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Gravitational Transport of Particles

in Pure Gases and Gas Mixtures


S. K. Dua, P. Brand, E. Karg, and J. Heyder
Clarkson Uniuersity, Department of Chemistry
Potsdum, NY 13699-5810, USA (S.K.D.)
GSF Forschungszentrum fir Umwelt und Gesundheit, Projekt Inhalation
P.O. Box 11.29, 0-85758, Oherschleissheim, Gemuny (P.B.; E.K.; J.H.)

Sedimentation velocities of 0.96- and 1.52-pm tation velocities. The measured sedimentation veloci-
monodisperse polystyrene latex particles in pure gases ties ranged from 28.5 p m s -'
in Ar to 40.2 p m s in -'
and gas mixtures at 23" and 37°C have been measured He for 0.96 p m and from 65.6 p m s - ' in
using a sedimentation cell. The gases used for the 80%Ar-20%0, to 96.8 p m s - ' in CO, for 1.52-pm
measurement were N,, O,, Ar, He, CO,, SF,, air, aerosols at 23°C. At 37°C the values were generally
80%He-20%0,, 70%He-20%0,-10%N,, 80%SF6- lower (within 5%) than at 23°C. The sedimentation
20%0,, 70%SF,-20%0,-10%N, and 80%Ar-20%0,. velocities in 80%He-20%02, 70%He-20%02-10%N,,
Calculations of the terminal sedimentation velocity were 80%SF,-20%0,, 70%SF,-20%0,-10%N, gases were
also done using the parameters appropriate for the within 11% and in 80%Ar-20%0, within 20.4% of
particles and the gaseous media. There was good agree- those in air.
ment between the observed and the predicted sedimen-

INTRODUCTION Svartengren et al., 1989; Heyder et al.,


For aerosol particles of diameters above 1991). Since the deposition of these parti-
0.6 pm, in still air, gravitational transport cles is strongly dependent on the mean
is the main mechanism for the deposition terminal sedimentation velocity, while
in the lungs (Davies, 1973). Particles of performing studies with different gases,
this size are often used to study particle the influence of the gas composition on
deposition and clearance in the lungs the sedimentation must also be consid-
(Swift et al., 1982; Anderson et al., 1988; ered. In the past, evaluations of the sedi-
Kreyling et al., 1991) and for lung func- mentation velocity of monodisperse parti-
tion testing (Beinert et al., 1990). Re- cles in various gases and gas mixtures
cently particle deposition in the lungs has were based on the theoretical estimations
been reported to depend not only on the (Briant, 1990). In the present study mea-
inhalation conditions (tidal volume, air surements of the sedimentation velocity
flow rate) but also on the composition of of monodisperse polystyrene latex parti-
the inspired gas (Swift et al., 1982; cles suspended in various pure gases and
gas mixtures are performed using a sedi-
mentation cell. A comparison between the
"Correspondencc should be addressed to: Dr. S. K. measured and the predicted values based
Dua, Chemistry Department, Clarkson University, on the theory is made. The pure gases
Potsdam, NY 13699-5810, USA. used are nitrogen (N,), oxygen (O,), ar-
A e m m l Scicncc a n d Technology 21:170 178 (1994)
O 1914 C l s c v ~ c rScience Inc.
Gravitational Transport of Particles in Gases

