&EPA
            United States
            Environmental Protection
            Agency
            Environmental Sciences Research
            Laboratory
            Research Triangle Park NC 27711
EPA-600/2-78-104
June 1978
            Research and Development
Generation of
Sulfuric Acid
Aerosols for Health
Effect Studies

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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development. U S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology.  Elimination of traditional  grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:

      1.  Environmental  Health  Effects Research
      2.  Environmental  Protection Technology
      3.  Ecological Research
      4.  Environmental  Monitoring
      5.  Socioeconomic Environmental  Studies
      6.  Scientific and Technical Assessment Reports (STAR)
      7.  Interagency Energy-Environment Research and Development
      8.  "Special" Reports
      9.  Miscellaneous Reports

This report has  been assigned  to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental  quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                               EPA=600/2-78-104
                                               June 1978
     GENERATION OF SULFURIC ACID AEROSOLS

           FOR HEALTH EFFECT STUDIES
                      by
       Benjamin Y. H. Liu and Jak Levi
       Particle Technology Laboratory
      Mechanical Engineering Department
           University of Minnesota
        Minneapolis, Minnesota  55455
              Grant No. R801301
               Project Officer

               Thomas G. Dzubay
  Atmospheric Chemistry and Physics Division
  Environmental Sciences Research Laboratory
      Research Triangle Park, NC  27711
  ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
      OFFICE OF RESEARCH AND DEVELOPMENT
     U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA  27711

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                                 DISCLAIMER

     This report has been reviewed by the Environmental Sciences Research
Laboratory, U.S. Environmental Protection Agency, and approved for publica-
tion.  Approval does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
                                     ii

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                                  ABSTRACT

     An aerosol generator has been developed for producing sulfuric acid
particles for animal exposure studies.  The generator has been designed to
supply sulfuric acid aerosols at 330 liters per minute to an animal exposure
chamber of 330 liters internal volume.  The sulfuric acid concentration in
                                        3
the chamber ranges from 0.13 to 1.3 mg/m .  The particle diameter ranges
from 0.04 to 0.15 ym, and the geometrical standard deviation of the aerosol
is about 1.6.
     The generator operates by atomizing a sulfuric acid solution to form a
polydisperse spray.  The droplets are then vaporized in a tube-furnace and
the vapor injected into filtered air at room temperature to form a high con-
centration of small sulfuric acid particles.
     The aerosol generating system has been evaluated by means of several
techniques.  The particle size distribution was measured by an Electrical
Aerosol Analyzer.  Four independent techniques were used to measure the
aerosol concentration.  These include the Electrical Aerosol Analyzer, the
Quartz-Crystal Aerosol Mass Monitor, filter collection and weighing, and
chemical analysis of collected particle samples.  Good agreement has been
found.
     The particular generator described in this report has been constructed
and delivered to the U.S. Environmental Protection Agency for use in its
animal exposure experiments.
     This report was submitted in fulfillment of Grant No. R801301 by the
University of Minnesota under sponsorship of the U.S. Environmental Protec-
tion Agency.  This report covers a period from September 1, 1976 to March 1,
1978, and work was completed as of March 1, 1978.
                                     iii

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                             CONTENTS
Abstract	ill
Figures	vi
Tables	vii
Acknowledgements	viii

   1.  Introduction	1
   2.  Design Criteria	2
   3.  Theoretical Considerations  	 3
            Coagulation Limit 	 3
            Properties of Sulfuric Acid Solution Droplets  	 6
   4.  Description of System	11
            Atomization of the Sulfuric Acid Solution 	11
            Evaporation of Solution Droplets	13
            Condensation and Growth of the Aerosol	13
            Exposure Chamber	13
   5.  Preliminary Experiments	15
            The Atomizer	15
            Vaporization Temperature	16
            Uniformity of the Aerosol in the Exposure Chamber  .  . .21
   6.  Performance of the Aerosol Generating System	24
            Mass Concentration	25
            Size Distribution	31
            Coagulation Chamber	36
   7.  Final Remarks	38

References	39
Appendices

   A.  Detailed size distribution data obtained by EAA	41
   B.  Operating instructions	46
            Introduction	46
            Unpacking and Setup	46
            Operating Principles and Characteristics of the
              Sulfuric Acid Aerosol Generator	49
            Operating Procedure 	54
            Notes on the Operation of the Aerosol Generator ... .56

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                                  FIGURES
Number                                                                  Page
   1  Coagulation limited mass concentration of aerosols for H-SO,
        particles at 50% R.H	  .....   5
   2  Properties of sulfuric acid droplets	   7
   3  Particle size growth factor taking into account the Kelvin
        effect	10
   4  Schematic diagram of system for generating sulfuric acid
        aerosols	12
   5  Variation of total EAA current with time during warm-up for a
        furnace temperature setting of "lo"	18
   6  Variation of total EAA current with time during warm-up for a
        furnace temperature setting of "2"	  19
   7  Variation of total EAA current with time during warm-up for a
        furnace temperature setting of "3"	  20
   8  Location of sampling probe on a horizontal plane within the
        exposure chamber	  22
   9  Schematic diagram of aerosol diluter	27
  10  H.SO, and aerosol mass concentration in exposure chamber as a
        function of solution normality	30
  11  Aerosol size distribution for 0.1N H-SO, solution	33
  12  Aerosol size distribution for l.ON H2SO, solution	34
  13  Aerosol particle size as a function of solution normality for
        primary dilution airflow of 30 1pm	  35
  Bl  Photograph of evaporator-mixer	47
  B2  Photograph of sulfuric acid aerosol generator installed on
        the exposure chamber	47
  B3  Calibration curve of orifice meter for total chamber flow.  ...  55
  B4  Calibration curve of rotameter for primary dilution flow	  57
  B5  Calibration curve of rotameter for atomizer flow	58
  B6  Dimensions of pyrex evaporator tube and mixing nozzle	59
                                     vi

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                                   TABLES


Number                                                                  Page

   1  Variation of Solution pH with Time for Liquid in Atomizer.   ...  16

   2  Characteristics of Atomizer	16

   3  Variation of Aerosol Concentration within Exposure Chamber.  ...  23

   4  Comparison of Aerosol Mass Measurement by Weighing and
        by SO    Analysis	28

   5  Comparison of Aerosol Mass Concentration Measurement by Several
        Different Techniques	29

   6  Summary of Aerosol Size Distribution Parameters for Various
        Generator Operating Conditions	32

  Al  Size Distribution Measurement by EAA	42

  A2  Size Distribution Measurement by EAA (10 1pm primary dilution
        air)	43

  A3  Size Distribution Measurement by EAA (20 1pm primary dilution
        air)	44

  A4  Size Distribution Measurement by EAA (30 1pm primary dilution
        air)	45

  Bl  Characteristics of Aerosol Produced by the Sulfuric Acid
        Aerosol Generator	50

  B2  Aerosol Particle Size as a Function of Coagulation Chamber
        Volume	53

  B3  Consumption and Concentration of H-SO, Solution by Atomizer
        as a Function of Time	53
                                     vii

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                              ACKNOWLEDGEMENTS

     The authors of this report wish to thank Dr. Thomas G. Dzubay of  EPA
for his help in establishing the basic design criteria for the aerosol
generator.  His interest in the project and his helpful discussions are
greatly appreciated.  The authors also wish to thank Mr. Mike Kirtz of EPA
for providing the animal exposure chamber used in the study.  A special word
of thanks goes to Dr. David Y. H. Pui of the University of Minnesota for his
help in the preparation of the report.
     This work is supported by EPA under Grant R801301.
                                     viii

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                                 SECTION 1
                                INTRODUCTION

     Under the sponsorship of the Environmental Protection Agency,  the Par-
ticle Technology Laboratory, University of Minnesota, undertook a study  on
methods for generating sulfuric acid aerosols.  The goal of  the study was to
develop a generator for producing sulfuric acid aerosols in  the 0.01 to  0.1
ym diameter range and at concentration levels that are sufficiently high for
studying the health effect of fine sulfuric acid particles.
     The impetus for the present research came from the finding that sulfu-
ric acid particles are emitted by modern, catalyst-equipped  automobiles.  The
particles are formed apparently by the catalytic conversion  of S02  in the ex-
haust gas due to the combustion of sulfur-containing fuel.   Studies conducted
by EPA at the General Motors Proving Ground and at Los Angeles freeways  con-
cerning this "sulfuric acid problem" (see the recent summary by Maugh, 1977)
showed that the particles emitted are very small in size, typically in the
0.01 to 0.1 ym diameter range (Whitby et al., 1977; Wilson et al.,  1977).
Since small aerosol particles can penetrate deeply into the  human respira-
tory system, the potential health effect of these fine sulfuric acid parti-
cles is of some concern.  The purpose of the present research is to develop
a sulfuric acid aerosol generator for studying the health effect of fine sul-
furic acid particles.

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                                 SECTION 2
                              DESIGN CRITERIA

     The generator described in this report has been developed specifically
for EPA for use in its health effects studies program.  The generator has
been designed for an animal exposure chamber having an internal volume of
0.33 m , and a design flow rate that would provide one complete air ex-
change per minute in the chamber volume, i.e., 330 liters per minute.
Therefore, the principal requirement of the generator is that it must be
capable of supplying the test aerosol at a sufficiently high rate to pro-
duce an adequate sulfuric acid concentration in the test chamber.  The
basic design parameters have been set as follows:
                                     3
     Exposure chamber volume:  0.33 m
     Chamber air flow:  330 liters per minute
     Aerosol diameter range:  0.02 to 0.2 ym
                                                              3
     Sulfuric acid aerosol concentration:  from about 100 yg/m  to a few
                                               3
                                           mg/m
Although the aerosol generated does not need to be monodisperse, both the
size distribution and aerosol concentration must be stable.  In addition,
the generator must be capable of unattended operations and be reasonably
maintenance- and trouble-free.

