Condensation: - in The Continuum Regime, Diffusion Theory Is Used. at Steady State

2013/8/18
Aerosol & Particulate Research Laboratory

1
Condensation
In the continuum regime, diffusion theory is used.
At steady state
0
2
2
=
c
|
.
|
\
|
c
c
c
=
c
c
r r
r
n
r D
t
n
( )
|
|
.
|
\
|
+ =
r
d
n n n n
p
d d
2
1
1
Rate of diffusional condensation
( )
( )
kT
p p D d
n n D d d
r
n
D R
d p
d p p
d r
CO Cond
p
= =
|
.
|
\
|
c
c
=
=
1
1
2
2 /
,
2
2
t
t t
Volume growth
( )
d
p
p p
kT
Dd
dt
d
=
1
1
2 u t
u
( )
d
p
p
p p
kTd
D
dt
dd
=
1
1
4 u
Q: Is n
d
equal to n
s
?
Q: How much is it?
Size growth
Reading: Chap 13
2013/8/18
2
In the free molecular regime, the gas kinetic theory is applied
( )
kT m
d p p d
c N
A R
p d p
p FM Cond
1
2
1
2
,
2
4 4
t
t o t
|

= = =
Volume growth
( )
kT m
p p d
dt
d
d p
1
1 1
2
2t
o u t
u

=
( )
kT m
p p
dt
dd
d
p
1
1 1
2
2
t
o u
=
Ex: For d
p
= 0. 1 and 1 m, calculate the new d
p
after 1 sec
of water vapor condensation at 20
o
C.
Q: How can the condensation rate be increased?
Q: How does the growth rate depend on size? Implication?
Size growth
2013/8/18
3
For the entire range
( )
|
.
|
\
|
+ +
+
=
2
1
333 . 1 71 . 1 1
1
2
Kn Kn
Kn
n n Dd R
d p Cond
t
(Sutugen, 1971)
CO Cond FM Cond Cond
R R R
, ,
1 1 1
+ =
(Pratsinis, 1988)
Kelvin effect
( )
(
(
=
(
(
=
p
p
s
p
s d
d
S d
p p
kT d
p p p p
ln
exp
4
exp
*
1
1
1 1
ou
Q: How does the growth rate depend on particle volume?
Particle size? Implication?
2013/8/18
4
Log-Normal Model
Pratsinis, S. J. Colloid & Interface Science, 124(2), 416-427.
?
0
=
dt
dM
3 / 2 1
1
) 1 ( M S B
dt
dM
=
3 / 4 3
2
) 1 ( 2 M S B
dt
dM
=
?
0
=
dt
dM
3 / 1 3
1
) 1 ( M S B
dt
dM
=
3 / 5 1
2
) 1 ( 2 M S B
dt
dM
=
Free Molecular
Continuum
( )
1
1
3 / 1
1
2
36
m
kT
n B
s
t
u t =
1
1
3 / 1
2
3
8
9
16
m
kT
n B
s
t
u t
|
.
|
\
|
=
2013/8/18
5
? =
u d
dN
N S
d
dV
) 1 ( =q
u
V S
d
dV
) 1 ( 2
2
= c
u
CO FM
q q q
1 1 1
+ =
( )
|
.
|
\
|
=
=
o u q
o u q
2 3 / 1
1
2 3 / 2
ln
2
1
exp '
3
4
ln 2 exp '
g Cont
g FM
Kn
CO FM
c c c
1 1 1
+ =
( )
|
.
|
\
|
=
=
o u c
o u c
2 3 / 1
1
2 3 / 2
ln
2
7
exp '
3
4
ln 8 exp '
g Cont
g FM
Kn
Non-dimensionalize the equations
t u / t =
| |
1 1
2 / / 1 m kT s n
s
t t =
2
1 2 2
1 1
0
/
/
/
u
u
s
s
s
n M V
n M V
n M N
=
=
=
1 1
1
/
/ '
r Kn
g g
u u u
=
=
N S
d
dS
) 1 ( = q
u
Q: N(t)? d
p
(t)? o
g
(t)? S(t)? Assuming condensation only.
2013/8/18
6
Asymptotic Behavior: after a long time