gon (Ar), helium (He), carbon dioxide window glass plate which consists of infra
(CO,), sulfur hexafluoride (SF,) and the red light (IR) absorbing materials. The
mixtures are air, heliox (80%He-20%0, laser beam passes the viewing field with-
and 70%He-20%0,-10%N,), sulphox out touching the walls and then vanishes
( 8 0 % SF,-20% 0 , a n d 7 0 % SF,- in a light trap.
20%0,-10%N2) and 80%Ar-20%0,. The particles are observed under a
Studies are carried at the laboratory tem- mean scattering angle of 90" by means of
perature (23°C) and the human body tem- a microscope, a charge coupled device
perature (37°C) using monodisperse latex (CCD) camera, a video screen and a pro-
particles of 0.96- and 1.52-pm diameters. cessing system. The objective lens of the
microscope is fixed inside a cylindrical
bore of the copper block and isolated
THE SEDIMENTATION CELL from the settling chamber by an IR ab-
Figure 1 shows the schematics of the sedi- sorbing glass plate. An area of 2 mm x 2
mentation cell used for the study. It is mm is viewed and the magnification factor
similar to the one used by Stahlhofen et at the screen is 64.
al. (1975). The settling path of the parti- The processing system automatically
cles has an internal diameter of 6 mm and observes single particles and analyses the
is located along the axis of a cylindrical data. As soon as a particle enters the field
copper block of 68 mm diameter and 180 of view of the lens it is marked and fol-
mm height. The aerosol to be studied is lowed up to a settling distance of about 1
filled in this channel and both ends are mm or less, if it runs out of focus. The
shut by vacuum tight valves. The aerosol time taken to travel this distance is mea-
particles are illuminated by a He-Ne laser sured and the sedimentation velocity is
beam of 5 mW output (Model PL-750, calculated and displayed on the screen.
Polytec GmbH Waldbronn, Germany). To calibrate the settling distance in
The beam enters the aerosol channel terms of the distance between two hori-
through a hole in the copper block. The zontal lines on the screen, a standard
inlet of the beam is closed by a double graticule (5 + 100/100 mm, Carl Zeiss,
Oberkochen, Germany) and monodis-
perse latex particles are used.
6 mm
I I
1 , aerosol in EXPERIMENTAL SETUP
valve Monodisperse polystyrene latex particles
copper block (Duke Scientific Corp., California, USA)
of nominal diameters 0.966 p m and 1.53
p m were used for the study. The count
median diameter and the geometric stan-
dard deviation of 0.966-pm particles mea-
sured by electron microscope (Scanning
Microscope, Model 7300F, Joel, Tokyo,
Japan) were 0.961 p m and 1.024 respec-
tively, and that of 1.53-pm particles by
optical microscope (Axioplan, Carl Zeiss,
Oberkochen, Germany) were 1.518 p m
FIGURE 1. Schematic diagram of sedimentation and 1.018. The sizes reported in this paper
cell. correspond to microscopic measurements.
172 S. K. Dua et al.

The stock suspensions of latex were where


diluted with filtered deionized water and
the surfactant was removed by centrifug- V is the terminal sedimentation veloc-
ing (Allen and Raabe, 1985). The latex ity (m s - ' )
p, is the density of the particle (kg
aerosol particles were dispersed with a
medical nebulizer (Paul Ritzau Pari-Werk, m-3)
p, is the density of the gas in which the
Starnberg, Germany) by using the desired
filtered gas, diluted with the gas, and dried particles are suspended (kg m p 3 )
by passing through a diffusion drier. They g is the acceleration due to gravity (m
were then passed through the sedimenta- sC2)
tion cell. The gas flushing time was large d is the diameter of the spherical parti-
enough to ensure that the cell was at the cle (m)
gas atmosphere. The cell valves were then is the viscosity of the gas (Pa s)
shut and the measurements were per- C(d) is the Cunningham slip correction
formed after 5 minutes for the cell to The gas density, p,, at any temperature
attain thermodynamic equilibrium. T and pressure P is obtained from
The measurements were carried out at
two temperatures namely the laboratory
temperature (23°C) and the human body
temperature (37°C). The cell was covered
with a heating element and isolated from where p , is the gas density at the refer-
the surroundings by covering with an alu- ence temperature TJK) and p, at tem-
minum foil. For the measurements at the perature T (K). Po and P are the refer-
body temperature, the heating element ence pressure (Po = 101.325 kPa) and the
was switched on. laboratory pressure respectively. For the
For the measurements at the body tem- gas mixture p, is given by
perature the temperature on the surface
of the cell was continuously monitored
and was checked to be the same as inside
the cell before making the measurements. where yi is the component molar fraction
The temperatures during the entire study and p, the density of the ith gas compo-
were within the range 37"-38°C and steady nent.
during any measurement. The atmo- The mean free path, A, of the gas
spheric pressures were in the range molecules at any temperature, T, and
94.4-98.0 kPa. The sedimentation velocity pressure, P , is obtained from Eq. 4 (Wil-
values (both observed and predicted) pre- leke, 1976).
sented in this paper correspond to the
actual temperatures and pressures.

