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Studies on Sulfuric Acid Mist Downwind from a

Sulfuric Acid Manufacturing Plant
a b
James V. Kerrigan+ & Karel Snajberk
a
Lockheed Research Laboratories , Palo Alto , California , USA
b
University of California, Richmond Field Station , Richmond , California , USA
Published online: 16 Mar 2012.

To cite this article: James V. Kerrigan+ & Karel Snajberk (1965) Studies on Sulfuric Acid Mist Downwind from
a Sulfuric Acid Manufacturing Plant, Journal of the Air Pollution Control Association, 15:7, 316-319, DOI:
10.1080/00022470.1965.10468386

To link to this article: http://dx.doi.org/10.1080/00022470.1965.10468386

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 JAMES V. KERRIGAN, j
Lockheed Research Laboratories,
Palo Alto, California,
and KAREL SNAJBERK,
University of California,
Richmond Field Station,
Richmond, California
Downloaded by [Case Western Reserve University] at 10:49 06 November 2014
Studies on Sulfuric Acid Mist
Downwind from a Sulfuric Acid
Manufacturing Plant
Air pollution downstream from a sulfuric acid manufacturing plant is comprised of two
aspects, the amount of acid mist fallout and the concentration in the atmosphere. This
investigation shows that it is desirable to determine each of these by an independent method
of collection. Pans of distilled water were used to collect and determine the sulfuric acid
mist fallout and an electrostatic precipitator was used to determine the sulfuric acid
mist concentration in the atmosphere. The use of Stokes' Law to convert the results
obtained by one method to those obtained by the other requires a knowledge of the particle
size of the sulfuric acid mist droplets. Data presented show that tho uso of an average
particle size can yield a picture of pollution which is in error by many orders of magni-

tude. The study shows that areas adjacent to a plant may be subjected to fallout of rather
large particle size when there are not adequate methods for removal from the emission or
byproduct gases.