3 / 4 3
2
) 1 ( 2 M S B
dt
dM
=
3 / 1 3
1
) 1 ( M S B
dt
dM
=
For the Continuum regime
Eliminating dt
3 / 1
2
3 / 1
1
3 / 2
0
3 / 4
3 / 1
2
1
2 2 M M
M
M
M
dM
dM
= =
Integrating and noting that the initial values are very small
1
2
1
2 0
=
M
M M
Note
|
|
.
|
\
|
=
2
1
2 0
2
ln
9
1
ln
M
M M
o
o = ?
Important!!!
|
|
.
|
\
|
=
|
|
.
|
\
|
3
2
0 , 2
3
2
2
3
2
0
3
4
0 , 1
3
4
1
2
3
2 4
3
M M
M
M M
2013/8/18
7
Condensation Characteristic Time
Constant Particle Size: Limited vapor with a high particle loading
0) then vapor, the sink to is surface if (or
exp
0
=
|
|
.
|
\
|
=
s
C
Cond s
s
t
C C
C C
t
0
, ,
2
0
1
, ,
2
1
2
1
p
dpo CO Cond
p
dpo FM Cond
DNd
Nd
m
kT
t
t
t
t
=
=
Constant Vapor Concentration: a small particle loading with unlimited vapor
Co FM Cond p
p
t
d
d
, , 0
1
t
+ =
( )
s av
p
Co FM Cond
C C N
m
kT
d
=
0 1
1
0
, ,
2
u
t
t
Co CO Cond p
p
t
d
d
, ,
2
0
2
1
t
+ =
( )
s av
p
Co CO Cond
C C DN
d
=
0 1
2
0
, ,
8 u
t
Q: When?
Q: When?
Q: Physical meaning?
2013/8/18
8
Characteristic time for simultaneous particle growth
and vapor consumption
Free Molecular regime
3 / 1
1
3
0
0
3 / 1
1
3
0
0
6 /
6 /
|
|
.
|
\
|
+
|
|
.
|
\
|
+
=
+
s
av
p
av
p
C
N
d N
C
C
N
d N
C
C
u
t
u
t
3 / 1
1
6
|
.
|
\
|
=
u
+
N
C N
d
d
av
p
p
t
u
( )
( )
( )
( )
FM Cond
p
p
p p
p
p
t
d
d
d d
d
d
,
0 ,
1
3
0 ,
3
0 ,
1
3
3
3
1 2
tan 3 2
1
1
ln
3
1 2
tan 3 2
1
1
ln
t
=
+
+
+
+
+
+ +
+
+
t
t
u
t
N
N
C N
m
kT
av
FM Cond
3 / 2
1
1
,
6 2
1
|
.
|
\
|
=
u
(same for C
+
)
Wu, C. Y. and Biswas, P., Aerosol Sci. Technol., 28:1-20, 1998
Q: Physical meaning?
2013/8/18
9
Continuum regime
( )
( )
( )
( )
CO Cond
p
p
p p
p
p
t
d
d
d d
d
d
,
0 ,
1
3
0 ,
3
0 ,
1
3
3
3
1 2
tan 3 2
1
1
ln
3
1 2
tan 3 2
1
1
ln
t
=
+
+
+
+ +
+
+
3 / 1
1
,
6
4
1
|
.
|
\
|
=
u
N
C N
ND
av
FM Cond
t
u
t
t
(same for C
+
)
Free Molecular
Continuum
s
av
p
C
N
d
N
C C + =
u
1
3
0 ,
0
6
u
t
2013/8/18
10
Free Molecular Regime
2013/8/18
11
Comparison of the characteristic times
2013/8/18
12
Condensation Nuclei Counter
Q: What if we combine a DMA and a CNC?
Q: How to measure N by
light scattering intensity
if d
p
is different?
Q: Can we use CNC to measure dp?
2013/8/18
13
2013/8/18
14
Effects of Temperature
Temperature at the surface may be different
from that away from the surface

Droplet heating may take place due to the
release of latent heat
u
|
|
.
|
\
|
=
d
d
p
p
T
p
T
p
kd
D
dt
dd
1
1 1
4 u
u
|
|
.
|
\
|