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                                  SECTION  3
                         THEORETICAL CONSIDERATIONS

COAGULATION LIMIT
     An important consideration in  the  design  of  aerosol  generating systems
to supply highly concentrated aerosols  for  animal exposure  experiments  is
the following:  what is  the maximum aerosol concentration that  can be ob-
tained?  Among the factors limiting the maximum obtainable  aerosol concentra-
tion is the limit imposed by coagulation, which takes place whenever aerosol
is transported from the  point of  formation  to  where  it  is used.   In this
Section, this limit will be determined.
     Consider a monodisperse aerosol undergoing coagulation according to the
following equation:

     f - - KN2                                                        (1)
     dt
where N is the aerosol number concentration and K is the  coagulation coeffi-
cient.  Separating variables and  integrating between appropriate  limits, we
have:
      N    J>T   ft
                                                                       (2)

                                                                       (3)

where N0 is the initial  aerosol concentration  and N  is  the  aerosol concen-
tration at the time t.   It follows  from Equation  (3) that,

     N	^y-                                                       (4)

which can be approximated by
N
No
L
1 ~
dN
~ 2 ~
N
t
Kdt
0
1
IN o

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     N -
if No > ^TT.  The above result states that, if the initial aerosol concen-
        Kt
tration, N0, is sufficiently high, the aerosol concentration N at time t
will be independent of the initial concentration, the concentration N being
solely a function of the coagulation time, t.
     The coagulation coefficient for monodisperse aerosols is a function of
particle size.  The following table, taken from Fuchs (1964), gives the coag-
ulation coefficient for various particle sizes:
     D , ym          0.02          0.04          0.1            0.2
     K,  cm3/sec     12 x 10~10    11 x 10~10    7.2 x 10~10    5.2 x 10"10
Over the particle size range from 0.02 to 0.2 pm, the coagulation coeffi-
cient does not vary greatly.  For the present purpose of making an estimate
                                                                   -9
of the limiting particle concentration that can be obtained, K = 10
  3
cm /sec will be used as an approximate average for the coagulation coeffi-
cient in the above-mentioned size range.
                                                                 -9   3
     Using Equation (5) and the coagulation coefficient of K = 10   cm /sec,
we have for the coagulation-limited number concentrations at various coagu-
lation times:
     t, sec        1       10       100
     N, cm"3      109      108       107
The corresponding mass concentration of the aerosol is related to the number
concentration by:

     M = 7'7rD3pN                                                  (6)
         b    p
where p is the particle density.
     In Figure 1, the mass concentration of a coagulation-limited aerosol
based upon the above analysis is shown as a function of particle size for
various coagulation times.  The particles are sulfuric acid droplets in
equilibrium with ambient air at 50% relative humidity.  At this humidity,
the equilibrium sulfuric acid concentration in the solution is 42.5% by mass,

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      'l	   1  a 4 567*91     a   a 4 5676*1     a   34567891
       .001              .01                 .1                i

                        PARTICLE  DIAMETER, urn

Figure 1.   Coagulation limited mass concentration of aerosols

            for H2SO  particles at 50% R.H.

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                                           3
 and  the  solution  density  is  p  =  1.325  g/cm .   Similar graphs  for other humid-
 ity  conditions  can  easily be constructed.
      From  the above analysis,  it is  clear  that coagulation imposes a limit
 on the maximum  aerosol  concentration that  can be  obtained.  For example,  sup-
 pose  that  a  certain animal exposure  experiment requires  that  sulfuric acid
 particles  be transported  from  where  they are  formed  to where  they are inhaled
by  the  test animals  in 30  seconds.   Then,  according  to  Figure 1,  the maximum
sulfuric acid concentration will be  79  yg/m  if  the  particle diameter is
0.02 ym.   If the ambient relative humidity is 50%, the  maximum aerosol mass
concentration (sulfuric acid plus associated  liquid  water) will be 185 yg/m ,
also from  Figure 1.  Any attempt to  increase  the aerosol concentration to a
level above these limits would  only  result in more coagulation and the pro-
duction of larger particles.  This is an important factor that must be taken
into account in designing  human or animal  exposure experiments in health ef-
fect studies.
PROPERTIES OF SULFURIC ACID SOLUTION DROPLETS
     Sulfuric acid droplets are hygroscopic particles whose  size  will change
in  response to changes in  ambient humidity.   To  facilitate calculations,
Figure 2 has been prepared (Liu, Pui and Kousaka, 1977).
     In Figure 2, the pertinent sulfuric acid solution  properties are shown
plotted against x, the solution concentration expressed in g H»SO,/g solu-
tion.  Included in the plot are the  equilibrium  relative humidity over a flat
solution surface, the solution  density, p,  the boiling  point,  B.P.,  and the
surface tension, a.  The data have been taken from the  Chemical Engineers
Handbook (Perry and  Chilton, 1973) and  from Sabinina and Terpugow (1935),
as  indicated in the  figure.  In addition,  several calculated parameters are
shown. These include the solution normality,  the product, xp,  the particle
growth factor, D /D   , and the Kelvin effect parameter, D    In   — , which are
defined below.  To illustrate the use of  the various plotted quantities, the
following example is  given.
     Consider a 1 ym  diameter sulfuric acid solution droplet in  equilibrium
with relative humidity at 50%.  Using the curve denoted by R.H.  in Figure 2,

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O        o
g        «
It        (M
 11  I  I I  I
     D.  'iNIOd
                          o
                          o
  I I  I  I I  I  I  I I  I  I  I I  I  I

   ui9/*uXp • a • NOISN31
   1 1 1 1 1 it 1 1 1 1 1 1 1 1 1 1
              su»/6 ' 
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we  find  that  the  solution  concentration,  x,  is  0.425  g  of  H?SO,  per  g  of
solution,  or  a  concentration  of  42.5% by  mass.  At  this concentration,  the
                                       3
solution has  a  density, p,  of 1.32  g/cm  ,  a  boiling point, B.P., of  115°C,  a
surface  tension,  a, of 76  dyne/cm,  a normality  of UN,  and a mass concentra-
                                 3
tion, xp,  of  0.55 g lUSO,  per cm of solution.  The  particle size growth
factor, D  /D   , is 1.48, and  the Kelvin  effect parameter,  D    InCp/p^),  is
11.3 x 10   ym.  The last  two parameters are explained  in  more detail below.
     The particle size growth factor, D  /D   , shown  in  Figure  2,  is  the
ratio of the actual diameter  of the particle, D  ,  to the diameter of the
particle,  D  , if the water associated with the  droplet is completely re-
moved.  In the example given  above, the  1 ym diameter sulfuric acid  solution
droplet will become a droplet of pure sulfuric acid  of  1/1.48  = 0»68 ym  if
water is removed.  Similarly, if the ambient humidity is now increased to
90%, then  according to Figure 2, the equilibrium solution  concentration  is
17% by mass and the particle  size growth factor  is 2.12.   Consequently,  the
1 ym diameter particle at  50% R.H. will  now become a particle  of  (2.12/1.48)
(1) = 1.43 ym diameter at  90% R.H.  Thus, the particle  size growth factor
can be used to predict changes in particle size  when ambient relative humid-
ity around the particles is changed.
     In the above discussion  of particle size change, the  Kelvin  effect  has
been ignored.  The Kelvin  effect relates the increase in equilibrium vapor
pressure,  p, over a curved surface to that over  a  flat  surface, p ,
     -i / /  \    2 a M                                                 ,_.
     ^fr'"-' ' RTp-7                                                 (7)
where a is the surface tension of the solution,  M  is  the molecular weight of
water, R is the gas constant  for water,  T is the absolute  temperature, p is
the solution density, and  a is the particle radius.   The quantity plotted in
Figure 2 is the ratio D   InCp/p^) which, according  to Equation  (7),  is:
     V

where D   has the same meaning as that discussed above.  It should be noted
that the quantity on the right-hand side of Equation  (8) involves only
solution and vapor properties, which are functions of x, the solution

                                      8

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concentration.  Consequently, the Kelvin effect parameter is also a function
of x.
     To illustrate the use of the Kelvin effect parameter, let us consider
the example discussed earlier, viz. the 1 ym diameter sulfuric acid solution
droplet at 50% R.H.  Since D   =0.68 ym, and the Kelvin effect parameter is
         -4                 P°              -4                  -4
11.3 x 10   ym, we have InCp/pJ = 11.3 x 10  /0.68 = 16.62 x 10  .  Conse-
quently, P/P,,,, = 1.00166.  For this case, the Kelvin effect is negligible;
the increase in water vapor pressure is only 0.166% above that for a flat
surface.
     Let us now consider a 0.01 ym diameter sulfuric acid particle at 50%
humidity.  Since D   = 0.01/1.48 = 0.0068 ym in this case, we have InCp/p^)
= 11.3 x 10/0.0068 = 0.166, which gives p/pm » 1.18.  Consequently, the
Kelvin effect will cause the equilibrium vapor pressure over the curved drop-
let surface to be 18% higher than that over a corresponding flat surface.
Thus, the effect is substantial and generally cannot be ignored.  In Figure
3, the particle size growth factor, D /D  , taking into account the Kelvin
effect has been calculated and shown as a function of the relative humidity.

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  100
   80
^
>-"

9
ID
UJ
>
UJ
or
   60
   40
   20
                                      ,...., WITHOUT  KELVIN EFFECT
                                         !(INDEPENDENT OF PARTICLE SIZE)
PARTICLE SIZE  GROWTH FACTOR
TAKING  INTO ACCOUNT THE
KELVIN EFFECT
                           1.5                   2.0

                PARTICLE SIZE  GROWTH  FACTOR,  Dp/Dp0
                   Figure 3.  Particle size growth factor taking into account
                           the Kelvin effect.