where A,, To, and Po are the reference


THEORY mean free path, temperature, and pres-
The sedimentation velocity, V , of a sphere sure, respectively. S is the Sutherland
of diameter d is given by constant.
The slip correction, C(d), is given by
Gravitational Transport of Particles in Gases 173

where a , p, y are the slip parameters as- al. (1977). A,, is the fraction of molecular
sociated with the mean free path, h,. weight ratios.
Rader (1990) has tabulated the values of
the mean free path, A,, and slip parame-
ters of some gases at the reference pres-
sure and at 23°C and has recommended
values for the slip parameters for other
gases.
Rader (1990) and Weast et al. (1989-
1990) have tabulated the values of q and
h for some gases at P, and at some tem-
peratures. The q at any other tempera-
ture is obtained from Eq. 6: where

where q, and r) are the gas viscosities at


temperatures TOand T , respectively. S is and Mi; = M i / M j , where Mi and M, are
the Sutherland constant. Its values for the molecular weights of the ith and the
some gases are readily available and for jth components, respectively.
others, it is often calculated from the The mean free path, A, for a gas or a
known values of q at two temperatures gas mixture at the standard pressure is
using Eq. 6 (Briant, 1990). given by
The viscosity of a gas mixture by
Brokaw method is given by (Reid et al.,
1977)
where the quantities at a given tempera-
ture are
h the mean free path of the gas
molecules (m),
q the viscosity of the gas or the gas
mixture (Pa s),
where n is number of gases in the mix-
p, the average gas density (kg m-3) at
ture, 7 is the viscosity of the gas mixture, the standard pressure,
y, is the component molar fraction, and 77, C- the mean molecular speed (m s-')
is the component viscosity. and is calculated from the Eq. 12
(Briant, 1990):

where rl, and rl, are the viscosities of the where R is the universal gas constant
ith and jth components. For nonpolar (8.31448 kg m2 s-2 K-' mol-I), MI the
gases S i j = Sji = 1. For a polar gas expres- molecular weight and y, the molar frac-
sions for Sij and Sji are given by Reid et tion of the ith component. Table 1 ex-
174 S. K. Dua et al.

TABLE 1. Gas Parameters at Standard Pressure (101.325 k pa), at 23°C and 37°C
Sutherland
Viscosity ai Density at Mean Free Path at Slip Constant
23°C 37°C 23°C 37°C 23°C 37°C Parameter S
Gas Pa s) (lo3 kg m-3) ( pm) (Y (K)

N2 1.762 1.824 1.153 1.101 0.0658 0.0697 1.150 98.2


0 2 2.041 2.119 1.317 1.258 0.0713 0.0757 1.150 138.9
Ar 2.248 2.335 1.645 1.571 0.0703 0.0747 1.227 141.4
Hc 1.971 2.036 0.165 0.158 0.1943 0.2054 1.277 73.8
COZ 1.481 1.546 1.823 1.741 0.0438 0.0467 1.150 220.5
SF, 1.541 1.615 6.011 5.740 0.0252 0.0270 1.207 336.0
Air 1.835 1.901 1.192 1.138 0.0674 0.0714 1.207 110.4
80%He-20%0, 2.144 2.219 0.395 0.377 0.1014 0.1073 1.270 96.5
70YoHe-20Y00,-10%N2 2.107 2.181 0.494 0.472 0.0858 0.0909 1.270 97.4
80%SF6-20%02 1.622 1.698 5.071 4.842 0.0256 0.0275 1.207 297.0
70%SF6-20%0,-10%N2 1.653 1.729 4.586 4.379 0.0261 0.0280 1.207 276.8
80%Ar-20%0, 2.209 2.294 1.580 1.509 0.0703 0.0747 1.207 141.4
51 .8%He-48.2%SF6 1.818 1.900 2.983 2.848 0.0166 0.0178 1.207 251.2