M study of sulfuric acid mist in an
area downwind from a sulfuric acid
manufacturing plant is comprised of
two aspects: (1) the concentration in
the atmosphere and (2) the quantity of
acid mist fallout in the area. The con-
centration in the atmosphere is an in-
dication of the effect on the respiration
processes of humans and animals, and the
photosynthesis processes of vegetation
while the quantity of fallout is a measure
of the corrosion effect by contact with
vegetation, buildings, and other phys-
ical objects. Attempts to convert data
on the concentration of acid mist in the
atmosphere to the amount of acid mist
fallout and vice versa through the use
of Stokes' law is dependent on the par-
ticle size used for conversion.
In the present study, an electrostatic
precipitator was used to determine the
concentration of sulfuric acid mist in the
atmosphere, and pans of distilled water
were used to collect and measure the
quantity of acid mist fallout per unit
area of ground surface. This study was
performed during a season of the year
when the prevailing winds, often ac-
companied by fog, showed little fluctua-
tion in wind direction.
In 1918, Wollcott1 reported that
moisture and free acid were excellent
conditioning agents for establishing the
best conductivity in a sample deposited
* The experimental work was supported
by the University of California Sanitary
Engineering Research Laboratory, Rich-
mond, California. Support for completion
of the work was provided by the Lockheed
Independent Research Fund.
t Current address Naval Electronics
Laboratory, San Diego, California.
** Mine Safety Appliance Company.
M.S.A. Precipitator, Cat, No. 48295, No.
598.
on the electrode of an electrostatic pre-
cipitator. Schadt and Cadle2 found the
electrostatic precipitator to be an effi-
cient sampling instrument. They com-
pared the Millipore filter, the Green-
burg-Smith impinger, and the Mine
Safety Appliance Company's Model F
electrostatic precipitator and found that
they showed no observable sensitivity to
the nature of the aerosol studied. At
a voltage between eight and 16 kilovolts
the electrostatic precipitator had an
efficiency of 98% or better.
Materials, Methods, and Reagents
An electrostatic precipitator** and
pans of distilled water were set up next to
each other at a downwind position from
the two emission stacks of the sulfuric
acid plant used in this study. The dis-
tance of this site from the two stacks was
332 and 508 meters. Control samples
collected at nondownwind locations
showed that background sulfuric acid
mist concentration was below the level
of detection.
The pans, located at ground level,
had an automatic feeder which main-
tained the distilled water at a depth of
approximately two inches. When the
period of exposure had expired, the
sample was made up to a volume of two
liters and analyzed. The pans of
water were intended for the collection of
falling sulfuric acid mist droplets, but
they were also capable of collecting
sulfur dioxide during weather conditions
involving turbulent down drafts. These
were observed during the study, but
were of such an infrequent occurrence
as to have little effect on the results.
The portion of the electrostatic pre-
cipitator containing the electrode was
supported about five feet from the
ground, while the case with the high
voltage source and control panel was at
the base of the stand. A suction device
mounted within the instrument provided
an airflowthrough the ionizing chamber
at aflowrate of 2.9 cubic feet per minute.
A known sample volume was passed
between the electrodes while the voltage
was kept just below the arcing level,
i.e., at about 12,000 V. Sulfuric acid
mist was collected by giving the droplets
a negative charge which resulted in
their being attracted to the positive
electrode. After collection the elec-
trode was capped with plastic lids to
prevent any loss of sample. Later it was
washed out several times with distilled
water to a 100-ml volume and analyzed.
Samples were collected by the elec-
trostatic precipitator for periods of 24
hours and longer. Four hours was the
minimum time suitable for the collec-
tion of a chemically analyzable field
sample at the lower concentrationranges.
This period was sufficient to collect
samples of air containing from 0.007 to
0.58 mg/cu m of sulfuric acid mist. The
precipitator determinations were made
for periods coincident with those of the
pans, and covered periods of one to two
weeks.
For a sampling instrument to yield a
valid picture of pollution, it is necessary
that it sample the air isokinetically when
the constituent particles are larger
than a few microns. An isokinetic sam-
pling results when large particles, owing
to their larger moment of inertia, have
difficulty following changes in direction
and velocity of air flow.
If an electrostatic precipitator is
pointed upstream and the velocity of the
stream is equal to the rate of sampling of
the precipitator, then the sample is col-
lected isokinetically. If the stream flow
rate is greater than the sampling rate,
high results are obtained because the
momentum of the larger particles carries

