Beruflich Dokumente
Kultur Dokumente
471
October 1967
NATIONAL CENTER FOR ATMOSPHERIC RESEARCH
Boulder, Colorado
TABLE OF CONTENTS
Page
iii
I.
INTRODUCTION . . . . . .
A.
. . . . . . . . . . . . .
. .
........
1.
Optical Effects
2.
Electrical Charging
3.
Physicochemical Phenomena
4.
Dynamical Properties
5.
6.
. .....
. .
..
. ....
. ..
. . . . .
2.4
. . . . . . .
13
. . . . . . .
. . . . . . .
14
11
. . . . . . .
15
. . . . . . .
a Gas of Infinite Extent . . .
12
16
B.
C.
13
Extent . . .
. ...
..
Mechanical Restrictions... . . ..
2.
Single Particles in
3.
Assemblies of Particles .
. . . . .
. 22
. . . &0
. . . 022
. ...
. . . . . . .
24
1.
. . . . . . .
25
2.
. . . . . . . .
27
3.
. . . . . . . . . . . . . .
29
4.
Single Spheres in
a Continuum . ..
. . .....
2.
. a.
. . .
1.
31
33
. 33
..
39
D.
III.
49
. .51
1.
Brownian Motion ..
2.
Conservation Equations
.............
3.
Homogeneous Nucleation
. ....
4.
Particle Interaction --
Coagulation . ......
..............
54
. ...
....
61
64
IV.
........
. . . . . . . . . .. . .
. . . . .
. . . . . ...
.
. ..
73
73
2.
75
3.
..
C.
REFERENCES
.....
71
1.
B.
SUMMARY .
.................
. . . . . . . . .
. .
. ....
........
. .
. ...
76
. .
77
82
.............
. . . . . ..
84
. . . . .
86
CAPTION LIST
Plate I A
type of deposit is
(Photo by P.
B
This
Brown)
pore diameter.
Figure 2
1.
The
iii
-3
(after
Figure 5
Figure 6
Self preserving size distributions observed for tropospheric aerosols (from Clark and Whitby, 92).
Figure 7
Table 1
Basic parameters for describing the dynamics of aerosol particles (from Hidy and Brock, 13).
Table 2
Table 4
Table 5.
Estimated values of the parameters T and o,.,from experimental data for the thermal force (from Brock, 53).
Table 6
The coefficient
Table 8
iv
Table 9
Table 10
Table 11
- 1 -
I.
INTRODUCTION
The generic term aerosols, apparently introduced by F. G. Donnan
early in the century, covers a broad range of microscopic and subThese aerial suspensions
are sufficiently small, they may remain in a gas for relatively long
periods of time.
of natural philosophers.
Much was
More
Fuel
In contrast, the
-3-
A.
Because
the size of suspended material may range from large molecules to bodies
several hundred microns in diameter, the development of collection
devices and analytical techniques has required much work.
Even
Direct means
Perhaps
-4-
Some of the
(9)
Optical Effects.
the rainbows and cloud bows in the atmosphere and the higher order
- 5 -
The theory
for light scattering was developed many years ago by Rayleigh (5)
and by Mie (6).
Electrical Charging.
The present
Because
of many uncertainties in the details of this interaction, electrostatic influences have often been invoked arbitrarily to explain the
deviations in aerosol behavior from expected observations.
It may
Physicochemical Phenomena.
-6
Some of the
I few
Some examples include the work of Goetz (11), and the article
- 7 -
(i)
- 8 -
for non-
Dynamical Properties.
microscope.
Because
D.
1
w
where T is
B.kT
1(6
kT(l + AX /R.)
g
,
(3)
tR.)
B.1 is
- 9 -
and the mean free path of the suspending medium, and A is given by (17)
=
(4)
.Wm.q.. >
I,
> 1,
ii
his fanous oil drop experiments, Millikan (18) found that the particle
mobility B. could not be predicted by Stokes law alone for very small
1
13].
The
- 10 -
M,
they appear to be
However, where
For
the transition range of 0.01 < Kn < 10, the tools of rarified gas
dynamics have to be used to predict the behavior of aerosols.
Particularly in this range, many of the details of gas-condensed
phase interactions are only partially understood so that the theory
of aerosol dynamics is necessarily incomplete.
This theoretical
Examples of
- 11 -
Application
- 12 -
In addition to understanding
the generation term mentioned above, one must be sure that the
application of continuous distribution functions for particles is a
meaningful statistical approximation to a physically discrete system
like an aerosol, which contains numbers of particles very much less
than the surrounding molecules of gas.
been discussed by Warshaw (21).
In a
- 13 -
II.
The material
Thus
an ideal one described by the kinetic theory of dilute gases, and the
collision of particles is assumed to occur with a sticking probability
of
e.
- 14 -
Nevertheless, the
A.
this model.
We
note that there can be twelve different variables for each particle
species, and nine variables for the suspending gas.
If the gas
Table 1
Basic parameters for describing the dynamics
of aerosol particles (from Hidy and Brock, 13)
Particles
Gas
-3
4
-r
"
9;
-r
T'.
~240-310
-2
10 -10
3
3
Aerodynamic Length
Coagulation or Reaction
Probability
0-10 3
(\
itt
Weakly
ionized
vit
10 -10
ft
_/ _
_ _ _
Pt_ ____
Number Density (#-cm
Air
Atmospheric
Aerosols
)l6x10"6 (N2
6 2
>10
1.9x10
10 -118-10-9
4.6x10
0-100
-88
(N2 )
-23
(N2)
Weakly ionized
single charge
f
0
Interaction Parameter
such coefficients for interaction between the gas and the particles themselves.
