for marketing of Humble Oil & Re-
fining Co. told a conference that the elec-
tric car poses "no immediate prospect of
competition for the gasoline-powered
engine in the area of long-distance, high-
speed, comfortable travel," and the fuel
cell "appears at leastfifteenyears away"
as a possible factor in the mass trans-
portation field.
Research and development efforts
by the auto industry and others will
produce a virtually smogless gasoline-
powered car long before a practical
electric vehicle can be developed. This
was the gist of a March 17 statement
presented by Robert G. Dunlop, API
board chairman and president, Sun
Oil Company, at a joint hearing before
the Senate Committee on Commerce
and Public Works Subcommittee on
Air and Water Pollution.
An improved gasoline engine, made
possible through cooperative research
by oil and auto companies, soon should
bring motor vehicle emission of pol-
lutants within acceptable limits, ac-
cording to Philip White, vice president,
research and development, American
Oil Co. This smogless car "promises to
cost less and yet be many times more
convenient for general use than any
foreseeable electric models."
Technology has not yet advanced
far enough for the electric car to replace
the internal combustion engine-driven
automobile for long distance or express-
way travel, says a report by the Fed-
eral Power Commission. It adds that
"the present scale of the research effort
is not likely to result in the necessary
technological advances in the reasonably
near future." And it reaches the con-
clusion that:" While electric automobiles
are still too limited in capability and
would be priced too high for common use,
short distance vehicles . . . could be-
come practical in the near future."
Journal of the Air Pollution Control Association