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                                 SECTION 4
                           DESCRIPTION OF SYSTEM

     There are three main steps involved in the method chosen for generating
H_SO, particles, and they can be summarized, as follows:
     (a)  Atomization of the sulfuric acid solution
     (b)  Evaporation of the solution droplets
     (c)  Condensation and growth of the aerosol
The complete system is shown in Figure 4.
ATOMIZATION OF THE SULFURIC ACID SOLUTION
     Since sulfuric acid is to be used in the experiments, it is necessary
that the aerosol generator be made of an acid-resistant material.  Also, it
is very important that under steady state conditions, the concentration of
the particles should remain constant at the outlet of the atomizing device
used.  The atomizer shown in Figure 4 proved to be most reliable in this re-
spect.  The atomizer is made of 304 stainless steel, and all other parts in
contact with the acid solution are made of either polyethylene or Teflon.
The basic atomizer design has been adapted from that described by Liu and
Lee (1975).  The only difference is that in the system described by Liu and
Lee, a syringe pump is used to feed the liquid continuously to the atomizer,
whereas in the present case, the liquid is drawn into the atomizer head by
suction, and the excess, non-aerosolized liquid is returned to the same
liquid reservoir.  The atomizer is normally operated with dry, filtered com-
pressed air at 35 psig (241 kPa).  At this pressure, the flowrate through
the atomizer is 2.4 1pm, as measured downstream of the atomizer as shown in
Figure 4.
                                     11

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                    OVEN
                  MIXING NOZZLES
                        (PYREX)
                             0-30J
                       Ipmr/   Ipm i
                ATOMIZER
                          PTAMETE
                           VALVES
-_ 1": SOLUTION
                                   AEROSOL (12.4 - 32.4 Ipm)
                                   	»

                                                   ORIFICE
                            OPTIONAL
                            20 LITER
                          COAGULATION
                            CHAMBER
                                                                T
                                                                         FILTER
                                                                             — AIR IN
EXPOSURE
CHAMBER
 (O.33m3)
                                                                  AP
CHAMBER
PRESSURE
                                                 BLOWER
                                                                -•-EXHAUST
                                     REGULATOR
                                                       COMPRESSED
                                                          AIR
ACCUMULATION
  CHAMBER
                             _
                  FILTER  DRYER FILTER
      Figure 4.   Schematic diagram of  system for generating sulfuric acid aerosols.

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EVAPORATION OF SOLUTION DROPLETS
     The atomizer produces a spray of solution droplets, which are polydis-
perse and relatively coarse.  This spray is passed through an accumulation
chamber to remove the liquid collecting on the walls of the connecting
tubing, and then introduced into a Pyrex evaporator tube.  The evaporator
tube is placed within a tube furnace, which is kept at a constant tempera-
ture of about 400°F (204°C).  The residence time of the flow in  the tube is
three seconds, and the gas is heated to a temperature of approximately 220°F
(104°C) at the exit.  At this temperature, the solution droplets are com-
                              »
pletely vaporized.  The specific furnace used is the Lindberg Model 55035
(Solar Basic Industries, 304 Hart St., Watertown, WI 53094).  Under normal
operation, the furnace temperature control is set to "lo" in order to produce
the required furnace temperature of 400°F (204°C) at steady state.
CONDENSATION AND GROWTH OF THE AEROSOL
     The hot gas leaving the evaporator is injected through a small orifice
at the end of the evaporator tube to form a turbulent jet, which is then
mixed with the primary dilution air at room temperature.  The dilution air
is obtained from a filtered air supply and is metered to the mixing nozzle
through a 0 - 30 1pm rotameter, as shown in Figure 4.  The rapid mixing of
the two streams causes the nucleation and condensation of the vapor and the
subsequent coagulation and growth of the sulfuric acid particles.
     The aerosol is then introduced into the exposure chamber by means of
a 1.27 cm i.d., 60 cm long Tygon tubing.  The volume of the flow passages
between the point where the hot gas first comes in contact with  the dilution
air to where the aerosol is further diluted by the exposure chamber air flow
         3
is 125 cm .  This results in a residence time of 0.25 sec for a primary dilu-
tion air flow of 30 1pm.  This residence time is normally too short to cause
substantial particle growth by coagulation.  If further coagulation is de-
sired, an optional coagulation chamber can be used, as shown in Figure 4, to
increase the size of particles produced.
EXPOSURE CHAMBER
     The exposure chamber is roughly cubical in shape, and has an internal
                3
volume of 0.33 m .  An exhaust blower at the chamber outlet provides the
                                     13

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needed air flow of 330 1pm.  This air flow is metered by an orifice meter of
1" (2.54 cm) diameter at the chamber inlet.  The aerosol is introduced into
the chamber just upstream of the orifice.  The rapid mixing of the aerosol
with the main chamber flow quickly dilutes the aerosol and causes the aerosol
size distribution to be "frozen" at that point.  Since the total chamber flow
of 330 1pm is much higher than the aerosol flow of 12.4 to 32.4 1pm, the hu-
midity of the aerosol in the exposure chamber is approximately the same as
the humidity of air at the chamber inlet.  In the experiments described below,
the main chamber air was taken from the air-conditioned laboratory room, and
the relative humidity was between 42 and 48%, with a mean of 45%.
                                     14

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                                 SECTION 5
                           PRELIMINARY EXPERIMENTS

     Several preliminary experiments were performed in order to establish the
performance characteristics of the major system components, and the best
operating conditions for the system.  These are described below, together
with the results obtained.
THE ATOMIZER
     The flowrate of the atomizer was measured by connecting a rotameter
downstream of the atomizer and operating the atomizer with compressed air at
35 psig (241 kPa).  The flowrate was found to be 2.4 liters per minute.
     Next, the atomizer was operated for 24 hours, and the quantity of liquid
consumed was measured.  The rate of liquid consumption was found to be 6..4
ml/hr.
     Since not all the liquid consumed by the atomizer was aerosolized —
some was lost through evaporation — an experiment was performed to determine
the evaporative loss of liquid from the reservoir.  This was done by placing
200 ml of the nominal 0.1 N H-SO, stock solution in the atomizer and mea-
suring the pH of the solution in the reservoir as a function of time.  The pH
was measured by periodically withdrawing 1 ml samples from the reservoir,
diluting the sample by a factor of 1000 with distilled water, and measuring
the resulting pH with a high resolution (0.001 pH) pH meter (Model 701, Orion
Research, Inc., 11 Blackstone St., Cambridge, MA 02139).  The result is shown
in Table 1.  It is seen that as water evaporated, the solution in the reser-
voir became more concentrated, resulting in a lowering of the pH, and an
increase in the solution normality.  The rate of evaporation of water was
calculated and found to be 1.9 ml/hr, or 30% of the total liquid consumption
rate of 6.4 ml/hr.
                                     15

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     TABLE 1.  VARIATION OF SOLUTION pH WITH TIME FOR LIQUID IN ATOMIZER
Time, hr
0
7
20
24
Vol. of Solution
in Reservoir, ml
200
	
	
46
pH
(1000:1 dilution)
3.83
3.71
3.58
3.54

     The liquid consumption and evaporation rates determined above were ob-
tained by operating the atomizer with dry, filtered compressed air at 35 psig
(241 kPa).  The relative humidity of the air, after expanding to atmospheric
pressure, was found to be 20%.
     In Table 2, the principal atomizer characteristics are summarized.

                   TABLE 2.  CHARACTERISTICS OF ATOMIZER
                   Operating Pressure:  35 psig (241 kPa)
                   Flowrate:  2.4 liters per minute
                   Liquid Consumption Rate:  6.4 ml/hr.
                   Liquid Evaporation Rate:  1.9 ml/hr.
                   Reservoir Capacity:  1,000 ml
VAPORIZATION TEMPERATURE
     To determine the furnace temperature needed to vaporize the sulfuric
acid solution droplets, the following experiments were performed.  All ex-
periments were carried out with a 0.1 N solution in the atomizer reservoir.
     First, a steady flow was established in the system by turning on the
compressed air supply and the exhaust blower.  An Electrical Aerosol Analyzer
(EAA) (Model 3030, TSI Inc., P. 0. Box 3394, St. Paul, MN 55165) was then
used to monitor the aerosol in the exposure chamber.

                                     16

-------
     Next, the furnace was turned on, and the total EAA current was recorded
on a strip chart.  The temperature, as indicated by the furnace temperature
indicator, was also recorded at regular intervals up to the maximum attain-
able temperature.
     The furnace was then allowed to cool down to room temperature.  A ther-
mocouple introduced into the exit orifice of the evaporator tube provided
the gas temperature at that point.  The furnace was then turned on, and the
gas temperature, as sensed by the probe, was recorded on a strip chart on the
same time scale as before.  Recordings from the two runs were mapped to give
the EAA current variation with time and with furnace and gas temperatures.
The runs were repeated for three furnace settings, resulting in three steady
state temperatures.  The plots are shown in Figures 5, 6, and 7.  From these
plots, the following observations or conclusions can be made:
     1)  As the furnace began to warm up, there was initially no change in
         the total EAA current, indicating that the size distribution of the
         aerosol was not affected by the initial warming of the furnace.
         This initial warming period varied between 33 minutes, for a furnace
         temperature setting of "lo", and 9 minutes, for a higher temperature
         setting of "3".
     2)  At an exit gas temperature of 138°F (54°C), the total EAA current
         began to rise sharply, reaching a peak at a gas temperature of 180°F
         (82°C).  Thereafter, the EAA current decreased and then finally
         stabilized.  The variation in EAA current was due to the fact that
         the instrument sensitivity is a function of particle size, and that
         as sulfuric acid droplets vaporized and recondensed, the size dis-
         tribution of the aerosol was changed.  The result indicates that
         the minimum vaporization temperature for sulfuric acid droplets
         was 130°F (59°C), and that complete vaporization of the droplets
         could be obtained at a somewhat higher temperature.
     3)  The time for the EAA current to become steady varied from 50 minutes
         for a furnace temperature setting of "3" to 130 minutes for a tem-
         perature setting of "lo".  Thus, sufficient time should be allowed
                                     17

-------
oo
                             135
                             200
160
250
190
300
 210
 350
        220 ~ GAS T (°F)
        375 — OVEN T (°F)
                                40
     60
  80      100

TIME, MINUTES
120
140
                                                                               160
                                                    180
200
                     Figure 5.   Variation of total EAA current with  time during warm-up
                                 for a  furnace temperature setting of "lo".

-------
    115  155
    150  250
200
350
14
12
10
240  260
450  500
280
550
320 — GAS T (°F)
625 — OVEN T (°F)
                                  OVEN SETTING:  2
                                  !        I    ,
                                        -f-
                                            r
                                  i
                                  i
                                T'
                                  i
                                „ i_
                                                              4  -

         20       40      60       80      100
                             TIME, MINUTES
                                  120
                                           140
                                            160
      Figure  6.  Variation of  total EAA  current with time  during
                  warm-up for a furnace temperature setting of "2",

-------
12
10
    120 158  198 240  300      380  430
    175 275  350 450  575      750  800
                              560  - GAS T(°F)
                             1000  - OVEN T(°F)
                                                            T r
                                              OVEN SETTING:
                                                 r
                                                                          	j_._  _.
                                                                                         i  r
         20       40      60       80       100      120

                                         TIME, MINUTES
140
         160
180
         200
220
          Figure 7.  Variation of total EAA  current  with  time during warm-up
                      for a furnace temperature setting of "3".