=
u
u
1
1
1
T
p
T
p
Rk
H MW D
T T
d
d
d
H: latent heat
k
v
: thermal conductivity of the gas
D
v
: diffusion coefficient of the molecule
Q: Whats the resultant
impact of latent heat on
condensation?
2013/8/18
15
Empirical equation for temperature difference
( )( )
( )S T
S T T
T T
d
1
2
1 1
1
00782 . 0 082 . 0 1
1 0031 . 0 345 . 0 65 . 6
+ +
+ +
=
T
1
in
o
C.
Fuchs correction factor (necessary for small particles)
Kn Kn
Kn
42 . 3 33 . 5 1
1
2
+ +
+
= u
Q: Resultant effect of on condensation?
2013/8/18
16
2013/8/18
17
Condensation with Soluble Nuclei & Ions
|
|
.
|
\
|
+
|
|
.
|
\
|
= =
3
6
1
4
exp
p s
w
p
w
s
d M
imM
RTd
M
p
p
S
t
o
Saturation ratio for droplets
containing dissolved materials
m: mass of the dissolved salt
i: number of ions each
molecule of salt forms
M
w
: molecular weight of
solvent (water)
M
s
: molecular weight of
salt

2013/8/18
18
Saturation ratio vs droplet size for 10
-16
g NaCl
(Solid sphere of 0.045 m in diameter)
2013/8/18
19
Relative humidify vs droplet size
(a larger scale)
Droplet formation
& crystalization
Q: Implication?
10
-14
g
2013/8/18
20
Evaporation
The reverse process of particle growth though there is no
ciritical size.
Droplet lifetime/drying time
Q: Where is evaporation important?
For volatile materials, cooling of the droplet due to the
latenet heat of evaporation needs to be considered.
(
T
p
T
p
M D
d R
t
d
d
p p
u
8
2
Droplet lifetime for d
p
> 1.0 m
|
|
.
|
\
|
=
1
1
1
T
p
T
p
Rk
MH D
T T
d
d
d
u
u
2013/8/18
21
2013/8/18
22
Q: How can we control evaporation time?
2013/8/18
23
Q: For a given aerosol
system, whats the effect
of heating followed by
cooling?
Condensation Aerosol Generator
2013/8/18
24
Reflection
2013/8/18
25
( )
d av d
C C kTN p p =
1 1
Volume growth is
( )
d
p
p p
kT
Dd
dt
d
=
1
1
2 u t
u
Vapor concentration change is
( ) ( )
N Dd k dt k Ndt Dd
C C
dC
C C N Dd p p
kT
Dd
N
dt
d
N
dt
dC
p p
d
d p d
p
2 here w 2
2
2
1 1
1
1
= = t =
t =
t
=
u
u
=
Constant d
p
(continuum regime)

(pressure-concentration conversion)
2013/8/18
26
Initial condition
( )
d
C C k t C C = = =
0 2 0
ln 0 at
The final solution is then
( ) ( )
|
.
|
\
|
t
= =
=
|
|
.
|
\
|
+ =
t
t k
C C
C C
t k
C C
C C
C C t k C C
d
d
d
d
d d
exp ) exp(
ln
ln ln
1
0
1
0
0 1
Integrate both sides
( )
2 1
ln k t k C C
d
+ =
N Dd k
p
t
= = t
2
1 1
where
1
2013/8/18
27
Constant C (continuum regime)

( ) ( )
( )
( )
av d
av d p p
av d
p
d
p
p
N C C D k
dt k dt N C C D dd d
dt N C C
d
D
p p
kTd
D
dt
dd
u =
= u =
u
=
u
=
1 1 1
1 1 1
1
1
1
1
4 where
4
4 4
Size growth
( )
d av d
C C kTN p p =
1 1
(pressure-concentration conversion)
Integrate both sides
2 1
2
2
1
k t k d
p
+ =
2013/8/18
28
Initial condition
2
0 2 0
2
1
0 at
p p p
d k t d d = = =
The final solution is then
( )
d av
p p
p p
p
p p
C C N D
d
k
d
t
d
t k
d
d
d t k d
u
= = t
+
t
= + =
+ =
1 1
2
0
1
2
0
2
0
1
2
0
2
2
0 1
2
8 2
where
1 1
2
2

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2013/8/18

Aerosol & Particulate Research Laboratory

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