- 15-
The
ij
Of course,
there may be more than one aerodynamic length which may be chosen
depending on geometrical considerations or wall effects.
1. Mechanical Restrictions.
<
R.
<<
m.
These limits in
However,
time by
this case.
in
the parameters,
and
- 16 -
In addition, the
R /
<<
R /L
(5)
that the gas is dilute, and that there exists relatively gradual
changes in the average properties of the gas (e.g., temperature and
pressure).
Most aerosols of practical importance, including those observed
in the earth's atmosphere, fall within the mechanical restrictions
discussed above.
- 17 -
an infinite gas.
one but, as we shall see in the next section, it provides the core
of virtually all of the mechanical theory of aerosols.
Considering the basic parameters listed in Table 1, we can
specify the behavior of a single sphere in the suspending medium
with average parameters like the number density nk, the lengths
ij,
or
ig. .
T ) where definitions
ij
has no meaning in
is arbitrarily
Rigorously
- co, but practically it has been found (16) that L >> 10 R.,
g
1
the mass of
Table 2,
Some characteristic transport properties of aerosol particles
of unit density at 1 atm.
Particle
Radius
B.
pressure,
<v>
D.
(=E6
1 x 10-3
2.94 x 105
1.19 x 10-8
8.13 x 102
4.96 x 103
6.11 x 106
5 x 104
5.96 x 105
2.41 x 10-8
3.24 x 103
1.41 x 10-2
4.34 x 10-6
1 x 104
3.17 x 106
1.28 x 10-7
7.59 x 10
0.157
2.07 x 106
5 x 10-5
6.71 x 106
2.71 x 10-7
2.85 x 105
0.444
1.54 x 10-6
1 x 10-5
5.38 x 107
2.17 x 10-6
4.44 x 106
4.97
1.12 x 10-6
5 x 10-6
1.64 x 108
6.63 x 10-6
1 x 10-6
3.26 x 109
1.32 x 10
5 x 10-7
1.26 x 10 1 0
1 x 10-7
3.08 x 10 1 1
11.7
x 106
14.9
1.20 x 10-6
6
7.35 x 10
157
2.14 x 10
5.09 x 10-4
1.52 x 108
443
2.91 x 10-6
1.25 x 10-2
7.79 x 108
4970
6.39 x 106
- 18 -
(8kTg/mg)
(6)
<v.)
(8kTi./m.)
a continuum.
it
is
the
suspended
said to be in
the free
Then
it can be assumed that the gas molecules hitting the particle are not
Table 3
Dimensionless ratios of dynamic significance for aerosols
[From Hidy and Brock, 13]
Knudsen No.
Kn
Mach No.
Ma
Schmidt No.
Sc
Brown No.
Br
Debye No.
NEgi
lim
X /R.
ig
R. n h
1
v.
gg
/ v
QiQj/kT
De
Z n.Q.
i=l
- 19 -
In the absence of
con-
It is
in
equations have been found for the behavior of spheres over 0.10 < Kn < 10.
Below Kn ^ 0.10 only crude, intuitive theory based on extensions of
continuum theory have been reported.
usage of this ratio incroporates the speed of sound of the gas for
(v ),
aerosol dynamics.
Ordinarily, the Mach number is less than unity for aerosol
systems so that the gas flow near the particles is considered
incompressible and independent explicitly of Ma.
The ratio of the Mach number and the Knudsen number is proportional
to the Reynolds number of the particle.
Re
1.
UR
g
4Ma/Kn
That is,
1
(7)'
>
We note that continuum theory applies to the limit Kn - 0.
this regime Re becomes very large unless Ma -' 0.
In
- 20 -
where v
In fact,
upper limits of aerosol theory often have been limited to the Reynolds
number restriction, Re -< 1.
The relative
The
The diffusivity of
(Eq. 3).
10 I0
I-I
100
4Ma
GAS DYNAMICS
10-2
-AERO
10-
DYNAMICS
AEROSOL DYNAMICS
I-3 4
IC' -4
o-4
d-3
S0
d-2
10
Kn
Figure 1
-1
O
100
Ion
10
- 21-
m.
Despite
this limitation most papers dealing with Brownian diffusion use the
customary definition,
Sc'.
Re - Sc' .
(8)
),
included in
earlier (62)
i=l
Table 3.
1 1
De,
is
allows the approximation that charged particles interact electrostatically virtually instantaneously.
a vital part of the concept of the single particle regime (See also p. 24).
- 22 -
3.
Assemblies of Particles.
To speak in
any
31.
truly complete statistical mechanical theory for an idealized gasparticle system is unrealistic, except in the simplest of cases where
particles are the same size and the same composition.
1.
- 23 -
In effect, a
stochastic theory for the behavior of aerosol clouds has been formulated
which makes use of the diffusional model based on solutions of the
Fokker-Planck equation (23).
studying homogeneous
n./n
<< 1
for all i
for all i
n.3 << 1
g i
1/3
<< 1
(d)
R.n.
ij
-1/3
1
(e)
QiQj./kt << 1
n.
Lg
-1
for all i
<< 1
(9)
for all i
for all i
Electrical inter-
1.
- 24 -
Two possible
B.
These
1.
- 25 -
1.
the equations governing steady gas motion about the sphere are:
(Conservation of momentum) Vp = PgV U
(Conservation of mass)
(10)
U = 0 .