-------
         for  the system  to stabilize before any  size distribution measurement
         was  made.
     4)  A furnace temperature setting of "lo" was adequate  to completely
         vaporize the sulfuric acid droplets.  At this setting, the  furnace
         reached a steady operating temperature  of 400°F  (204°C) and the gas,
         220°F  (104°C).
UNIFORMITY OF THE AEROSOL IN THE EXPOSURE CHAMBER
     The exposure chamber was probed at 27 different locations in order to
obtain an accurate picture of the uniformity of  aerosol distribution within
the chamber.  Figure 8 shows the nine probe locations on  each of three hori-
zontal planes, and the location of these planes within the chamber.  For each
experiment, the aerosol was sampled at the indicated probe locations with the
EAA, and the  total EAA current was recorded.  Table 3 lists  the results for
several dilution and chamber air flows.  The data include the average EAA
current and the standard deviation of current in each plane, as well as the
average current and the standard deviation for the entire 27 probe locations.
As one would  expect, increasing the chamber flow generally resulted  in more
uniform aerosol distributions.  For instance, at a chamber flow of 132 1pm,
the standard  deviation of the total EAA current was only  6.2% of the average
EAA current.  This indicates that the exact probe location in the chamber is
not critical  for determining the aerosol concentration, since the aerosol
distribution within the chamber is quite uniform.
                                     21

-------
to
to
          Oi
           4»-
           6
•10"-
— 26".


 3"

 --O2
                          10"
                             03
             10"-
                                •SAMPLING LOCATION
                          11"
                           2"
                           FRONT
                                     26"
            Figure  8.   Location of  sampling  probe  on a horizontal plane within the exposure chamber.

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TABLE  3.   VARIATION OF AEROSOL CONCENTRATION WITHIN EXPOSURE  CHAMBER

Sampling Q-- 10 1pm
Point Q-- 132 1pm
I. ID'11 A
*
1-1
1-2
1-3
1-4
1-5
1-6
1-7
1-8
1-9
2-1
2-2
2-3
2-4
2-5
2-6
2-7
2-8
2-9
3-1
3-2
3-3
3-4
3-5
3-6
3-7
3-8
3-9



2.40
2.31
2.35
2.32 1=2.44
2.26 0=0.16
2.37 0/1=0.066
2.60
2.58
2.77
2.05
2.29
2.35
2.45 T-2.37
2.27 a-0.17
2.34 o/T-0.072
2.35
2.49
2.72
2.36
2.40
2.45
2.38 1-2.43
2.38 a-0.10
2.41 o/Y-0.041
2.30
2.50
2.65
Overall: Y-2.41
0-0.15
o/T-0.062
0- 28 1pm Q-- 10 1pm
Q2- 132 1pm Q-- 44 1pm
I, 10~U A I, 10~U A
4.00
3.89
4.20
3.85
3.92
4.10
4.40
4.48
4.40
4.20
3.87
3.83
3.64
3.53
3.51
4.00
4.00
4.50
3.84
3.80
3.92
3.60
3.50
3.55
3.80
3o38
4.45



3.95
3.50
3.15
1=4.14 3.50 1-3.57
0=0.23 3.27 0-0.33
o/Y-0.056 3.61 o/T-0.092
3.28
3.63
4.27
3.00
2.82
• 2.85
Y-3.90 2.61 Y-2.81
0=0.30 2.61 0-0.18
o/Y-0.077 2.50 o/Y-0.064
2.90
2.94
3.06
2.61
2.75
2.78
1-3.76 2.48 1-2.66
0-0.30 2.58 a-0.13
a/I-0.080 2.55 o/T-0.049
2.64
2.62
2.94
1-3.93 1-3.01
0-0.32 0-0.46
o/T-0.081 o/T-0.153
Q." 28 1pm
Q2- 44 1pm
I, 10~U A
4.45
4.23
4.00
4.48 1=4.49
4.13 0-0.33
4.79 0/1=0.073
4.40
4.92
5.02
3.60
3.45
3.60
3.61 Y-3.49
3.22 0-0.12
3.58 o/Y-0.034
3.38
3.47
3.48
3.35
3.30
3.33
3.40 Y-3.35
3.20 o-O.ll
3.41 o/Y-0.033
3.27
3.26
3.61
Y-3.78
0-0.55
o/Y-0.146

Q- • primary dilution air flow
Q2 • total chamber air flow
The first digit indicates the plane location and the second digit, the
location of the probe on that plane.  Thus, 2-5 indicates plane 2 and
probe location 5 (see Figure 8).

                                23

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                                  SECTION 6
                 PERFORMANCE OF THE AEROSOL GENERATING SYSTEM

      As a result of the preliminary experiments described above, the fol-
 lowing operating conditions were adopted as the standard for the aerosol
 generating system:
      Atomizer pressure:  35 psig (241 kPa)
      Furnace temperature:   Control set to "lo" giving a steady state furnace
           temperature of 400°F (204°C) and a gas temperature of 220°F (104°C)
      Chamber air flow:   350 liters per minute*
 The system was then evaluated under these conditions.
      The experiments to evaluate system performance were carried out using an
 auxiliary blower,  rather than with the exhaust blower on the chamber, since
 the latter was found to have inadequate capacity to draw the needed chamber
 flow through the absolute  filter at the chamber intake, as shown in Figure 4.
 During these experiments,  two filters were used, one at the inlet to the
 chamber, as shown in Figure 4, and the other at the chamber outlet and up-
 stream of the exhaust blower.  This arrangement insured that there would be
 no leakage of the sulfuric acid aerosol into the laboratory room, the whole
.system being under vacuum.
      In each experiment, the chamber flow was always turned on prior to the
 atomizer flow. When both flows were on, the furnace would be switched on and
 set to the "lo" setting, or if the heating process was to be speeded up, the
 dial would be set  to "high" for a couple of minutes and the furnace tempera-
 ture closely watched.  When a temperature of 400°F (204°C) was reached,
 the temperature control was then returned to "lo".  Usually hali an hour
 * In these experiments, a  Variac was used to vary the blower speed.  It
   was difficult to set the chamber flow exactly to 330 1pm.  All the ex-
   periments were consequently made with the chamber flow at 350 1pm.
                                      24

-------
was allowed after  the furnace had reached  a  steady  temperature  and before
any measurements were made.
MASS CONCENTRATION
     Four different methods were used to measure the aerosol mass concentra-
tion in the exposure chamber.
                                                                        3
     The aerosol was collected by drawing  a  sample  flow of at least  1 m
through a 1.0 ym pore Fluoropore filter  (Millipore  Corp., Bedford, MA 01730).
This was achieved by timing a flow of 14 1pm through a critical orifice for
a minimum of 71 minutes.  The filter was weighted before and after the  ex-
periment, and the mass concentration of the  aerosol was deduced.  An elec-
tronic microbalance (Model AD-1, Perkin Elmer Corp., Main Ave., Norwalk, CT
06856) was used for this purpose.  The filters were subsequently analyzed by
wet chemical methods at EPA to give the SO,   concentration.  Previous  ex-
periments (Liu and Kuhlmey, 1977) have shown that the efficiency of  the
Fluoropore filter is in excess of 99.9%.
     A quartz-crystal mass monitor (QCMM)  (Model 3500 Piezobalance,  TSI Inc.,
P. 0. Box 3394, St. Paul, MN 55165) was used simultaneously during the  ex-
periments.  The instrument measures the aerosol mass concentration by sensing
the change in vibrational frequency of a quartz crystal as particles are
deposited onto its surface by a small electrostatic precipitator.  The  sam-
pling period of the instrument is 24 seconds for high mass concentrations or
120 seconds for low concentrations.  Several readings were taken for each
run and averaged to give a representative  concentration.
     The fourth method used was the Electrical Aerosol Analyzer, or  EAA.
This instrument measures the size distribution of the aerosol in the 0.0032
to 1.0 ym diameter range by charging the particles  and measuring the result-
ing particle mobilities.  The operating principle of the instrument  has been
described by Liu and Pui (1975) and Liu et al. (1976), who also presented the
basic calibration data for the instrument.   However, in order to convert the
instrument readings into a size distribution, a "data reduction scheme" must
be used.  In the present case, the "simplex minimization" technique  described
by Liu and Kapadia (1977) was used.  From  the measured size distribution, the
aerosol volume was calculated.  The mass concentration was then calculated by
                                     25

-------
                                                         3
multiplying the aerosol volume concentration by 1.35 g/cm , which  is the den-
sity of sulfuric acid droplets at 45% relative humidity.
     The EAA measurement was made by drawing all the required 50 1pm flow
from the exposure chamber.  Except for the case of the 0.1 N solution, all
EAA samplings required a dilution.  This diluter is shown in Figure 9, and
the flow of aerosol to the diluter was monitored by a linear flowmeter in
order to obtain the dilution ratio (130 to 1 dilution was used in  these ex-
periments) .
     The experiments were performed with 0.1 N and 1.0 N H.SO, solutions.
Table 4 shows a comparison of the measured aerosol mass by filter  weighing
and by SO,   analysis.  The agreement between the two methods is seen to be
satisfactory — the mean difference is about 13%, and the maximum  difference,
29%.
     The discrepancy between the two methods of measurement for samples A
and C may have been due in part to the partial neutralization of the col-
lected H,,SO, by ammonia in the laboratory air.  Neutralization of  H_SO, on
the filter would not affect the measured SO,   mass by chemical analysis.
However, if the collected H_SO, particles had been partially neutralized by
ammonium at the time of weighing of the filter, the particle mass  would be
reduced.  The calculated SO,   mass would then also be lower, since it was
calculated assuming no neutralization had taken place.  This may have been
an important factor contributing to the discrepancy between measurement
methods for samples A and C, since the total collected mass for these samples
was quite small (about 0.1 of that for samples D, E, and F).
     In Table 5, the aerosol mass concentrations measured by the several
techniques described above are summarized and compared.  Again, there is good
agreement among the four independent measurement techniques.  In view of the
differences in the operating principles involved, the agreement may indeed be
considered as excellent.
     The experimental results obtained above are summarized and plotted in
Figure 10, showing the aerosol concentration in the exposure chamber as a
function of the normality of the H^SO, solution in the atomizer.   Also shown
in Figure 10 are the results obtained by the EAA for several intermediate
                                      26

-------
        IN
(0.38 - 1.38 1pm)
CAPILLARY TUBE U 	 	 — ... 	 Clu 	 	 '
FLOWMETER I 	 •&* \ \
LS* 	 p— -I 	 H ^ 2 cm T—^ ™J^ .
1pm) [/^°\J 1
L
Px
L^
i
r \ r~"" ou ipm;
r— =*- ^ ^ |
J \ — i mm DIA. NOZZLE
pi ABSOLUTE
pJ FILTER
i
                                        DILUTION AIR
                                      (48.6 - 49.6 1pm)
                    Figure 9.  Schematic diagram of aerosol diluter.