hibits the values of 9,p,, A, a,and S for greater than 2% deviation between the
various gases. The sedimentation velocity observed and predicted values. The maxi-
is calculated using the parameters corre- mum difference between repeat measure-
sponding to the actual temperature and ments was 1.5%.
pressure at which the measurements are Tables 2 and 3 show that there is good
performed. So, the observed and the pre- agreement between the observed and the
dicted sedimentation velocities can be predicted values. It is possible to measure
easily compared (Tables 2 and 3). accurately even small changes ( < 4%) in
sedimentation velocity of pure gases re-
sulting from changes in either a gas (e.g.,
RESULTS N, to air) or the temperature (23" to
Table 2 gives the observed mean sedimen- 37°C) or pressure.
tation velocity and the relative standard The maximum deviation between the
deviation for 0.961-pm polystyrene latex observed and the predicted values is for
aerosols in different gases at 23" and 37°C. the gas mixtures 70%SF,-20%0,-10%N,
It also presents the predicted values based at 23°C and 80%He-20%0, at 37°C. It is
on the parameters 9,pg, A, and P corre- 11% for 0.961-pm and 5% for 1S18-pm
sponding to the conditions prevalent dur- aerosols.
ing the measurements. Table 3 gives simi- The sedimentation velocity in 80%
lar values for 1.518-pm aerosols. For each He-20%0,, 70%SF,-20%0,-
experiment measurements were made on 1 0 % N 2 , 80%SF6-20%0,, 70%SF6-
about 100 aerosol particles. A number of 20%0,-10%N, gases is within 11% of
measurements were made on the sedi- that in air for the sizes and the tempera-
mentation velocity in air and even small tures studied. In 80%Ar-20%0, it is
change (increase or decrease due to within 20.4% of that in air.
change in atmospheric pressure) could be For most of the sedimentation veloci-
accurately predicted. The experiments ties the relative standard deviation is in
were repeated for all gases showing the range 5%-lo%, the higher values be-
Gravitational Transport of Particles in Gases 175

TABLE 2. Scdirnentation Velocity of 0.961-prn Polystyrene Latex Particles in Different Gases


at 23°C and 37°C
--

Sed~mentattonVelocity Deviation Sedimentation Vclocity Deviation


at 23°C from at 37°C from
Observed (RSD) Predicted Predicted Observed (RSD) Predicted Predicted
Gas (~rns-I) ( ~ r n s ' ) (%) (pm s-') (Frn s ' ) ('%I
N2 + 0.21
0 2 + 1.45
Ar + 0.52
Hc - 0.44
CO, +1.37
SF6 + 2.36
Air - 0.85
80%He-20%0, + 11.12
70%1He-20%0,-1O%N, + 8.05
80%SF;,20%02 + 3.35
70%SF6-20960,-10%N2 +5.92
80%Ar-20%02 - 1.53
51.8%He-48.2%SF,
-
Observed (RSD) observed mean and (Relative standard deviation); particle density
to gravity = 9.81 m s-'.
= 1046.8 kg m " aceeelration due

ing for 0.961-pm particles. Table 3 also predicted values for the temperatures and
presents the ratio of the relative standard the sizes studied suggesting that the sedi-
deviation (Ratio RSD) of 0.961-pm and mentation cell is a very useful tool for the
1.516-pm particles at 23" and 37°C. measurement of the sedimentation veloc-
ity of aerosols.
The maximum observed deviation of
11% in helium gas mixtures and SF, gas
DISCUSSION mixtures cannot be explained. Some ideas
The observed values of sedimentation ve- for the explanation of the results are
locities of pure gases are within 4% of the brought out in following:
TABLE 3. Sedimentation Velocity of 1.518-pm Polystyrcnc Latex Particles in Different Gases
at 23°C and 37°C
Scdimentation Velocity Deviation Sedimentation Velocity Deviation
at 23°C from at 37°C from
Obscrved (RSD) Predicted Predicted Ratio Obscrved (RSD) Predicted Predicted Ratio
Gas (,urns') (pm s-') (%) RSD ( ~ r n s - ' ) ( ~ r n s ' ) (96) RSD

N2
0 2
Ar
He
C02
SF6
Air
80%He-20960,
70%He-20%0,-10%N,
80%SF6-20%02
70%SF6-20%02-10%N,
80%Ar-20%O,
Obaerved (RSD) = ohscrved mean and (relative standard deviation); ratio KSD = ratio of the relative standard deviation
of thc vclocitics of 0.961- and 1.518-prn particles.
176 S. K. Dua et al.

