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


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.
c
a> Results
o
Rate of Solution
a. The rate of solution of atmospheric
sulfur dioxide in distilled water is shown
Concentration in Fig. 1. The amount of sulfur dioxide
0.81 mg. SO2/M3 found in solution increased at a steadily
2.54 decreasing rate at all atmospheric con-
centrations. No further increase in
0-0-0 5.5 4
amount was found after 2 hr exposure,
x-x-x 8.7 3 which indicated that a saturation or
equilibrium condition had been reached.
The solubility of sulfur dioxide at an
0.5 1.0 1.5 2.0 atmospheric concentration of 0.81 mg
SCVm3 was 4.53 Mg/ml and this was
T i m e - Hou rs proportionately greater than the solu-
bility at an atmospheric concentration
Fig. 2. Rate of solution of sulfur dioxide in distilled water as per cent of
of 8.73 mg SO2/m3 when 16.75 Mg S02/ml
final saturation value.
was found. An increase in the atmos-
pheric concentration greater than ten
pended on the concentration within the The pH of the exposed water solution times resulted in a less than four times
test chamber. Results of the analyses was determined before the sample was increase in the dissolved sulfur dioxide.
were averaged to determine the concen- transferred to the sodium tetrachloro- From Fig. 1 it can be seen that the
tration of airborne sulfur dioxide that mercurate solution. approach to the saturation value was
existed in the chamber during the test. more rapid at the higher atmospheric
Samples concentration that at the lower. This
Analytical Exactly 20 ml of distilled water were is illustrated more clearly in Fig. 2,
Samples exposed in the chamber were placed in Petri dishes that were 12 mm which shows the per cent of final satura-
analyzed by the colorimetric method. deep and 89 mm in diameter. This re- tion reached in each time increment
The water solutions after exposure in the sulted in an area of 62.2 sq cm of solution calculated for each dissolved sulfur
test chamber were transferred to a exposed with a depth of 0.32 cm. The dioxide concentration. It can be seen
sodium tetrachloromercurate solution, samples were placed on a shelf that that, although all of the samples reached
the trapping media used in the colori- passed through the test chamber and a saturation value in less than 2 hr, those
metric method. The absorbed sulfur left exposed, in the dark, to the atmos- samples exposed to higher atmospheric
dioxide was complexed immediately and pheric sulfur dioxide for different peri- concentrations reached saturation
could be held for subsequent analysis. ods of time. The procedure was re- sooner.
404 Journal of the Air Pollution Control Association
While the general shape of the curve The partial pressure of SO2 above the for the hydrogen ion concentration in
suggested a first-order reaction, a solution times a constant H is in equilib- solution that could be used to compute
single rate constant did not describe the rium with the uncombined gas in the the pH which was compared to the
solution of gaseous sulfur dioxide in solution. The constant H is Henry's observed value. The results are pre-
distilled water. If the solution of constant for the solution of gases. sented in Table I, and it can be seen
atmospheric sulfur dioxide followed a Rewriting eq (1): that very close agreement was obtained
first-order reaction, then a single con- between calculated and observed values.
stant would have been obtained re- [S02]Sola. ^ HP From eq. (7), the amount of bisulfite
gardless of the concentration. There- The reactions in solution are: in solution was equal to the amount of
fore, the atmospheric concentration hydrogen ion in the solution, and from
of sulfur dioxide is not the only factor H2O + SO2 ^ H2SO3 (2) eq. (5), the amount of un-ionized sul-
influencing the rate of solution of the furous acid was equal to the total sulfite
gas in distilled water. H2SO3 ^ H+ + H SO3- (3) in solution minus the amount of bi-
It was observed that the pH values sulfite.
of the water samples decreased rapidly (4) Equation (1) states that, if the
upon exposure to atmospheric sulfur amount of un-ionized gas in solution
dioxide. An example is given in Fig. The values for K\ and Ki are as is divided by the partial pressure (the
3 which shows the pH of the distilled follows: air concentration), the result should be
water samples exposed to 5.54 mg Ki = 1.7 x 10- 2 a constant if the gas follows the law of
SO2/M3. partial pressure. The column headed
The rate of solution of the gas was K2 = 5 x 10- 6 "H" in Table I shows the result of this
rapid for the first V2 hr during which With the great difference in the ioniza- calculation for air concentrations rang-
time the pH decreased from 6.1 to tion constants, it can be assumed that ing from 0.81 to 8.73 mg SO2/m3. It
approximately 4.0. As the rate of the hydrogen ion from the second ioniza- can be seen that the solubility of un-
solution of atmospheric sulfur dioxide tion does not contribute appreciably ionized sulfurous acid does follow the
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decreased the pH of the water decreased to the pH of aqueous solutions of sulfur law of partial pressure.