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TABLE 4.  COMPARISON OF AEROSOL MASS MEASUREMENT BY WEIGHING
          AND BY S04~  ANALYSIS


Sample
A
B
C
D
E
F

Cone.
0.1 N
0.1 N
0.1 N
1.0 N
1.0 N
1.0 N

Primary
Dilution
Air , 1pm
10
20
30
10
20
30

Sample
Volume ,
3
m
1.0
1.24
1.06
1.35
1.48
1.44

Aerosol
Mass,
mg
0.24
0.34
0.25
4.41
4.87
4.92
SO ™
4
by Aerosol*
Mass,
0.106
0.150
0.110
1.945
2.148
2.170
Mass
Measured,
0.121
0.148
0.154
1.66
1.97
1.98

Ratio
VM2
0.88
1.01
0.71
1.17
1.09
1.10

* The values given are obtained by multiplying the measured aerosol
  mass by the factor

      Off) (0.45) = 0.441

  where 96 and 98 are respectively the molecular weights of SO,
  and H_SO,, and 0.45 is the equilibrium mass concentration of
  HS0  in the solution droplet at an R.H. of 45%.
                                28

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     TABLE 5.  COMPARISON OF AEROSOL MASS CONCENTRATION MEASUREMENT
	BY SEVERAL DIFFERENT TECHNIQUES*	

H_SO, Concentration                   0.1 N           	1.0 N
Primary Dilution Air, 1pm        10     20    30       10       20       30
                                 Aerosol Mass Concentration
                                 (H2S04 + H20), mg/m3

Filter Weighing                  .24    .27    .24    3.26    3.29     3.42
S04~~ Analysis**                 .27    .27    .33    2.79    3.02     3.12
QCMM                             .16    .25    .24    2.75    3.00     3.00
EAA***                           .25    .30    .27    2.73    3.00     2.65

       * Measured at 45% relative humidity.
      ** Obtained by multiplying the measured SO,   concentration by
         (1/0.45)(98/96) = 2.27, where 0.45 is the mass concentration of
         H_SO  in the solution droplet at 45% R.H., 98 is the  molecular
         weight of H2S04, and 96, that of S04~.
     *** Obtained by multiplying the measurement aerosol volume concen-
         tration by.
         at 45% R.H.
                    3
tration by.1.35 g/cm , the density of the sulfuric acid droplet
                                     29

-------
2000
                                                             -rrrt 5000
           0.1           0.2


                 NORMALITY OF
      0.5

SOLUTION
                                 co
                                  a

                                  00
                                                                 2000
                                                                 1000
Oi
0
O
                                                                       o
                                                                        CM
                                                                       O
                                                                       CO
                                                                        Csl
                                                                       as
                                                                       o
                                                                       M
                                                                       H
S CONC
SOL
AE
   Figure 10.  I^SO^ and aerosol  mass  concentration in exposure chamber

               as a function  of solution normality.
                                 30

-------
 solution normalities.   These  additional  EAA measurements  are described in
 more  detail  in  the next section.
      It is interesting  to note  in Figure 10 that  the  aerosol mass  concentra-
 tion  is proportional to the solution normality, and that  over the  normality
 range of 0.1 N  to 1.0 N, the  H-SO, mass  concentration in  the chamber varied
                     3
 from  0.13 to 1.3 mg/m .
 SIZE  DISTRIBUTION
      The aerosol size distribution was measured by the EAA  for various sul-
 furic acid concentrations and for primary  dilution airflow  of 10,  20,  and 30
 1pm.  The data were reduced by  means of  the "Simplex  Minimization" technique
 of Liu and Kapadia (1977).  The results  are summarized in Table  6,  and a  few
 selected size distribution curves are plotted and compared  in Figures  11  and
 12.   More complete size  distribution data  are given in Tables Al to A4 in
 Appendix A.
      Although the aerosol volume concentration is not greatly affected by
 primary dilution airflow, the particle size is seen to decrease  with in-
 creasing dilution airflow.  This is to be  expected, since the aerosol volume
 concentration is determined primarily by  the atomizer output,  which was un-
 changed in these experiments.   The smaller particle size  obtained  at the
 higher primary dilution  airflows was apparently the result  of the more rapid
 mixing of the vapor with the  dilution air.  With  more rapid mixing,  a greater
 number of small particles are produced,  resulting in  a reduction in the over-
 all size distribution of the  aerosol.  In  all cases,  the  a   of the  aerosol
                                                          O
was not greatly affected, the a being in  the range from  1.5 to  2.0 with  an
                                O
 average of about 1.7.
      Experience with the aerosol generator shows  that the generator has good
 operational  stability when the  primary dilution air was kept above  20  1pm.
 The result in Table 6 shows that the measured size distribution  of  the aero-
 sol was quite stable when primary dilution airflows of 20 and 30 1pm were
 used, whereas at a primary dilution airflow of 10 1pm, less stable  results
were  obtained.  Consequently, 30 1pm has been chosen  as the standard operat-
 ing flowrate for the primary  dilution air.  In Figure 13, the variation of
                                     31

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     TABLE  6.   SUMMARY OF AEROSOL SIZE DISTRIBUTION PARAMETERS  FOR VARIOUS  GENERATOR OPERATING CONDITIONS
to
Solution
Normality
0.1 N 0.2 N
Primary
Dilution (1pm) 10 20
VMD
VMD
a
g
CT
g
\*
\
* t
(2)f
(1)
(2)
(1)
(2)
.14 .056
.082
1.9 1.7
1.8
189 226
215
30 10 20 30
.041
.038 .077 .051 .049
1.5
1.6 1.7 1.6 1.7
204
167 424 425 408
10
.077
.083
1.7
1.7
823
787
0.3 N
20
.058
.058
1.6
1.6
680
640
30
.056
.072
1.7
1.8
622
718
0.6 N
10 20 30 10
.088
.093 .080 .081 .16
1.5
1.6 1.7 1.8 2.0
2060
1530 1430 1400 1830
1.0 N
20
.082
.11
1.5
1.8
2264
2077
30
.082
.089
1.7
1.7
2000
1910
         *

           VMD = geometrical volume mean diameter, ym




            (1) and  (2) refer to the first and second runs, respectively



                                 3, 3
+                       3
  V , total volume in urn /m

-------
                         600
u>
(-0
                                  1 DILUTION VOLUME,  D
                                  •!           1 ,  ^   P»v
                                  ••' AIR, 1pm ymJ/cm->    ym
                                                  i PRIMARY

                                                   DILUTION

                                                   AIR,  1pm
                            .005
0.01
                                                              0.05
                                                                         0.1
                                                                                                  0.5
                                                                         1.0
                                                           PARTICLE DIAMETER,  D  , ym
                                 Figure 11.   Aerosol size distribution for  0.1N H?SO,  solution.

-------
                                                   SOLUTION NORMALITY:   1.0 N
          DILUTION  VOLUME
         ! AIR, 1pm  um^/cm*   pm"   ag
             30      1910  0.09   1.7
             10      1830  0.16   2.0
0.005
0.01
                         0.05
0.1
0.5
           1.0
                               PARTICLE DIAMETER, D ,  urn
      Figure  12.  Aerosol  size distribution  for l.ON H2SO, solution.

-------
                 0.1
u>
                 0.05
                 0.02
                 0.01
                     0.08  0.1
      0.2

NORMALITY OF
1.0
                                                          SOLUTION
                     Figure 13.  Aerosol particle size as a function of solution normality
                                 for primary dilution airflow of 30 1pm.

-------
the geometrical mean volume diameter of the aerosol with  solution normality
is shown for a primary dilution airflow of 30  1pm.
COAGULATION CHAMBER
     The result of the above-described studies shows  that the  aerosol gener-
ator is capable of generating sulfuric acid aerosols  in the  0.04 to  0.087  ym
diameter range when sulfuric acid solutions in the 0.1 N  to  1.0 N range is
used.  Although larger particles can be produced by means of more concen-
trated solutions, it was decided to investigate the use of a coagulation
chamber for increasing the size of particles produced.
     The experiment was performed with 1.0 N solution in  the atomizer.   The
size distribution of the aerosol was measured with and without the optional
20 liter coagulation chamber shown in Figure 4.  It was found  that the geo-
metrical mean volume diameter increased from 0.087 ym when no  coagulation
chamber was used, to 0.130 ym when a 20 liter chamber is  inserted into the
system.  It was found that the measured aerosol volume concentration remained
essentially unchanged, indicating that there was negligible  aerosol  loss in
the coagulation chamber.
     To determine the aerosol particle diameter for other coagulation chamber
volumes, we note that for a coagulation-limited aerosol,  the number  concen-
tration, N, is inversely proportional to the coagulation  time, t, according
to Equation (5).  Since t a V, we have
     N cc (1/v1)                                                        (9)
where V1 is the total effective coagulation volume in the system.  In addi-
tion, the aerosol mass concentration is given by

     m = Or Dp3/6)(N)(p)                                              (10)

If there is no loss of aerosol mass during coagulation, we have, according to
                     -1/3
Equation (10), D  <* N    , and with Equation (9),

     D  <* (V')1/3                                                     (11)
      P
The total effective coagulation chamber volume in the system is the  sum of
                                      36

-------
 the  coagulation  chamber volume,  V ,  in the absence of a coagulation chamber,
 and  the volume,  V,  of  the  coagulation chamber,  or
     V = V + VQ                                                     (12)