The important parameters influencing viscosity and mean free path of the
the sedimentation velocity, for a given 80%He-20%0, mixture containing 1.1%
aerosol, are the gas density, particle den- water vapor were calculated using the Eqs.
sity, particle size, acceleration due to grav- 7 and 11, respectively, treating the mix-
ity, gas viscosity, and the slip correction ture as a three component system. Their
(Eq. 1).The gas and particle density, and values at 23°C work out to 2.118 * lo-' Pa
the acceleration due to gravity are accu- s and 0.0973 pm, respectively, compared
rately known, hence they have negligible with 2.144* 1 0 - 9 a s and 0.1014 p m (Ta-
contribution to the observed deviation. ble 1) when water vapor is not considered.
The helium gas mixtures have higher vis- Use of these values gives the predicted
cosities than any of their component gases sedimentation velocity of 31.81 p m s-' as
(Table 1). A higher viscosity results in compared with the observed value of 33.89
lower sedimentation velocity. Since the p m s-'. Now the deviation between the
calculated viscosity values are within 2% observed and the predicted values is
of the experimental values (Turner et al., 6.54%, i.e., 1% less than of the case in
1989) and since SF6 mixture viscosities are which water vapor is not considered. Sim-
in between those of the component gases, ilar is the situation in 70%He-20%0,-
the small uncertainties in the viscosity val- 10%N2 mixture. For SF, gas mixtures the
ues, if at all, cannot explain the observed viscosity of the gas mixtures containing
deviations. The slip correction, C(d), for a the water vapor remains practically the
given size depends on a ,3!, and y (mainly same (difference < 0.15%) as without it.
a ) and A. a values for the gas mixtures So there is no influence of water vapor on
are not available in the literature. A value the sedimentation velocity in SF6 gas mix-
of 1.27 for H e gas mixtures (close to 1.277 tures. Thus the presence of the water
for He) and 1.207 for SF, gas mixtures, as vapor does not explain the higher ob-
recommended by Rader (1990) for gases served mean sedimentation velocities in
whose a values are not known, has been helium and sulfur hexafluoride gas mix-
used. The small errors in a have smaller tures.
effect on C(d) for He gas mixtures and no The gas mixtures exhibiting maximum
effect on C ( d ) for SF, gas mixtures be- deviation are composed of molecules that
cause of lower values of h (Eq. 5). For have significantly different molecular
example, for a = 1.207, C(d) = 1.O69 for weights from each other. For example, the
0.961-pm aerosols in 80%SF,-20%0, at molecular weight ratio of helium and of
the standard pressure and at 23°C. A 10% oxygen in helium gas mixtures is 0.125
increase in the value of a results in C(d) and that of sulfur hexafluoride and oxygen
= 1.076, an increase of only 0.65%. Thus in SF, gas mixtures is 4.564. The deviation
small changes in a cannot account for the between the observed and the predicted
deviations in these gas mixtures. sedimentation velocities for these gas mix-
The relative humidity of the aerosol tures for 0.961-pm particles is between
after passing through the diffusion drier 3% and 11%. The deviation for this size is
was about 40%. This means that the water between -1.5% and 2.7% in air and
vapor in the gas mixture was nearly 1.1%. 80%Ar-20%0,, the molecular weight ra-
The viscosity of the water vapor at 23°C is tios of whose molecules are 0.875 and
9.85 * 1 0 - 9 a s (Turner et al., 1989), a 1.248, respectively. The molecular weight
value lower than that of other gases (Ta- ratio has a bearing on the mean molecu-
ble 1). This may change the value of the lar speed of the molecules in a gas mix-
viscosity of the mixture, when the pres- ture (Eq. 12). The mean molecular speed
ence of the water vapor is considered. The ratios of the gas mixtures to the main
Gravitational Transport of Particles in Gases 177