to a final value of 3.8. dioxide and that eq (3) represents the It also can be seen from this table
All of the distilled water solutions conditions that exist in the solution. that the un-ionized sulfurous acid in
showed the same pattern of pH changes If the amount of bisulfite can be de- the solution represented only a small
with changes in the rate of solution of termined for (3), then the amount of fraction of the total sulfite in solution.
the gas. Slightly lower pH values unionized sulfurous acid can be de- Most of the sulfite was present in the
were noted with increasingly higher termined, and from this the value of H form of bisulfite. The concentration of
atmospheric sulfur dioxide concentra- computed for eq. (1), which would show bisulfite, which was equal to the hydro-
tions. The observed pH values found whether the solution of atmospheric gen ion concentration shown on Table
when the solution of atmospheric sulfur sulfur dioxide at low concentrations I, was 100 times the concentration of the
dioxide had reached equilibrium are followed the low of partial pressures. un-ionized sulfurous acid.
shown in Table I. It can be seen that
The information available is the Summary
within the range of atmospheric con-
total amount of sulfur dioxide in solu- A laboratory study was conducted to
centration tested, the pH of the exposed
tion shown in Table I, and the value for determine the rate and extent of ab-
water samples decreased to approxi-
the ionization constants of sulfurous sorption of atmospheric sulfur dioxide
mately 4.0 when solution of the gas
acid. by distilled water surfaces. The infor-
ceased.
The relationships that are known are mation was desired to aid in the assess-
It should be pointed out that the as follows:
distilled water samples were exposed ment of damage to materials by solu-
essentially as surface films with only tions of acid gases and to provide infor-
[H2SO3] + [H SO8-] =
slight depth. The rate of solution of mation that would be useful for the de-
T (total sulfite in solution) (5) termination of possible health effects.
atmospheric sulfur dioxide in deeper
samples of water cannot be determined [H+j [H SO3-] The rate of solution of atmospheric
=
from this study. 1 W sulfur dioxide in distilled water films was
[H2 SO3] found to be a function of the concentra-
Discussion [H+] = [H SO,"] (7) tion of sulfur dioxide in the atmosphere.
The absorption of atmospheric sulfur The higher the concentration in the air,
Solving the simultaneous equations the more rapidly the solution reached a
dioxide by water results in the forma- gives:
tion of sulfurous acid which in turn is saturation value. It was found that
ionized in the solution. The equilib- [H+]2 + Ki [H+] - KxT = 0 (8) over the range of atmospheric concen-
rium conditions that exist are given by trations of 0.81-8.73 mg SO2/m3 distilled
the following equation: Solution of the quadratic equation, water samples reached saturation in less
using the amount of sulfite found in than 2 hr. Even during the 2-hr period
[S02]som. ;= H [SO2]ga3 (1) solutions listed on Table I, gave values 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 4. H. G. Hqughston, "On the Chemical Effect of Wind Speed and Rainfall
the later portions of the exposure period. Composition of Fog and Cloud Water," on the Concentration of Sulfur Diox-
/ . Meteorol, 12: 355 (1955). ide in the Atmosphere," Int. J. Air
These findings indicate that removal 5. H. F. Johnstone, and D. R. Cough- Water Poll, 6: 173(1962).
of atmospheric sulfur dioxide by rain anowr, "Absorption of Sulfur Dioxide 10. T. K. Sherwood, "Solubilities of Sul-
water can be very effective as far as the from Air," Ind. Eng. Chem., 50: 1169 fur Dioxide and Ammonia in Water,"
rate of solution of the gas is concerned. (1958). Ind. Eng. Chem., 17: 745(1925).
6. H. F. Johnstone, and P. W. Leppla, 11. T. H. Sims, "Contributions to the
Rain water passes through the air "The Solubility of Sulfur Dioxide at Knowledge of the Laws of Gas Ab-
which contains the gas and removes the Low Partial Pressures. The Ioniza- sorption," / . Chem. Soc, 14: 1
sulfur dioxide by solution of the gas. tion Constant and Heat of Ionization (1862).
By exposing new water surfaces con- of Sulfurous Acid," / . Amer. Chem. 12. F. P. Terraglio, "Laboratory Evalua-
Soc., 56: 2233 (1934). tion of Methods for Sulfur Dioxide,"
tinually, the rate of absorption of the 7. C. E. Junge, "Sulfur in the Atmos- M.S. thesis, RutgersThe State Uni-
gas into the water remains at a relatively phere," J. Geophys. Res., 65: 227 versity, New Brunswick, N. J. (1962).
high level. (1960). 13. P. W. West, and G. C. Gaeke, "Fixa-
In addition, the findings indicated 8. A. R. Meetham, Atmospheric Pollu- tion of Sulfur Dioxide as Disulfito-
tionIts Origins and Prevention, Per- mercurate (II) and Subsequent Colori-
that surfacefilmsof water are essentially gamon Press Ltd., London (1952). metric Estimation," Anal. Chem.,
saturated in 2 hr so that long-term 9. H. E. Newall, and A. Eaves, "The 18: 1816 (1956).