 By means of Equations  (11)  and  (12),  we have
                  1/3
     D  oc (V + V )  '                                                  (13)
      p          o
Using the experimental result,
     D  = 0.087  ym     for  V = 0
      P
                                                                      (14)
     D  = 0.13 ym     for  V = 20  liters
      P
and  treating V   in  Equation (13)  as an empirically adjustable  parameter,
we have

     Dp = (^|~)1/3(0.087),  ym                                   (15)

which can be used as an interpolation or extrapolation formula to  estimate
 the  aerosol particle size for various coagulation chamber volumes.   The re-
sult of the calculation is  shown in Table  B2  in Appendix B.  The result shows
 that with a 30 liter coagulation chamber,  particles as large as 0.144 ym can
be obtained using a 1.0 N solution in the  atomizer.
                                     37

-------
                                 SECTION 7
                               FINAL REMARKS

     The aerosol generator described in this report may be considered as a
developmental prototype.  Although it performed satisfactorily during the
evaluating phase of the program, we believe certain improvements can and
should be made.  In addition, certain precautions need to be taken in order
to insure proper operation of the generator.  These are described below.
     1)  Due to its availability in our Laboratory, Tygon tubing was used
         throughout as the connecting tubeing in the generator.  For long-
         term operation, a more chemically inert tubing such as Teflon
         should be used.  It is recommended that the existing tubing be
         replaced with Teflon for long-term operation of the generator and
         in any new generator to be constructed following the basic design
         reported here.
     2)  To avoid neutralizing the generated sulfuric aerosol particles by
         NH_, which may be present in the compressed air line or in the
         supply air for the main chamber air flow, it is recommended that
         these airstreams be purified by passing through an absorbent mate-
         rial with high affinity for NH~.
     3)  Although the generator has been found to be quite stable during
         its operation over a period of several days, its true long-term
         stability needs to be established.  It is recommended that during
         the operation of the generator in the actual animal exposure experi-
         ments, the performance of the generator be monitored closely in
         order to obtain some practical working experience to determine how
         frequently the generating system needs to be cleaned and serviced.
                                     38

-------
                                 REFERENCES
Fuchs, N. A.  1964.  The Mechanics of Aerosols.  MacMlllan Company,
     New York.  408 pp.

Liu, B. Y. H., and A. Kapadia.  1977.  A Computer Data Reduction Program
     for the  Electrical Aerosol Analyzer.  Publication Number 325, Particle
     Technology Laboratory, Department of Mechanical Engineering, University
     of Minnesota, Minneapolis, MN 55455.  26 pp.

Liu, B. Y. H., and G. A. Kuhlmey.  1977.  Efficiency of Air Sampling Filter
     Media.   In: X-Ray Fluorescence Analysis of Environmental Samples, T. G.
     Dzubay,  ed.  Ann Arbor Science, Ann Arbor, MI.  pp. 107-119.

Liu, B. Y. H., and K. W. Lee.  1975.  An Aerosol Generator of High Stability.
     Am. Ind. Hyg. Assoc. J., 36:861-865.

Liu, B. Y. H., and D. Y. H. Pui.  1975.  On the Performance of the Electrical
     Aerosol Analyzer.  J. Aerosol Sci., 6:249-264.

Liu, B. Y. H., D. Y. H. Pui, and A. Kapadia.  1976.  Electrical Aerosol
     Analyzer:  History, Principle and Data Reduction.  Presented at the
     Aerosol Measurement Workshop, University of Florida, Gainesville, FL,
     March 24-26, 1976.  To be published in the Proceedings of the Workshop.

Liu, B. Y. H., D. Y. H. Pui, and Y. Kousaka.  1977.  Properties of ^SCyp
     H20 Solution Droplets.  Particle Technology Laboratory, University of
     Minnesota, Minneapolis, MN 55455.

Maugh, T. H., II.  1977.  Sulfuric Acid from Cars:  A Problem that Never
     Materialized.  Science, 198:280-284.

Perry, R. H., and C. H. Chilton, eds.  1973.  Chemical Engineers1 Handbook,
     5th Edition.  McGraw-Hill Book Company, New York.

Sabinina, L. and L. Terpugow.  1935.  Die Oberflachenspannung des Systems
     Schwefelsaure-Wasser.  Z. Phys. Chem., A173:237-241.

Whitby, K. T., D. B. Kittelson, B. K. Cantrell, N. J. Barsic, and D. F.
     Dolan.  1976.  Aerosol Size Distributions and Concentrations Measured
     during the General Motors Proving Grounds Sulfate Study.  Presented
     before the Division of Environmental Chemistry, American Chemical
     Society, San Francisco, CA, August, 1976.
                                     39

-------
Wilson, W. E., L. L. Spiller, T. G. Ellestad, P. J. Lamothe, T. G. Dzubay,
     R. K. Stevens, E. S. Macias, R. A. Fletcher, J. D. Husar, R. B. Husar,
     K. T. Whitby, D. B. Kittelson, and B. K. Cantrell.  1977.  General
     Motors Sulfate Dispersion Experiment:  Summary of EPA Measurements.
     J. Air Pollut. Control Assoc., 27:46-51.

-------
                   APPENDIX A
DETAILED SIZE DISTRIBUTION DATA OBTAINED BY EAA
                       41

-------
                                      TABLE Al.  SIZE DISTRIBUTION MEASUREMENT BY EAA
M

Date of Experiment: July 11 (0.1 N) and July 14 (1.0 N) , 1977
Solution Normality 0.1 N
Primary Dilution
Air. 1pm 10 20 30
AT AV AT AV AT AV
AlogD "* AlogD "•"• AlogD
P P P
Channel, D , pm
.0100 - .0178 .3 .64 6.0 12.8 10 21.2
.0178 - .0316 2.4 8.2 27 114.8 45 204.8
.0316 - .0562 1.7 43.8 11 300 13 343
.0562 - .100 4.3 195.7 11.2 382 10.1 222.8
.100 - .178 2.45 263.7 2.34 79.2 1.6 12.7
.178 - .316 .61 173 .32 14 .2 .64
.316 - .562 .14 53.7 .07 .68 .04
.562 - 1.00 .04 8.4 .02 .036 .01
> 1.00 .06 — .05 — .05 —
Measured Aerosol
Volume, pm3/cm3 186.8 225.8 201.4
Dilution No No No
Aerosol Volume in
Chamber, um3/cm3 186.8 225.8 201.4
Geometric Mean Volume
Diameter, pm .14 .056 .041
o 1.9 1.7 1.5
g

1.0 N

10 20 30
AT AV AT AV AT AV
AlogD Ui AlogD "* AlogD
P P P

0 0 0 0 .05 .104
.2 .35 .35 .76 .60 2.07
.3 7.6 .42 11.2 .45 12.28
.7 35.9 .82 40 .70 30.68
.255 18.2 .265 16 .215 13.96
.035 1.96 .035 1.72 .027 2.64
.007 .048 .007 .04 .005 .20
.003 — .003 — .003 .016
000—00

16.0 17.5 15.49
129:1 129:1 129:1

2064 2258 1998

.088 .082 .082
1.5 1.5 1.7


* ,T ,,,-11, AV pm3
AI. 10 A* — — — J-—
* • AlogD ' 3 *
6 p cm




-------
                   TABLE A2.  SIZE DISTRIBUTION MEASUREMENT BY EAA   (10 LPM PRIMARY DILUTION AIR)
u>

Date of Experiment: July 21, 1977
Solution Normality




Channel,
.0100
.0178
.0316
.0562
.100
.178
.316
.562

Measured




Dp, urn
- .0178
- .0316
- .0562
- .100
- .178
- .316
- .562
- 1.00
> 1.00
Aerosol
3 3
Volume, vim /cm
Dilution
0.

AI


3.0
13
7.3
10.2
2.14
.25
.04
.01
.06

1 N
AV
AlogD
P

6.4
52
197
420
147
36
4.4
.4
—

215.4
Ho
0.2 N
AV
AlogD
P

2.0 4.0
23 84
15 412
20.7 868
4.5 272
.54 52
.13 4
.03 —
.08 —

424
No
0.3 N
AI AV
AlogD
P

.1 .22
.9 3.3
.7 19
.99 43
.258 17
.036 4
.009 .6
.003 —
.004 —

21.9
36:1
0.6

AI


.05
.9
1
1.83
.55
.086
.018
.008
.008

42.
36:
N
AV
AlogD
P

.1
3
27
86
43
11
1
—
—

5
1
1.0

AI


.1
.4
.3
.99
.7
.154
.033
.012
.011

50.
36:
N
AV
AlogD
P

.2
1
8
45
80
49
16
4
—

8
1
    Aerosol Volume in
               3   3
    Chamber, vim /cm
    Geometric Mean Volume
    Diameter, ym
          215.4


          .082

          1.84
 424


.077

 1.7
787


.083

1.72
1530


.093

1.64
1830


 .16

1.97
         *       -11
           AI, 10   A;
AV

-------
               TABLE A3.   SIZE DISTRIBUTION MEASUREMENT BY EAA  (20 LPM PRIMARY DILUTION AIR)
Date of
Experiment: July 21, 1977
Solution Normality



Channel ,
.0100
.0178
.0316
.0562
.100
.178
.316
.562

Measured
Volume,
Dilution



Dp, urn
- .0178
- .0316
- .0562
- .100
- .178
- .316
- .562
- 1.00
> 1.00
Aerosol
3 3
pm /cm

0.1 N 0.2 N
AT AV AT AV
AlogD " AlogD
P P

11 24
54 232
25 688
21.7 672
3.6 76
.45 8
.09
.03
.09

425
No
0.3 N
AT AV
AlogD
P

.22 .4
1.74 7
.88 25
.92 32
.195 6
.032 .8
.006
.003
.004

17.8
36:1
0.6
AI


0
1.9
1.3
1.83
.47
.073
.015
.005
.007

39.
36:
N
AV
AlogD
P

0
7
36
79
30
7
.6
— -
—

7
1
1.0
AI


.2
1.1
.9
2.17
.76
.123
.026
.009
.012

57.
36:
N
AV
AlogD
P

.4
3.8
24
98
72
27
6
.7
—

7
1
Aerosol Volume in


Chamber, urn /cm



Geometric Mean Volume

Diameter, urn
                           425




                          .051



                          1.61
640




.058



1.6
1430




 .08



1.67
2077





 .11



1.82
     *       -11
       AI, 10   A}
AV

-------
               TABLE A4.  SIZE DISTRIBUTION MEASUREMENT BY EAA  (30 LPM PRIMARY DILUTION AIR)