component of the pure gas in the mixture also conducted. In this case the observed
a r e : 8 0 % H e - 2 0 % O , / H e = 0.871; sedimentation velocity in 80%He-20%0,
70%He-20%0,-10%N,/He = 0.818; was 8.48% higher than the predicted sedi-
80%SF,-20%0,/ SF, = 1.227; 70%SF,- mentation velocity, suggesting thereby that
20%0,-10%N,/SF, = 1.35; air/N, = the slip parameter a is not the cause for
0.982 and 80%Ar-20%O,/Ar = 1.02. It is the higher observed values in the gas mix-
observed that the mean molecular speed tures. If a were the cause it would have
ratios for He gas mixtures and SF, gas led to higher deviation for smaller size
mixtures to their main gas are signifi- particles.
cantly different from that of N, gas mix- Some additional experiments in air and
ture (air) to N, or Ar gas mixture in 80%He-20%0, were conducted with
(80%Ar-20%0,) to Ar, whose values are and without a charge neutralizer in aerosol
close to unity. Does the mean molecular passage. There was no influence of the
speed play some additional role than what charge neutralizer on the value of the
appears in the value of h (Eq. 11)? mean sedimentation velocity or the rela-
To test this an experiment was con- tive standard deviation.
ducted with 51.8%He-48.2%SF6. The The flushing time through the diffusion
mean molecular speed ratios of this mix- drier and the sedimentation cell, to bring
ture to He and SF, are 0.598 and 3.611, the system at the gas atmosphere, was
respectively, the values significantly dif- nearly 40 min. For some of the experi-
ferent from He gas mixtures and SF, gas ments, the diffusion drier was bypassed
mixtures. The observed sedimentation ve- and dilution air increased to attain nearly
locity for 0.961-pm particles in this gas the same relative humidity. The observed
mixture was higher by 9% than the pre- sedimentation velocities were within 1.5%
dicted sedimentation velocity, a deviation of those with the diffusion drier suggest-
of the same order as in He or SF, gas ing that the residence time in the diffu-
mixtures. Thus the mean molecular speed sion drier was enough to bring the system
ratio cannot be the cause for the discrep- to the gas atmosphere.
ancy; if it were, the observed differences The relative standard deviations of the
between the observed and predicted val- particle diameter measured by microscope
ues would be much higher in 51.8%He- was 2.4% for 0.961-pm particles and
48.2%SF6 gas mixture. 1.8% for 1.518-pm particles. This corre-
Tables 2 and 3 show that 0.961-pm sponds to nearly 6% standard deviation of
particles have about 4% higher deviation the sedimentation velocity for 0.961-pm
from the predicted values than 1.518-pm particles and 3% for 1.518-pm particles
particles have in 8 0 % H e - 2 0 % 0 , , from their mean values. The observed
70%He-20%0,-10%N,, 80%SF,- relative standard deviations were in the
20%0,, 70%SF,-20%0,-10%N,. Higher range 5%-lo%, the upper range being
slip correction is expected for small size for smaller size. The ratio of the pre-
particles (Eq. 5). But the uncertainties in dicted root mean square displacement
the values of a cannot explain 4% addi- (J1.518 C(0.961)/(0.961 C(1.518)) ) for
tional difference in 0.961-pm particles. 0:961 to 1.518-pk particles due to the
Further SF, gas mixtures have small mean Brownian motion ranges from 1.27 for SF,
free paths (Table 1) and 51.8%He- to 1.35 for He (Fuchs, 1964). C(0.961) and
48.2%SF6 still smaller (0.0166 p m at 23°C) C(1.518) are the slip correction factors for
and hence small uncertainties in a have 0.961 and 1.518-pm particles, respectively.
practically no effect on the slip correction. Table 3 gives the ratio of the observed
An experiment with 0.60-pm particles was relative standard deviation (Ratio RSD)
S. K. Dua et al.

of 0.961-1.518-pm particles. Although the tist's Fellowship and Dr. P. K. Hopke for his interest in
observed ratios of the RSD for some mea- the work.
surements are within the range and RSD
values for 0.961-pm particles are higher
than for 1S18-pm particles as predicted,
the random process of the Brownian mo- REFERENCES
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The first author expresses h ~ sstneere gratitude to the 70th ed. CRC Press, Boca Raton, FL.
authorltles of GSF for the grant of the V ~ s ~ t ~Sc~en-
ng Willeke, K. (1976). J. Aerosol Sci. 7:381-387.

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