316 Journal of the Air Pollution Control Association

 Table I—Measurement of Sulfuric Acid Mist
Sample Period of Time,
No. days
1 14
2 7
3 14
4 7
5 7
6 7
7 8
8 9
them into the instrument. If the
streamflowrate is less than the sampling
rate, low results are obtained because
the inertia of some of the larger particles
prevents the precipitator from sucking
them in.
It has been shown3 that high errors of
two percent can result from particles
of four microns in size, and of 40% from
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particles 32 microns in size, when the air
velocity is twice that of the sampling
device. When the air velocity is
half that of the sampling device,
similar magnitude low results are
obtained. The diameter of the outer
electrode of the electrostatic precipi-
tator used in the field studies was 1.4
inches and the sampling rate was 2.9
cubic feet per minute. This represents
a sampling rate of 3.1 miles per hour.
Since the prevailing wind velocities
studied were, in general, greater than
three miles per hour, it would be ex-
pected that the electrostatic precipitator
would yield results that could be some-
what high.
Both the turbidimetric4 and the Fritz
titrimetric5-6 methods of sulfate analysis
were used in this study and were found
to be equally reliable.
The chemicals used were reagent
grade or better.
Experimental Results
The atmosphere down stream from
the sulfuric acid manufacturing plant
was sampled for sulfuric acid mist for
periods of one to two weeks. The re-
sults obtained by the pans of distilled
water showed the quantity of sulfuric
acid mist fallout. Those from the electro-
static precipitator indicated the con-
centration of sulfuric acid mist in the
atmosphere. The results are shown in
Table I and suggest that periods of
high concentration in the air were ac-
companied by low fallout and vice
versa.
To convert the data obtained by one
method of collection to that obtained
by the other it is necessary to know the
particle size of the pollutant to be used
with Stokes' Law. Conversion of the
pan fallout data to the concentration in
the atmosphere requires the following
treatment of Stokes' Law.
The relation between volume, V, of
air containing the absorbed aerosol, the
area the of fallout surface, and the dis-
July 1965 / Volume 15, No. 7
portional to the square of the particle
M'H-
size. If the particle size is large, the
Cone, in the particles fall out rapidly; therefore, the
Atmosphere, Fallout, fallout could be heavy as measured by
mg/cu m mg/sq m/day the pans of distilled water, while the
0.011 24.9 concentration in the air might be low,
0.008 47.8 as determined by the electrostatic pre-
0.033 19.3 cipitator. Conversely, if the pollution
0.005 96.6 consisted of small particles, the elec-
0.015 77.4 trostatic precipitator could show a high
0.003 40.2
0.008 41.1 concentration, but the fallout, as shown
0.003 61.6 by pans of distilled water, might be low
because of the small size of the particles.
tance of fall of the particles may be ex- These considerations are depicted graph-
pressed as: ically in Fig. 1, which shows the rela-
V = area of pan x distance of fall of tionship between particle size, concen-
particle = m2xm = ms, in which m is in tration in the atmosphere, and mass
meters. Since the distance is the flux across the distilled water surface.
product of the velocity and time, It is thus seen that both acid fallout and
droplet concentration in the air must
V = vtxA, be measured if a clear picture of the
pollution problem in any particular
in which
location is to be drawn.
v = velocity of a particle, in meters/ If either the pan collection method or
day, the electrostatic precipitator collection
t = time, in days, and method is used alone and it is desired to
A = area of pan, in cu m; estimate the value obtainable by the
or: other method of collection, then a par-
PTY1
ticle size would have to be chosen for
PTY1 SPO
m3 = — x -— x day x 10~2 x m2. use with Stokes' Equation. On the
sec day basis of published data, a particle size
of 2.5 microns might be taken as a
The terminal velocity of a falling par- representative particle size in sulfuric
ticle is calculated from Stokes' Law:
acid mist.7 If data obtained by the
2 pgr2 pgD2 distilled water pan at the same location
v= 9n 18n' as the electrostatic precipitator are con-
verted to concentration in mg/cu m on
where: the basis of a 2.5 micron particle size
and compared with the results obtained
p =
density of a particle, in g/cu cm, by the electrostatic precipitator, as in
g =
gravitation, 980 cm/sq sec, Table II, it is at once evident that on
r =
radius of a particle, in cm, this basis the pan data would grossly
n =
coefficient of viscosity of air, overestimate the concentration in the
182 x 10 ~6 poises, and air.
D = diameter of a particle, in cm. In a similar manner, the use of a 2.5-
Substituting, micron particle size when used with the
electrostatic precipitator data to deter-
9.80 x 102 x pD2 x 1Q-* _ mine the amount of sulfuric acid mist
v= 18 x 182 x 10-6 ~ fallout would lead to results which would
differ from the pan data by similarly
0.003 pD2 (cm/sec).
large factors, and would present a pic-
Then, ture of fallout which was considerably
lower than actually occurs.
V = 8.65 x 104 x lO- 2 x 0.003 x pD2
= 865 x 0.003 x pD2 (cubic meters). Table II shows the factors by which
the pan results and the electrostatic
The density of falling particles W (mass precipitator results would differ if a
per unit volume) equals R/V, when R particle size of 2.5 fx were assumed and
is the amount collected in the pan as also shows the particle size which, when
mg/sq m/day (average mass flux across used with Stokes' Law, would yield
the collecting surface). Substituting results equivalent to those obtained with
for V, the electrostatic precipitator.
R This conclusion may be checked by
W = the consideration that wind velocity
865 x 0.003 xpD2 would help to determine the size of
Taking p = 1.8 g/cu cm, particle which would be deposited at a
site downwind from the particle source.
R If the distance from the source to the
W = collector and the height of the stack dis-
4.7 D2
charge above the ground surface were
From the foregoing it is evident that constant, the size of the particle which
the concentration of sulfuric acid mist could be deposited in a pan would be
per unit volume of air is inversely pro- given by the following relationship:
317
 Table II—Particle Size Necessary for Agreement of Pan and Precipitator nVw
Results D =
0.003 pd'
Period Factor by where
of Pan Precipitator Which Pan and Particle Size n = height of source, in cm,
Run Exposure, Cone, Pan Cone, Precipitator Satisfying Both Vw = wind velocity, in cm/sec,
No. days mg/cu m mg/cu m Differ Instruments p = density of a particle, in g/cu
1 14 0.011 0.85 80 23 cm, and
2 7 0.008 1.63 200 35 d = distance from the source, in cm.
3 14 0.033 0.65 20 11
4 7 0.005 3.29 600 64 The stacks of the sulfuric acid plant
5 7 0.015 2.64 200 33 studied are 175 feet in height (5350 cm),
6 7 0.003 1.37 400 53
150 33 and are located at distances of 33,200
7 8 0.008 1.40
8 9 0.003 2.10 600 65 and 50,800 cm, respectively, from the
location of the pan and precipitator.
Table III shows the distances which dif-
Table III—Relationship of Particle Size, Wind Velocity, and Distance Traveled ferent sized particles would travel before
striking the ground, using Stokes' Law
Rate of Fall Time of Fall Distance Traveled, cm . for wind velocities of one and five miles
Particle of Particle, from Source, Wind Velocityr Wind Velocity per hour.
Size, D ' cm/sec sec of 1 m/hr a of 5 m/hr a
From Table III it is seen that the pan
10 0.54 9900 450,000 —
of water could have received particles
20 2.16 2470 111,000b —
of 30 to 80 microns in size from the
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30 4.86 1100 49,500b 246,000