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
FIRMS SEEK POLLUTION-FREE CAR
a fixed amount of gas and no further
sulfur dioxide would be removed unless Ford Motor Co. and the Mobil Oil for marketing of Humble Oil & Re-
the gas in solution reacted with mate- Corp. are beginning a $7-million re- fining Co. told a conference that the elec-
rials dissolved from the supporting ob- search program designed to develop tric car poses "no immediate prospect of
jects. fume-free gasoline-powered automobiles, competition for the gasoline-powered
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The pH of distilled water samples according to The New York Times. engine in the area of long-distance, high-
exposed in the test chamber decreased These auto emissions, including un- speed, comfortable travel," and the fuel
very rapidly and reached value of 4.0 or burned hydrocarbon or gasoline fumes, cell "appears at leastfifteenyears away"
less and remained at that level for the oxides of nitrogen, and carbon monoxide as a possible factor in the mass trans-
period of the exposure. These findings are considered major air pollutants, and portation field.
can be compared to the report by Cop- in some areas, a heavy contributor to
son2 who found the pH of fog and cloud smog. Research and development efforts
water at Bayonne, N. J. to be as low as A Ford statement said, "It is ex- by the auto industry and others will
4.5 and to the findings of Houghton4 pected the study will lead to develop- produce a virtually smogless gasoline-
who reported the pH of fog and cloud ment of a fuel-engine system that will powered car long before a practical
water occasionally dropped to a value virtually eliminate automobile emissions, electric vehicle can be developed. This
of 3.0 but most often was near 4.0. with minimum cost to the consumer and was the gist of a March 17 statement
Both of these investigations credit the minimal effect on car performance." presented by Robert G. Dunlop, API
solution of acid gases emitted by indus- The Ford-Mobil study will concen- board chairman and president, Sun
trial operations as the cause for the low trate on all elements of the engine, fuel Oil Company, at a joint hearing before
pH values. and lubricant composition, catalysts and the Senate Committee on Commerce
The over-all solubility of sulfur di- after-burners that could help oxidize and Public Works Subcommittee on
oxide in distilled water did not follow unburned gasoline; methods of control- Air and Water Pollution.
the law of partial pressure. Computa- ling evaporation from the fuel tank and
tion of the amount of un-ionized sul- carburetor. An improved gasoline engine, made
furous acid in the solution showed that If Ford and Mobil could develop possible through cooperative research
the solubility of this portion of the dis- fume-free gasoline engines, it could elim- by oil and auto companies, soon should
solved sulfite did follow the law of partial inate the need for an electric-powered bring motor vehicle emission of pol-
pressure. It was found that over 98.5% automobile, which Ford also has been lutants within acceptable limits, ac-
of the sulfite in solution was in the form promoting as a possible cure for auto- cording to Philip White, vice president,
of the bisulfite ion, the remainder was fume pollution. research and development, American
present as un-ionized sulfurous acid. The company continues to see a pos- Oil Co. This smogless car "promises to
This can be compared to the value re- sible market in the United States and cost less and yet be many times more
ported by Falk and Giguere3 of only 10% elsewhere for a special-purpose electric convenient for general use than any
of the sulfite in a \M sulfurous acid so- vehicle designed initially for use in cities foreseeable electric models."
lution being ionized. The very dilute and suburbs. Both Ford and Mobil
solutions formed upon exposure of dis- expect that emissions from gasoline-
powered vehicles can significantly be Technology has not yet advanced
tilled water to atmospheric sulfur far enough for the electric car to replace
dioxide contain mostly bisulfite ion. reduced before a really practical electric
car can be developed. the internal combustion engine-driven
REFERENCES Last fall, Ford's president, Arjay automobile for long distance or express-
1. D. Bienstock, L. W. Brunn, E. M. Miller, announced that Ford was work- way travel, says a report by the Fed-
Murphey, and H. E. Benson, "Sul- ing on an electric car and he predicted eral Power Commission. It adds that
fur DioxideIts Chemistry and Re- then that a practical model would be "the present scale of the research effort
moval from Industrial Waste Gases," is not likely to result in the necessary
Burea of Mines Information Circular available withinfiveto 10 years.
7836, U. S. Dept. of Interior (1958). Others, however, did not share Mr. technological advances in the reasonably
2. H. R. Copson, "A Theory on the Miller's faith in the electric car and near future." And it reaches the con-
Mechanism of Rusting of Low Alloy said they did not think a practical elec- clusion that:" While electric automobiles
Steels in the Atmosphere," Proc. are still too limited in capability and
A.S.T.M., 45, 554 (1945). tric automobile could be developed in
the near future: would be priced too high for common use,
3. M. Falk, and P. A. Giguere, "On the
Nature of Sulfurous Acid," Can. J. short distance vehicles . . . could be-
Chem., 36 : 1121 (1958). Samuel E. Charlton, vice president come practical in the near future."

406 Journal of the Air Pollution Control Association