(11)
(12)
in 1851.
= 6nrT R.iU
for Kn " 0, Re
0.
(13)
B.F
(14)
= (6TAgR.)
-1
.(15)
that the theory and experiment agree within less than 5% (16, 27).
Such a confirmation gives considerable justification for belief in
the soundness of physical laws based on continuum mechanics within
the appropriate restrictions of Kn and Re.
- 26 -
l10].
More
recent work of Proudman and Pearson (29) made more rigorous Oseen's
early approximations for inertial effects in slow flow.
Their
JD = 66TgUlm
+F
Re + 0 (Re2)
(16)
0, Kn - 0, represents
However,
0.1.
JD/(PgU 2)
Fig. 2.
Interestingly enough,
Oseen's result works as well as any for describing data for the drag
on spheres below Re = 0.4.
One classical application of Stokes law is the estimation of
the terminal fall velocity vs of a small particle in a gas.
To
3.00
1000
2.75
2.50
2.25
0 2.00
0.75
..J
1.50
1.25
1.00
0.75
0.50
Re
0.25
n
-2.0
-1.5
-1.0
-0.5
LOG Re
Figure 2
0.5
- 27 -
(Pi- Pg) g rR
= 6TgR U
c
UO = vs =
(Pi- Pg)g
(17)
g
Similarly the steady particle velocity v. in a uniform electric
field so may be calculated by balancing the electrostatic force and
the frictional resistance.
v
(18)
moving in a viscous medium was examined many years ago by Basset (31).
His equation, for Re -" 0, Kn - 0, is written as:
4R P.
3
l dt
= 6
1 g dt
i(
(d
t
+ 6R/--T
g
d+
R.(q
1 g
T
dt'
1 gdt
- dq /dt')
--
/dt'
g (t
dt
+ F,
(19)
is the frictional
- 28 -
the force resulting from the pressure gradient in the gas immediately
surrounding the moving particle.
This is
Therefore, the
where
and a
A -U
(20)
+ ae
9T /2R.2 ,
= F /m..
e 1
Equation [20] has been used extensively for analyzing the inertial
deposition of particles on surfaces and for other dynamical studies
(e.g., Fuchs, 16, or Hidy and Brock, 13).
From various experimental observations discussed in reviews in
Davies' book (17), it would seem that it should be necessary to add
one additional force in the balance of Equation [19] if the gas is
non-uniform.
Nu
is disassociated from heat transport to the sphere' (See also Sect. 2C.2).
1.
- 29 -
3.
In addition to momentum
in a continuum.
conductivity k
6PC/
'-+ U'VPa = Do
(vapor)
(heat)
Here k /Pgc
g
g p
Pa
(21)
-2
6T
-T + UNT = (kg/PgCp )T
(22)
P9 = Ps(Ts)
P, -SPL
(heat)
r = R,
-
= T
r = R
Tm -f T,
g
r - 0
(21a)
.
(22a)
Here P/s is
T .
S
30 -
velocity field,
as in
the Stokes'
exists
far
Nu,
2kR
(mass transfer)
Sh:
(PCo.- Pcas)
- =
Sh
lPa
2hR.
(heat transfer)
Nu
(Tw-
k
g
In
(23)
dA
r=R.
1D
-1
iT
3)
dA
2nR.
1
(24)
r=R.
these expressions k and h are the mass and heat transfer coefficients
respectively,
and A is
transfer to spheres using the flow field of Proudman and Pearson (29).
By a perturbation method equivalent to Proudman and Pearson, Acrivos
and Taylor found that:
S Pe
Sh = Nu = 2 1
+
2
Pe
+
Pe
In 2Pe
+ (0.0608)
Pe
+ --4
for Pe
Here Pe(H
= Pr
Re,
Pr = (Cp
g /kg).
In 2Pe
(25)
<< 1.
(M = Re
number would be the same except that Pe (M)
g
Sc ,
g
Sc
= Vg/D a-
Equation [16].
- 31 -
Pe
That
- 0.
4.
The application
Strictly speaking,
from the body and at the surface of the body is small, one may
assume that the rate process is quasi-stationary, and solutions
like Equation [25] may be applied.
Quasi-stationarity is also
- 32 -
dR
4TTR.Da(P
a form
Ps?7(Re, Pr g)
(26)
stationary assumption nor the heat effect will cause large deviations
In the limit Pe - 0,
The scatter
1.5
1.4
1.3
Nu
2
1.2
1.0
1.0
0
O.I
0.2
0.3
0.4
Pe
Figure 3
0.5
0.6
0.7
- 33 -
C.
1.
number, where Kn
To illustrate
To calculate the
dF =
where v
m v v f d
+
g
S g g gn
gj dA(27)
m gv gv gn
(27
is the component of
gn
(g ),
and f
(g )
= f,
- 34 -
and (b)
f+(l -
defined by
a , is
m)f- + am(n
it
the absence
/n)f
(28)
(29)
where
f(
= f = n (/T)3/2exp[ -P(
g
with
S = m /2kT .
SJ)=R
31
(36):
n /mkTg
g
gg
8m)i
estimate.
Equation [30] is
(30)
in
We
proportional to R.
instead of R.
as in
Equation [13].
the free
B.
n/2TmgkT
g
(
+ -a
(31)
the value of
- 35 -
gas.
Unfortunately,
predicting
virtually nothing is
additive,
in
or D.