40 8.75 612 27,000 143,000 nearest stack and of 30 to 60 microns
50 13.5 396 17,800 88,000 from the stack farthest away. These
60 19.4 276 12,400 62,000bb particle sizes are of the same magnitude
70 26.4 202 9,100 45,200b
80 34.5 155 7,000 34,600 as those which were needed to make the
90 43.8 122 5,500 27,300 distilled water pans and the electrostatic
100 54.0 99 4,450 22,200 precipitator results agree when Stokes'
a
One m/hr = 45 cm/sec; 5 m/hr = 224 cm/sec. Law was used, as was shown above.
b
Indicates distance certain sized particles could travel. The occurrence of particles larger than
30 microns is possible, especially when
there is high humidity or fog. In addi-
tion, sulfuric acid stacks are known to
emit large particles if filters are not used.
The local conditions, high humidity and
fog, and the presence of condensing
nuclei such as salts, could also cause
coalescence which would result in par-
ticle sizes of 30 microns or greater. In
any event, the pans would certainly
collect the larger particles from a nearby
source, such as the sulfuric acid plant
stacks. The smaller particles and in
the limiting case sulfur dioxide would be
carried downwind and deposited at
distances up to several miles or more.
The fallout of sulfuric acid mist per
square meter of surface area as shown by
the distilled water pans may be a more
valid measure of corrosion and vegeta-
tion damage than are values showing the
concentration of pollutant in the air. If,
for example, a pan collected 70 mg of
sulfuric acid mist per square meter per
day, in a year this same area might be
expected to collect 25.6 grams. It is
reasonable to expect that this quantity
would contribute to corrosion and plant
damage. For example, some of the
pine trees downwind from the plant
were dead or dying. A Thomas au-
tometer showed that the sulfur dioxide
concentration was below the lethal level
for vegetation (0.4 ppm). Some of the
pine tree needles were weighed and
washed with distilled water which was
analyzed for sulfate. The results
10
showed that the needles contained
20 30 40 50 60
12,000 ppm sulfate. These samples
PARTICLE SIZE, microns
were collected during the dry season of
Fig. 1. Relationship between particle size, concentration In atmosphere, and mass flux the year and lower results might be ex-
across distilled water surface. pected during the rainy season.