Date of Experiment: July 21, 1977
Solution



Channel,

.0100
.0178
.0316
.0562
.100
.178
.316
.562

Measured
Volume ,
Dilution



D , um
P
- .0178
- .0316
- .0562
- .100
- .178
- .316
- .562
- 1.00
> 1.00
Aerosol
Urn /cm

0.1 N
AT AV
AlogD
P


14 30
45 209
11 280
7 139
.83 5.6
.09 .3
.02 —
.01 —
.05 —

167
No
0.2 N
AT Av
AlogD
P


22 48
69 304
22 588
20 600
3.3 80
.5 14
.08 ~
.03
.09

408
No
0
AI



.2
2.08
.83
.86
.185
.03
.077
.003
.005


Normality
.3 N
AV
AlogD
P


.4
9
22
34
11
3
.4
—
—

20
36:1

0.6
AI



.2
2.4
1.2
1.74
.465
.065
.016
.005
.009


N
AV
AlogD
P


.4
9
33
72
31
8
1
.1
—

39
36:
1

1.0
AI



.1
1.7
1.4
2.25
.7
.105
.022
.011
.012


N


AV
AlogD_



•
6
38
101
52
13
1
•
—

V


2






1


53
36:
1

Aerosol Volume In


Chamber, um /cm



Geometric Mean Volume

Diameter, um
            167





            .038



            1.56
408





.049



1.68
718





.072



1.82
1400





.081



1.77
1910





.089



1.70
     *       -11
       AI, 10   A;
  AV     	

AlogD  '   3 '
     p   cm

-------
                                 APPENDIX B
                           OPERATING INSTRUCTIONS

INTRODUCTION
     The sulfuric acid aerosol generator described in this manual has been
developed at the Particle Technology Laboratory, University of Minnesota.
The generator was designed for the Environmental Protection Agency for use
               3
with its 0.33 m  animal exposure chamber.  It was tested with the chamber
at the University of Minnesota and shipped to EPA together with the test
chamber.
     This manual covers the operating instructions for the aerosol generator
only.  More detailed information concerning the generator is given in the
main body of this report.
UNPACKING AND SETUP
     As the schematic diagram of the system in the next section shows, there
are three main parts to the generator:  (1) an atomizer sub-assembly, (2) a
flow control panel, and (3) an evaporator-mixer unit.  The atomizer sub-
assembly, the flow control panel, and the evaporator-mixer are placed within
the test chamber during shipment, whereas the furnace for the evaporator is
shipped separately in its own container.
     Following the receipt of the shipment at EPA, carefully unpack and
remove the contents from the test chamber.  Carefully unwrap the atomizer
sub-assembly, the flow control panel, and the evaporator-mixer.  The
evaporator-mixer is made of pyrex glass (see Figure Bl).  Be careful not
to break it.  Two units are supplied, one to be used in the generator, and
the other as a spare.  A detailed drawing of the evaporator-mixer is shown
in Figure B6.
     Set up the system as follows:

                                     46

-------
Figure Bl.  Photograph of evaporator-mixer,
Figure B2.
Photograph of sulfuric acid aerosol generator installed
on the exposure chamber.


-------
     1.  Mount the atomizer sub-assembly on the front of the test chamber
         near the upper left-hand corner as in Figure B2.  The acrylic back
         panel of the atomizer sub-assembly is fastened to the front of the
         test chamber with eight screws.
     2.  Mount the flow control panel on the front of the test chamber above
         the chamber door as in Figure B2.  The panel is fastened to the
         stainless steel bracket - the original mounting bracket for the
         Magnehelic pressure gauge - with four screws.
     3.  Set up the furnace on top of the test chamber on the piece of ply-
         wood supplied.  Set up the metal stand and clamp, and install the
         evaporator-mixer in the furnace as shown in Figure B2.  Adjust the
         evaporator-mixer so that the evaporator is inserted all the way
         into the furnace.
     4.  Make the following interconnections with tubings supplied:
         a)  Connect the outlet of the atomizer-flow rotameter to the com-
             pressed air inlet of the atomizer with the 1/4" nylon tubing
             and Swagelok fitting.
         b)  Connect the outlet of the settling chamber to the inlet of the
             evaporator with the 5/16" i.d. Tygon tubing supplied.
         c)  Connect the outlet of the primary dilution air rotameter to the
             side-inlet on the mixing nozzle with the 5/16" i.d. Tygon tubing
             supplied.
         d)  Connect the outlet of the mixing nozzle to the aerosol inlet of
             the test chamber with the 1/2" i.d. Tygon tubing supplied.
         e)  Connect the Magnehelic gauge to the orifice meter with the
             3/16" i.d. Tygon tubing supplied.
     The completed system should appear as in Figure B2.  Compare the con-
nections you have made with those shown in the photograph.
                                     48

-------
OPERATING PRINCIPLES AND CHARACTERISTICS  OF
THE SULFURIC ACID AEROSOL GENERATOR
     This section provides a brief description of the operating principles
and characteristics of  the aerosol generator.  A schematic diagram  of  the
system is shown in Figure 4.
     Dry, filtered and  regulated compressed air at 35 psig (241 kPa) is sup-
plied to the atomizer via a 0 - 9 1pm rotameter.  In the atomizer,  the H»SO,
solution is atomized to form a polydisperse spray.  The spray is  then  intro-
duced into a one-liter  settling chamber to remove the large drops and  to
allow any accumulated liquid on the connecting tubing to settle.  The  spray
then enters the evaporating tube, which is heated externally by the tube
furnace.  In the evaporating tube, the droplets are vaporized.  The vapor
is then injected into the mixing nozzle where it encounters the primary
dilution air supplied to the nozzle via the 0-30 1pm rotameter.   The rapid
mixing of the vapor and the primary dilution air causes a fine H«SO, aerosol
to be formed.  This aerosol is then introduced into the chamber inlet  where
it is further diluted by the chamber air  flow just upstream of the  orifice
flowmeter.  This diluted aerosol is used  in the test chamber.
     Under normal operating conditions, the temperature control on  the tube
furnace is set to "lo".  At this setting, the furnace will reach a  steady
operating temperature of 350 - 400°F according to the front-panel meter on
the furnace.  The actual gas temperature  at the exit of the evaporator will
be approximately 220°F.
     Under a given set of operating conditions, e.g., for a fixed furnace
temperature and fixed primary and secondary dilution air flows, the size and
the concentration of the sulfuric acid aerosol produced by the generator are
determined by the concentration of the H»SO, solution used in the atomizer.
This is the primary means by which the aerosol size and concentration  are
varied.  Table Bl shows the characteristics of the aerosol produced by the
generator for various H^SO, solution concentrations.  Normally, H^SO,
solutions in the 0.1 N to 1 N concentration range are used.  This results
                                                   3
in an H2SO, mass concentration of 130 to  1,300 yg/m .  The corresponding
particle size range is from 0.04 to 0.87  urn diameter.
                                     49

-------
           TABLE Bl.   CHARACTERISTICS  OF AEROSOL  PRODUCED BY THE SULFURIC ACID AEROSOL GENERATOR


                                Primary  dilution  air flow = 30 1pm (see Note 1)
                                         Chamber  air flow = 350 1pm
                                    Relative  Humidity = 45% (see Note 2)
Ln
O



Run 1






Run 2





Measured Values
3
Filter: Mass Cone., yg/m
3
TSI Piezobalance: Mass Cone., yg/m
3 3
EAA: Volume Cone., ym /cm
D (volume median dia.). ym
P
a
g 3
EPA sulfate: yg/m of sulfate
3 3
EAA: Volume Cone., ym /cm
D (volume median dia.)> ym
P
a
g

0.1
240
240
204
0.041

1.5
145
167
0.038

1.6

H_SO, Solution Normality
0.2 0.3 0.6 1.0
3420
3000
2000
0.056 0.082

1.7 1.7
1375
408 718 1400 1910
0.049 0.072 .081 0.089

1.7 1.8 1.8 1.7

Calculated Mass Concentration of H2SO,, yg/m
Run 1



Run 2
Filter x , _,.
> (see Note 3)
TSI Piezobalance
EAA (see Note 4)
EPA Sulfate (see Note 5)
EAA (see Note 4)
108
108
128
148
101
1540
1350
1220
1400
248 437 851 1160

                                               (continued)

-------
                           TABLE Bl (continued)
                                   Notes
Note 1  Due to flow instability, the experiments were run with a mean chamber
        flow of 350 1pm rather than the standard chamber flow of 330 1pm.
        It is expected that reducing the chamber flow from 350 to 330 1pm
        will have a negligible effect on the measured aerosol characteristics.
Note 2  The relative humidity varied between 42 and 48% during these experi-
        ments, with a mean of 45%.  At a 45% relative humidity, the droplet
        will have an equilibrium concentration of 0.45 g of H~SO, per gram
        of solution and a solution density of 1.35 g/cc.
Note 3  Obtained by multiplying the measured aerosol mass concentration by 0.45.
Note 4  Obtained by multiplying the measured aerosol volume concentration by
        (1.35M0.45) = 0.608.
Note 5  Obtained by multiplying the measured SO,   concentration by the ratio
        of molecular weights of H2SO, and SO,   or (98/96) = 1.021.