B.
and at worst,
however,
It
an equation for the net force acting on the particle may be written
in
B.
given, of course,
to non-uniformities
in
40).
Since,
in
this case,
ff(0) 1
where r is
2m k
my
v
5PkT
v
2kT
=--
Remarkably,
relation.
0
g
15
R2
i
(36):
-2
kT
aT
g a-
(32)
- 36 -
If
Therefore,
k
3
Sg
=5(1+(TT/
8 )Om)
aT
(33)
n kT ag
in this case.
The thermal forces arise with heat transfer from the gas to the
particle.
non-uniformities in
In
this case,
(0)
f1
when q" is
ma
kTggqa
given by
exp[-P (- a
)g].
-32 R
FD = ~
/3
n (o./T)
--
a gas mixture is
1
I +
P(Qi-
wherg
where <v==
[SkT/Tm J]2 and pa = n kT
) ',
(34)
- 37 -
The relation between the mass average velocity of the gas mixture
and the velocities of each of its
-h
qg -
components
>
mnmq .
nq
mana(
Z m
AB
that
-
nA A + nBqB
g
mA
mA+
mB
mB
_
nA + nB
q, =
(n-"
mAA(1+(/8)amA)
(nA+nB
mA nA (l+(/8)mA)
If
ap
AB
-1
'1
V^(l+(/8) )A
B
+ mB 2 nB(+(1
(2P
x D
/AmB)
mA and
mA
(35)
r
'm
mB
are equal,
Equation
DA
AB
(35a)
the direction
the
indicated above,
Brock (42)
Brock gives
- 38 -
^-^'^cma
a
(1 + 8
2kT
2kT
2 R 2r
21o(=A
i=
Mm
2 1<)
a
(36)
)},
+ exp(
act is
j (Ri)
J (R.)
+
ca
Ju(Ri)
j,and j
are,
(Ri)
respectively,
surface.
surface, while
specularly reflected.
absorbed at
The functions
, have been
the form
tabulated in
S=
and
is
and
f-
exp (-Ma
l 2 /n)
average velocity is
0,
2TR.
B
E
CA A
r 2kT
n
l
2kT
-9 - J
ga
n g"m-
CA( 2 mgkT)
+
'=A
Pg
DAB
VPcPg
Kn
m, Ma
(36a)
- 39 -
found to be (42)
mixture:
12kT
JH = 4TRR
T[1m
kT
n2
m lf
kT(
kT
g Th,
0=A
X
1 + 8
+ exp - 4 M)
(37)
= 4HR.
STg
S+
As in
\
2kT
kT +
g
gmg
- n
2kT-
kT
(37a)
g Lm
and a .
T
is
Very little
known
In fact,
From a view of
of principal interest.
the
Yet
Some
The
- 40 -
have been applied to explain the form of the Factor A (e.g., Fuchs
and Stechkina, 43), only recently have there been completely successful
theoretical approaches to estimate the frictional resistance in this
Kn range.
Early theories relied on intuitive adjustments of continuum
theory to account for slippage of gas at the particle surface when
The slip flow condition revises one boundary condition
Kn r 0.
+ 1/r(Ur/8))],
I r r(U./r)
r = R'
S(38)
(radial component of U)
U
= 0
2c Kn'
m
aJ> 6TTGi R.
n
S1 il + 3cMKnJ
Kn >
(39)
Kn > 0
Equation
[3] should give a linear relation between Kn and the frictional resistance
as Kn
-'
0, with C
= A s 1.0.
- 41 -
~ (0) + (1/Kn)f(1)+
The form
...
C.
Willis' result
is:
p~s
where
(40)
[1 - 0.366 Kn'-],
This expression agrees with Equation [3] in the free molecule limit.
And comparison between the correction Factor (1 + AA /R.) with Davies'
coefficients, and those given by Willis' equation substantially agree,
as indicated in Table 4.
The regime below Kn < ~1 remains unspecified theoretically,
but the functional form of A can be taken relatively well established
by extrapolating to Kn
0.
flow analysis (38, 46, 47), and by arguments based on the theory
of irreversible thermodynamics (48, 49) that these forces can be
predicted from the theory of gas dynamics.
In cases where Kn - 0,
Table 4
(45)
Kn
6(
(Slip Flow) Eq.[39j
U.
(BGK)
[U/
Eq. f403
(Expt.)
Eq.[4]
-im= 1
m= 1
0.1
1.082
1.13
0.5
1.25
4.18
1.65
1.0
2.67
2.39
5.0
9.13
8.89
10.0
17.5
17.2
- 42 -
(41)
'(
t
Kn < 0.05,
where ct and ct
Here k
g
conductivities of the gas and the particle.
note that FT - 0 as Kn -
0.
Derjaguin and Yalamov's theory [48] for the thermal force predicts
a relation differing from Equation [41].
Evidently the
difference lies in the form of the slip conditions used at the boundary.
that their theory agrees best with data taken for oil droplets in helium
with a flow method by Derjaguin, Rabinovich and Storzhilova (52).
The
results of workers (42, 48, 49) were obtained by the Millikan cell
technique, which Derjaguin has criticized as being inaccurate.
Drift of large aerosol particles where Kn
0 in a gas containing
- 43 -
0.
<
Kn
In
where F
= F texp -TR./X },
(42)
1g
+ 0.280
11[- Gk /2k.].
Tg
1
(43)
m.
T:
T
Table 5
Eq.
Ref.