318 Journal of the Air Pollution Control Association

 Pans of distilled water may have im- WELCOME NEW MEMBERS
portant advantages in determining the
source of pollution. Being inexpensive,
a large number can be positioned about COMPANY MEMBERSHIP Fox, Robert A.
(National) New York, New York
a suspected source. A profile map of Freilicher, Ira L.
the resultant concentration in the pans, Canada Cement Company Limited Mineola, New York
when combined with wind data, could Montreal, Quebec, Canada Gansler, Marvin H.
be used to indicate the source of pollu- Celanese Corporation of America Mt. Vernon, Washington
tion. Charlotte, North Carolina Gellman, Isaiah
Maxwell House Division Baltimore, Maryland
Preliminary studies of this nature were Hoboken, New Jersey
made on the sulfuric acid plant used in Golber, Myron B.
Signal Oil and Gas Company Chicago, Illinois
this study. Pans of water were set up Houston, Texas
downwind from the plant during periods Graber, Ralph C.
COMPANY MEMBERSHIPS (Local) Washington, D. C.
of labor unrest and periods of normal Harper, Bently F.
operation. The results obtained, when Air Preheater Company Philadelphia, Pennsylvania
combined with a knowledge of the pre- Los Angeles, California Harrison, Charles'JL.
vailing winds, showed that the plant was Kremer Construction Co., Inc. Camden, Arkansas
the cause of pollution in downwind areas. Commack, L. I., New York Harwood, W. W.
Northern Natural Gas Company Bartow, Florida
Conclusions Omaha, Nebraska Incorvia, Joseph
From the experimental results it is Scientific Industries, Inc. Cleveland, Ohio
concluded that: Queens Village, New York Jacobs, Benjamin J.
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(1) The area downwind from a sul- INDIVIDUAL MEMBERSHIPS
furic acid manufacturing plant can be
monitored by pans of distilled water. Alper, Stanley
Analysis of the water is indicative of the Silver Spring, Maryland
amount of sulfuric acid mist incident Andrews, A. I.
on the water surface. It is possible Buffalo, New York
Angus, H. T.
that such information may be as valid Birmingham, England
a measure of the ability of a polluted Banyasz, John L.
atmosphere to corrode metal and Garwood, New Jersey
damage vegetation as are values showing Baruch, Stephen
the actual concentration of the pollu- Brooklyn, New York
tant in the air. Benesch, John T.
(2) The electrostatic precipitator Elizabeth, New Jersey
can be used to determine the concen- Benforado, David M.
tration of sulfuric acid mist in the atmo- Wellsville, New York
sphere. Both the pan and electrostatic Bolo, Eugene R.
East Alton, Illinois
precipitator methods of collection, how- Bostick, Arthur W.
ever, are necessary to obtain a clear Hartford, Connecticut
picture of the pollution problem result- Bradstreet, Jeffrey W.
ing from sulfuric acid mist. Selkirk, New York
(8) Extrapolation of the analytical Brewer, Gerald L.
data obtained by the distilled water Streamwood, Illinois
pans to the concentration of sulfuric acid Brokaw, Arthur T.
mist in the air requires a knowledge of Princeton, New Jersey
the particle size incident upon the water Buck, Joseph A. Jr.,
Fords, New Jersey
surface, so that the concentration in air Bulba, Ely
may then be calculated from Stokes' Cambridge, Massachusetts
Equation. A reasonable particle size Chaumont, A. J.
may be obtained by using an indepen- Strasbourg, France
dent method of sample collection. Con- Coe, John E.
versely, it is necessary to know the Montreal, Quebec, Canada
particle size in order to convert electro- Compton, Robert R.
static precipitator data into meaningful St. Louis, Missouri
fallout data. Connell, Joseph M.
Pittsburgh, Pennsylvania
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July 1965 / Volume 15, No. 7 319