-------
     The mass concentration of the sulfuric acid aerosol was measured with
several different techniques as shown in Table Bl.  The techniques  used  in-
clude filter collection and weighing, the integration of the measured size
distribution by the electrical aerosol analyzer to obtain  the  total aerosol
volume, direct mass measurement by the quartz-crystal microbalance  (TSI
Model 3500 Piezobalance) and sulfate measurement by the EPA wet chemical
technique.  The agreement is seen to be good with the spread of data gener-
ally within ±20% from the mean.  The results are also shown plotted in
Figures 10 and 13, which can be used to interpolate between the measured
values.
     To generate sulfuric acid aerosols larger than can be obtained by the
use of a 1 N solution, an optional coagulation chamber is  inserted  between
the aerosol generator and the test chamber as shown in Figure  4.  This causes
the particles to coagulate and grow to a larger size.  Experiments  show  that
with a 20-liter coagulation chamber, the 0.087 ]im diameter aerosol  produced
by a 1 N solution with a 30 1pm primary dilution air flow will grow to a
size of 0.13 pm diameter with negligible reduction in mass concentration.
Other chamber sizes can also be used.  The corresponding particle size at
the chamber can be estimated by means of Table B2.
     The rate of liquid consumption by the atomizer has been measured and
found to be 6.4 ml/hr when dry, filtered compressed air at 35  psig  (241  kPa)
was used as the atomizing air.  Of this, 1.9 ml/hr, or 30%, represents an
evaporative loss, and the remaining 4.5 ml/hr, or 70%, represents the actual
liquid consumed by atomization.  Due to evaporation, the solution in the
atomizer reservoir will become more concentrated during operation.  The  rate
of increase in solution concentration will depend upon the amount of liquid
that is in the atomizer reservoir.  Table B3 shows the calculated volume of
liquid remaining in the atomizer reservoir and the concentration of the  re-
maining liquid at various times for an initial liquid volume of 1,000 ml.
As the table shows, although 1,000 ml will provide sufficient  liquid to  op-
erate the generator continuously for six days, the increase in solution  con-
centration due to evaporation will necessitate more frequent liquid changes.
For instance, if the solution concentration in the reservoir is to  be main-
tained within 30% of the initial concentration, the solution must be replaced
                                     52

-------
   TABLE B2.  AEROSOL PARTICLE  SIZE AS A FUNCTION OF
	COAGULATION CHAMBER VOLUME	

Chamber Volume, liters       Volume Mean Diameter, ym

           0                          0.087 (measured)
           5                          0.101
          10                          0.113
          20                          0.130 (measured)
          30                          0.144
  Calculated by means  of  the  interpolation formula

             DP = Nds^]13  (0-087) *m
  where V is the volume of  the coagulation chamber in liters.
TABLE B3.   CONSUMPTION AND CONCENTRATION OF H-SO, SOLUTION
           BY ATOMIZER AS A FUNCTION OF TIME

Time,
hr
0
16
31
47
63
78
94
109
125
141
Liquid Volume in
Atomizer, ml
1,000
900
800
700
600
500
400
300
200
100
H2S04 Cone, at t
fc ° H-SO, Cone, at t = 0
1.00
1.03
1.07
1.13
1.20
1.30
1.45
1.69
2.19
3.68
                          53

-------
whenever the liquid volume in the reservoir is down  to  500 ml, or  after  about
78 hours of continuous operation.  Other solution changing intervals  can be
easily determined from Table B3 when the maximum allowable concentration
change is known.
OPERATING PROCEDURE
     In order to operate the aerosol generator, you will need a source of
regulated compressed air.  The compressed air should be dried and  filtered
as shown in Figure 4 before it is introduced into the aerosol generator.
A suitable filtered air supply unit is available commercially (Model  3074
Filtered Air Supply, TSI Inc., P. 0. Box 3394, St. Paul, MN 55165).
     Connect the compressed air supply to the inlet of  the rotameters as
shown in Figure B2.  Then operate the generator as follows:  .
     1.  Set the pressure regulator on the filtered air supply unit to zero
         output pressure.
     2.  Fill the atomizer reservoir with H-SO, solution of the desired
         concentration.  Use more or less liquid in the reservoir  depending
         upon the length of operating time needed.  One full bottle (one
         liter) will provide sufficient liquid to operate the generator
         continuously for about six days, or three days if the concentra-
         tion change is to be kept within 30% of its initial value (see
         preceding section).
     3.  Turn on the exhaust blower on the test chamber and adjust the flow
         to obtain a deflection of 0.7" H~0 on the Magnehelic gauge.  This
         will provide a chamber air flow of 330 1pm, or one chamber volume
         per minute.  (For other chamber air flows, refer to the calibration
         curve for the orifice meter given in Figure B3.)
     4.  With the rotameter inlet valves closed, adjust the pressure  regu-
         lator to obtain an output pressure of 35 psig  (241 kPa).
     5.  Adjust the inlet valve on the primary dilution air rotameter to
         obtain a full-scale reading of 150 mm.  This will produce a  primary
         dilution air flow of 30 1pm.  (To obtain other dilution air  flows,
         refer to the calibration curve in Figure B4 for the rotameter.)

                                     54

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                     CHAMBER INLET ORIFICE
                     For Air at 21°C and 1 atmosphere
                      O ASME Orifice
                      O Gas Meter
                                          200
                                  Flovrate, 1pm
Figure B3.   Calibration curve of orifice meter for  total chamber  flow.
                                     55

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     6.  Open the inlet valve on the atomizer flow rotameter.  The rotameter
         should read 25 mm on the scale corresponding to an atomizer flow of
         2.4 1pm.  If the reading is substantially lower, the orifice in the
         atomizer is probably plugged.  The atomizer should then be cleaned.
         (See Figure B5 for the rotameter calibration curve provided by the
         manufacturer.)
     7.  Turn on the furnace and set the temperature control to "lo".  When
         starting with a cold furnace, it will take about two hours for the
         generator output to become steady.  If the heating process is to be
         speeded up, the temperature control dial can be set to "high" for
         a couple of minutes and the \furnace temperature closely watched.
         When a temperature of 400°F (204°C) is reached, the dial should
         then be returned to "lo".
     8.  To shut down the generator, turn off the compressed air supply and
         the furnace.  If the aerosol generator is to be shut down tempo-
         rarily for short periods, say from a few hours to overnight, the
         furnace may be left on its "lo" setting.  Simply turn off the com-
         pressed air.  When the generator is started up again with a warm
         furnace, it will take only one hour for the output to become steady.
NOTES ON THE OPERATION OF THE AEROSOL GENERATOR
     1.  Under no circumstances should the furnace be operated above a tem-
         perature of 1000°F, corresponding to a temperature control setting
         of "3".  The pyrex evaporator will soften or melt at high tempera-
         tures.
     2.  When changing from a concentrated H-SO, solution to a more dilute
         solution, the atomizer reservoir, the settling chamber, the
         evaporator-mixer, and all connecting tubing in contact with H^SO,
         aerosol or vapor should be thoroughly cleaned and dried.  Over a
         period of time, H^SO, solution will accumulate at various points
         in the system.  If the system is not cleaned, the H_SO, solution
         may act as a desiccant, a humidifier, or as a source of H^SO, vapor
         to change the characteristics of aerosols produced by the generator.
                                     56

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                 ROTAMETER
                 PRIMARY DILUTION AIR
                 For Air at 21°C and 1 atmosphere
                 Tube Number:  FM044-40S
                                 12      16       20

                                    Flowrate,  1pm
Figure B4.   Calibration curve of  rotameter for primary  dilution flow.

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                            1140
L/i
CO
                                          ROTAMETER
                                          ATOMIZER FLOW
                                          For Air at 21°C and  1 atmosphere
                                          Tube Number:  FM034-39G
                                   Figure  B5.  Calibration curve of rotameter for  atomizer flow.

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VO
* IT V »
* 13. 0 *
II . . II -i_


r
1
- 	 •' 	 — o
4" to

| ^


                          //
rr
  l/4
                                        2"

fc^
              Figure B6.  Dimensions of pyrex evaporator tube and mixing nozzle.

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the rvvrsc before completing)
1. REPORT NO.
  EPA-600/2-78-104
                                                           3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE

    GENERATION OF  SULFURIC ACID AEROSOLS
    FOR HEALTH EFFECT  STUDIES
             6. PERFORMING ORGANIZATION CODE
             5. REPORT DATE
               June  1978
7. AUTHOR(S)

    B. Y. H. Liu and  J.  Levi
                                                           8. PERFORMING ORGANIZATION REPORT NO,
9. PERFORMING ORGANIZATION NAME AND ADDRESS
    Particle Technology  Laboratory
    Mechanical Engineering Department
    University of Minnesota
    Minneapolis, MN   55455
             10. PROGRAM ELEMENT NO.
               1AA601 CA-24  (FY-78)
             11. CONTRACT/GRANT NO.
               R-801301
 12. SPONSORING AGENCY NAME AND ADDRESS
    Environmental Sciences  Research Laboratory  -  RTF,  NC
    Office of Research  and  Development
    U.S. Environmental  Protection Agency
    Research Triangle Park,  NC  27711
             13. TYPE OF REPORT AND PERIOD COVERED
               Interim  9/76-3/78
             14. SPONSORING AGENCY CODE
                    EPA/600/09
 15. SUPPLEMENTARY NOTES
16. ABSTRACT
       A generator has been developed and constructed for producing sulfuric acid
  aerosols at 330 liters  per minute to an animal  exposure chamber of 330  liters
  internal volume.   Sulfuric acid concentrations  in the chamber range  from 0.13 to
  1.3 mg/m3.  Geometrical mean volume diameters of  the aerosol range from 0.04 to
  0.15 urn, and the geometrical standard deviation of the aerosol is about 1.6.

       The generator operates by atomizing a sulfuric acid solution to form a poly-
  disperse spray.  The droplets are then vaporized  in a tube-furnace and  the vapor
  injected into filtered  air at room temperature  to form a high concentration of
  small sulfuric acid particles.

       The aerosol generating system has been evaluated by means of several tech-
  niques.  Particle  size  distribution was measured  by an Electrical Aerosol Analyzer.
  Four independent techniques were used to measure  the aerosol concentration:   an
  Electrical Aerosol Analyzer, a Quartz-Crystal Aerosol Mass Monitor,  filter col-
  lection and weighing, and chemical analysis of  collected particle samples.  Good
  agreement was found.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lDENTIFIERS/OPEN ENDED TERMS
                           c.  COSATI Field/Group
  * Air pollution
  * Aerosols
  * Sulfuric acid
  * Aerosol generators
  * Development
                               13B
                               07D
                               07B
                               13D
18. DISTRIBUTION STATEMENT

    RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
  UNCLASSIFIED
21. NO. OF PAGES
    68
                                              20. ."CCURITY CLASS (Thispage)
                                                UNCLASSIFIED
                                                                         22. PRICE
EPA Form 2220-1 (9-73)
                                          60

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