43
Aerosol
Gas
M300
0.39 + 0.01
0.80
48
M300
N2
0.38 + 0.01
0.81
48
M300
CO2
0.36 + 0.02
0.80
48
M300
H2
0.22 + 0.04
0.79
48
TCP
Air
0.41 + 0.02
0.88
49
0.47 + 0.01
0.91
42
0.46 + 0.02
(0.91)
52
NaCI
(Amorph.) A
NaC|
(Cryst.)
Air
- 44 -
reported using the flow method, e.g. (51) yield unrealistically low
values of T, departing markedly from the other data in Table 5.
Results of the flow method that T
reduction in thermal force to zero from the free molecule value must
occur in the region 0
Kn I
1
0.2.
Here
theory
Some very
Mass transfer
- 45 -
here must reach the order of the thermal velocities of the gas molecules
to be important in modifying in the collisional trajectories.
Thus,
when the gas contains an evaporating species in flow past the particle
in the regime 0 < Kn < 10, two distinct effects may contribute to
increasing the evaporation rate over that expected in a stagnant
medium.
of the sphere.
I /
<< 1,
0.
For small values of R./X Brock (57) finds that the overall
i B
evaporation rate of component A from a sphere is:
- 46 -
J0A=+
JM
3. AnAO
where nAO is
)12
"(I B
(44)
Kn >1, Ma << 1,
(RA+
lo
2/2
In Table
- 0,
mB and nB,
RA/RB -' 0.
JM is
largest for
decreases.
Physically this result may be interpreted that the mean free path of
component A,
.A, is
0.
decreases.
directly related to
their first
A,
As
A gets larger,
or the evaporation
for example,
Ri
AnAOA
/ (1
B Kn).
term in
Therefore,
it
AY , and
Table 6
System
RA
mA + mRB
A - B
1.000
0.000
0.060
A - B
0.500
1.000
0.206
0.616
1.235
0.264
0.21
2.00
0.46
0.08
2.8
1.18
Diamyl-sebacate
(A)-Air (B)
- 47 -
AnAO
JM =R
BR./B)
(45)
give
BA
of 4f
These authors
1.18.
Such
Fuchs'
Fuchs' analysis
will yield
JM
M
1 - 4Ri /a )
(1
<
at small values of Kn
Though the
theory should be valid for small Knudsen number in the sense that a
slip analysis is valid, this model may seriously underestimate
corrections for transitional behavior at high Kn, provided that Brock's
theoretical calculations are correct.
- 48 -
R.
/D
6 (g)aRi./(v
Evaluation of 6()and
c
(g)
nc
10-
sec.
where
c(
= R.2 PC /k
1 gp
Such a restriction is
satisfied in general, for example, with particles with thermal conductivities of ordinary liquids, but not with particles of conductivity
equal to many solid metals.
regimes,
general.
terms
- 49 -
Brock (60)
<^
((47)
, is
defined
and
D.
of isolated bodies in
in
terms
Examples of problems
filtration, etc.
- 50 -
In the single
This is readily
droplets.
C is a constant.
, and nearly
Such crude
- 51 -
We restrict
1.
Brownian Motion.
(48)
The
The
- 52 -
---- '-
2t
where t
-c0
(49)
>> (m.B.).
11
i.e., where tr
m.B..
3r
.i
In analogous
displacement
(, ffv
't,
idt
- 53 -
2 4
>
(50)
, )
,t)
where
Ij t,"
so that
)t-t-
<X
<
">p
>.,tLt.
practice by assuming that the drift velocity B.F equals the mass
average speed of the gas,
q .
It
is
fundamentally unjustified.
Nevertheless
- 54 -
2.
Conservation Equations.
to Equation [48].
This type
However, it is not clear at this time exactly what form the complete
rate equations should take for aerosol clouds.
In the absence of a
If
another
- 55 -
An internal parameter
The only
This restriction
This is done by
1.
This
- 56 -
w(m, I, r,
t),
(51)
m to m, I, r,
in
at
For example,
When no agglomeration
occurs, each point retains its identity, and the number of points in
w-space is conserved.
The mass
- 57 -
time of w,
I,
r and t.
For
the surface of Q is
A,
in number of points in
If
Ji (^/n)) 4
where
d( df drdI
The term m,
i,
j,
<?W
"
00
dA
and
and v is
the velocity
of a point in w-space.
Making use of Gauss'
(dt)
"(.}
derived:
V(o(52)
vsdr;.
given by the
- 58 -
(7,)
8//
(53)
= /
Ifff#rV
where
I+S
ldl
mass m.
c0.1iM1)
is
J,
(53a)
break u)
Sparticles.
s~,c
and
Similarly
the loss of species of a class with mass m may occur from collision
and agglomeration of m with any other particle, including a molecule
of condensable vapor,
say
Or
yl^
,fjuoff 'T._d
c'{
?l
ff
f
Idr
(53b)
Thus,
the process
- 59 -
In
general,
irreversible,
is
and break up is
disregarded.
aerosols is
considered
given by
r(5
n'
4)
Here
It
swept
out per unit time of a larger sphere with respect to a smaller sphere,
or (particles/unit volume)-
X (time)-"
[53]
Jbv S+ Vf(&^)
This relation is
(55)
m.w) it
is
(a) In contrast to
not a function
integrals given by
1.
is
moments (like
(b)
derived:
(c)
the collision
- 60 -
The
, J,
+-W
2r =
wow,
"
"5
J
t)]'
- 61 -
3.
Homogeneous Nucleation.
rate equation [53] is the theory of spontaneous nucleation of a supersaturated vapor in the absence of foreign particles (nuclei).
classical theory of Becker and Doring (74,
The
and Frenkel, 73) assumes that all terms in [53] are neglected except
for four involving single molecular species of condensable vapor.
Suppose [53] is integrated over real space r and internal parameters I
are disregarded.
(56)
In
- 62 -
other words,
vapor is
a highly supersaturated
occur.
S -,y
Here jKnl is
4/
4 k+,
(57)
K+ /
JK is
and AK is
n1 is
different forms.
is
that given
by kinetic theory:
where pi is
the partial
and CQ
is
the
and one,
el,
to give an embryo of
That is,
ek,
(5 8)
(58)
- 63 -
The flux
now is
k
e/l"2AL
(27r7
[58] is
or
Ak ,(AK
LA
) '/k
where b
is
However,
considered unstable,
T^ K72,pi-^/^T]
{^)
where the pre-exponential factor has been given by Becker and Doring (74)
A^-- /inY
^r
^.j/(TI~I~
- 64 -
Because of uncertainties in
and
recent years.
this field is
Of possible
modification of Eq.
4.
Particle Interaction-Coagulation.
Suppose
[53].
which is
much larger
yields the well known rate equation for the coagulation of aerosols
in
a stagnant medium.
the relation
0
icO
(60)
- 65 -
Thus, in the
- 66 -
for kinetic
Perhaps best
known are Smoluckowski's results for Brownian motion, and the sweep
out results for collisions of droplets in rain clouds.
To illustrate how different mechanisms may control collision
processes in clouds, consider an aerial dispersion in a weakly turbulent
medium that contains particles of uniform density over the size
radius range of 0.1 - 10 P.
1.
-8
10
-9
I0
Un
.0
-I0
I0
Ib
0.1
1.0
R, MICRONS
Figure 4
10
Table 7
Collisional parameters for several kinetic mechanisms in aerosols of unit density particles.
Mechanism
_
I.
Ref.
(cm /sec)
__
Continuum, Kn-- O
A.
Brownian Motion
B.
(62)
tial field (
C.
+onpI
1 7r
interaction of poten-
~-
(16)
Shear
(k
+R;
JA
.r
(62)
3
D.
Turbulence
E.
)
(geometrical)
d is
T (i
= collision
R~)j
RJ )(j
) (l
Yj
7T(
efficiency (Ref.
___
__ _ _
re
--
i) )
'
(79)
(80), (81)
)eo
24).
__
KONOMOMM
Table 7 (continued)
Mechanism
____
II.
_ ___
__
(cm 3 /sec)
Ref.
I_
__
Free Molecule, Kn
A.
B.
Brownian Motion
+)
Tb"s(Ri~i)'(
L(
Generalized
4 k)
(64)
11667
4
Transition of Kn
A.
(f j)
*J
9i = ^*1 ^^
III.
1J
^-
ip
(63)
Brownian Motion
1.
2.
Theory (monodisperse)
+~~j
*Rj)
A 0'
I'..
i]v
Tz)-)
-/
Jw
^^(R
(AM
7rA/A
^j) +-
(16)
PLX
(64)
O(R;+)
'*l
In (la
0 ,9 77
(RZ+Rj
4i8^--
.-
_,,
IV
3.
Fokker-Planck (monodisperse)
/'
+ ooi
,(o/
//
L
v-cRr
^ to^(Xi;)Zt4o,(
~
aQ^i/
(82)
o,;(
i/^])
- 67 Kn
Since
attempted to extend
This theory
This re-
For
an extension of Smoluchowski's theory using only the Stokes-Cunningham correction for particle mobility.
Brock and Astakhov show departures from Fuchs' "forced" theory in ranges of
Kn beyond their applicability.
(64).
molecule regime.
gest that the theory for Kn >10 underestimates the collision rate.
Table 8
Kn
-
Fuchs
(16)
-- ---
Hidy and
Brock (64)
Astakhov
(82)
7 - - --- -
--
0.10
1.13
1.13
1.14
0.5
1.65
1.79
1.76
1.0
2.39
2.42
2.45
5.0
8.89
4.04
3.95
4.04
3.03
2.14
3.03
10.0
50.0
17.2
1.51
1.51
- 68 -
Because of the
to [60].
Perhaps the first solution to Equation[60]of physical interest
was found sometime ago by Smoluchowski (62).
in a different form by Schumann (84), referred to the initial coagulation of aerosols by Brownian motion where b..= constant.
For this case, the solution toL60]
At ./
lo)
is:
-N /
Y b- j
(61)
is
which are
appli-
and
The latter
The integral
(88).
(e.g.,
4(e (f7
where g (t)
and v
(62)
)^
equation with
) is
termed
and v
(t)
used are
V/01
I=w(i
, and
90)
'
t)-
(f63)
~(v/1
but per-
where / (t)
(90).
The
5.
satisfactory.
For comparison,
and agree-
Smoluchowski's result
5.
behavior for combinations of shear and Brownian motion, and for Brownian
motion in non-continuum conditions.
1.0
0.8
z
0.6
C
II
3-
0.4
0.2
0.001
0.01
0.10
s~p
vN
Figure 5
1.0
5.0
- 70 -
Junge (91)
discovered many years ago that such aerosol distributions have similar
shapes, which have a form
w'(R, t)
(64)
^-jR
Several examples of
The R
However,
i.e.,
aw'/ 6 t = 0.
2 Af
I
0
z
I
ri
0*1%&#
1/
71
R(N
/(D)
100
Figure 6
- 71 -
To attain a steady
However,
Mockros et al. (94) have shown by numerical calculation that distributions having the form R
-n
attributes
We can
- 72 -
important influences;
aerosol particles.
It has
Intrinsic properties
are defined as those which are inherent to any particle because of their
small size, or large -A.
ratio.
from bulk behavior resulting, for example, from the smallness in size
of the particles.
A-
increases.
Extrinsic
vapor pressure,
1.
Indeed it
has been all too easy, in past work, to ascribe departures from predicted
dynamical behavior,
for example,
to various "unknown"
influences of the
Within this general framework now let us examine briefly some aspects
of the dependence on dynamic behavior of idealized aerosols in terms of
surface properties of the spheres.
A.
In particu-
lar, such uncertainties may come about in the case of heat, mass and momentum transfer through the various accommodation coefficients; indeterminacies
in vaporization processes also may stem from the presence of soluble materials
in the bulk phase of a condensation nucleus, and by adsorbed films on droplet
surfaces; variations in coagulation rates may derive from ionization in the
gas, additional dipolar interactions of adsorbed molecules, and differences
in the sticking probability, which depend on adhesive properties.
1.
various accommodation coefficients appear in the cases of heat and mass transfer to spheres in the non-continuum regimes.
' , Equation 4,
is proportional to
tive to
tdm.
and available data of this property have been reviewed recently by Wachmann
(95).
and their
(96).
lCm for
In contrast to
energy, as expressed by or
more.
9B.
taken
different gas-solid surfaces is much greater than for dm. Since heat
transfer in the non-continuum regimes is sensitive to OCT' it may be important to be able to correct the theoretical calculations for (T~1I.
Vaporiza-
tion rates of particles are directly proportional to the evaporation coefficient, so that one must exercise considerable care in making estimates of
these rates on theoretical grounds unless experimental values of .4
for
Table 9
A.
Momentum Accommodation
o m
Ref.
machined brass
1.00
(18)
Air on oil
0.895
(18)
CO2 on oil
0.92
(18)
Air on glass
0.89
(18)
He on oil
0.87
(18)
Air on Ag2
0.98
(96)
He on Ag20
1.0
(96)
System
Air on old shellac or
B.
Thermal Accommodation
Ref.
System
Air on machined bronze
0.91-0.94
(53)
0.87-0.93
(53)
0.89-0.97
(53)
0.95-0.97
(53)
02 on bright Pt
0.808
(96)
Kr on Pt
0.699
(95)
N2 on Wo
0.35
(96)
He on Na
0.090
(95)
Ne on K
0.199
(95)
He on Wo
0.017
(95)
Table 10
II
'z-:l
Temperature Range
898-1279
Copper
913-1193
Iron
1044-1600
Nickel
1034-1329
Ammonium Chloride
(3.9-29.0) x 10-4
118-
221
-21.4 to 70
Iodine
0.055-1
Mercurous Chloride
0.1
97,102
Sodium Chloride
0.11-0.23
601-657
Potassium Chloride
0.63-1.0
Water (liquid)
0.04->0.25
Benzene
0.85-0.95
Camphor (synthetic)
0.139-0.190
Carbon Tetrachloride
:1
Diamyl Sebacate
0.50
25,
Di-n-butyl phthalate
150-350
Ethyl Alcohol
0.0241-0.0288
12.4-15.9
Glycerol
Unity, 0.052
18-70
Napthalene
0.036-0.135
40-70
Tetradeconal
0.68
20
15-100
6
-14.5-5.5
-
35
In the atmosphere,
regions of supersaturation by condensation on nuclei composed of both inThe driving force for droplet growth by
it
If
the nucleus is
soluble
We have already remarked that the equilibrium vapor pressure for very small
droplets is
equation, Equation C 1
3.
as given by Kelvin's
(See,
for example,
.0) reads:
where nL is
90.)
//
ikT/
/'./
i
3
(%O)^i
1(65)
i is
the so-
increase the growth rate of such water droplets over that expected for
pure water.
<
^
U.8
0.6
0.4
0.2
0.
C
a.
0
a-
-0.4
-0.6
-0.8
o
DROPLET RADIUS G)
(
Figure 7
Uncertainties in the
coagulation rate can come about through changes in induced forces between
the particles by adsorbed species, or by differences in the sticking
probability
that the probability of sticking is associated only with phenomena contributing to the variability of adhesion of particles.
surfaces has been reviewed recently by Corn (17) and in articles of Fish's
-book (100).
By the 1930's it was known that certain materials could reduce coagulation rates of aerosols.
Their explanation
dence also appeared which indicated that adsorbed species, like surface
active agents on solid aerosol particles, could affect their coagulation.
Sussi (102)explained these observations by suggesting that the adsorbed
species changed the distribution of electrical charge on the particles.
- 77
Later Vold(103) developed a possible theoretical explanation.
She found
brought about by choosing adsorbates with Van der Waal's constants differing
from those of the particle.
12
-10
13
-2
molecules-cm
and this induced force field diminishes exponentially with increasing distance between particles.
B.
The considerations above largely stem from the assumption that the
surface curvature of particles may be disregarded.
dence now that one can expect deviations in a number of thermodynamic properties of spherical particles when their size is small enough.
These de-
(106).
These
quantities, of course, provide the framework for nearly all of the theoretical treatment of equilibrium and rate processes at the surface so that their
calculation from measurements is essential to colloidal theory.
To recapitulate
macroscopic arguments,
suppose
out first
Different choices
Use-
(101).
energy E
the surface
E = E, + E
+ E .
(66)
(fs)- ZI'
where f (s)
is
fkc
(67)
and r
is
is
(s
of the'6 component.
Surface work = 4
/d
A,
(T,A4 const.)
(68)
For no net surface work, one obtains the Gibbs adsorption relation
T<"r-
' -- s
(s)
where s(
is
<69)
(Z^<
(s)
.-
Further,
(70)
S)w7-
(surface work -
0)
(108).
- 79 in which conditions of [6
,9
or 70 are fulfilled.
Thus a quantitative
, A, T,
, at least
The size dependence of surface tension and other variables then arises
in a way out of the choice of a convention for the location of the dividing
surface.
vention that appeared most advantageous to Gibbs was that which made
explicit dependence of Y/on curvature zero.
that the change in AJ,
is satisfied.
surface work vanish for a normal displacement of the interface gives for
the fluid-fluid systems,
2.(71)
as the relation between the pressures of the two bulk phases and the mean
(1/2) of the two principal curvatures of the interface.
located such that[71
(R~)-
Any
Equation
curvature
by a microscopic analysis of Kirkwood and Buff (110), and by empirical considerations of Scherbakov (112).
usually unimportant and of less interest than other properties which involve
Imore
simply.
of the
This convention is also useful for fluid interfaces because the corrections
in[69) and[70] have particularly simple forms (109).
However,
this effect generally appears to introduce small corrections until the particles are very small,
-6
"
10
cm.
Table 11
Variation of some properties of aerosol particles with size
tabulation of thermodynamic variables as a function of
particle radius (from Hidy and Brock, 13).
Ratio of
710
E-ffective
rroperty Lo Same
-rarLtLcle
adius
O.,Ol
.01
O.
001
0.001
Reference
~)
Vapor Pressure,
of Water,
at 5C
P/P
1.0001
1.0012
1.012
1.124
3.32
From Eq.
0.999994
0.99994
0.9994
0.994
0.94
(114)
Surface Tension of
Water at 40 C
/Y/
0.9996
0.996
0.968
0.755
(114)
Solubility of
Crystalline Substances,
~2
(115)
Ol
1ij
- 81 -
Associatingo with the free angle ratio, the ratio of the rota-
T^/
(72)
This
the kinetics of surface reactions proceed at velocities higher than equivalent processes.in the bulk phase.
- 82
9-
(73)
curvature.
The sensi-
tivity stems not only from the radius of curvature increase, but also
from changes of gradients in 9at the particle surface.
C.
The discussion in the last two sections calls attention to the significance of the nature of the particle surface in relation to the bulk
phase, and particle geometry for introducing ambiguities in the equilibrium and kinetic behavior of small particles.
Further complications
physics, much of the research on this subject has been reported in the
crystallographic and metallurgical literature (see for example, Gomer
and Smith (118)), and consequently will not be discussed here.
Much of
It seems doubtful that potentially unique departures in physicochemical behavior of aerosols will be discovered until the ratio of intermolecular distance to particle radius-A-exceed about 10
ticles begin to reduce to sizes ofv 0.Ol^ or less.
-2
molecules in this size range may well exhibit only "bulk" properties which
will be characteristic of surface layers overlaid on much larger bodies.
One wonders, for example, what the implications are of very small
particle interactions with the gas phase in relation to surface forces.
Recent studies by Distler and Kobsarena (119) have implied
fluence of active centers for selective adsorption may extend 1-10." away
from a surface.
cause rather severe deviations in catalytic effects in reactive gases containing very small particles as contrasted to larger suspended material.
radius have
That
silica particles of the 0.1,c size range exhibited a more than 20% decrease
in density as compared with the bulk material.
in terms of the lattice constant, were examined some time ago by LennardJones(121).
Adamson, et al
4.
SUMMARY
This theory
surface roughness and shapes other than spheres are difficult to incorporate
in the dynamical theory, but probably can be taken care of by semi-empirical
geometrical factors.
- 85 -
Some
ACKNOWLEDGEMENTS
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J. P. Lodge, Jr. and E. Frank, J. die Microseopi,
2.
6,
1.
449,(1967).
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3.
4.
97.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
C. N. Davies, Ed., Aerosol Science, Academic Press, New YorkLondon, 1966, 468 p.
18.
19.
20.
21.
22.
24.
1 (1943).
also
26.
27.
28.
29.
J.
30.
31.
33.
34.
35.
387 (1962).
37.
38.
39.
40.
S.
42.
43.
44.
45.
D. R. Willis, "Sphere Drag at High Knudsen No. and Low Mach No.",
(1967).
58
1949 (1962).
47.
48.
49.
22, 195
(1966).
50.
51.
52.
53.
J.
54.
55.
(1968).
57.
Chem. Phs.,
59.
60.
61.
62.
63.
64.
65..
66.
67.
68.
69.
(1968).
70.
71.
19, 555
(1964).
72.
73.
p. 390.
75.
76.
77;
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
1321 (1962).
100.
W.
103.
104.
105.
16, 1 (1961).
106.
T. L. Hill, Introduction to Statistical Thermodynamics, AddisonWesley, Reading, Massachusetts, London, 1960, 508
107.
109.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
W.
121.
J. E. Lennard-Jones,Ziet f. Kristallog.,
122.
Stober,
Interface Sci.,
21,
445 (1966).
2 (1956).
75, 215 (1930).