Air Quality and Aerosol Mechanics Spring 2013

Jing Wang, IfU, ETHZ 1

Condensation and
Evaporation
Jing Wang
Assistant Professor
ETH Zrich
Institute of Environmental Engineering
jing.wang@ifu.baug.ethz.ch
Phone +41 44 633 36 21


Empa
Analytical Chemistry
jing.wang@empa.ch
Phone +41 44 823 61 15


1
List of Symbols
2
p
A
: the partial pressure of gas A;
p
T
: the total pressure of the gas mixture;
p
s
: saturation vapor pressure (vapor pressure);
p: pressure; T: temperature; v: volume;
p
1
, p
2
, T
1
, T
2
, v
1
, v
2
: the above parameters at different statuses;
S
R
: saturation ratio; : the specific heat ratio;
d
*
: critical diameter for a droplet at equilibrium;
K
R
: Kelvin ratio;
p
d
: partial pressure near the droplet surface pressure to maintain
the equilibrium according to the Kelvin equation;
: surface tension; M: molecular weight of the vapors;

l
: density of the liquid; : gas constant 8.314 Joule K
-1
mole
-1
;

v
: density of the vapor; h: height of liquid;
d : the droplet diameter; g: gravitational acceleration;

R

List of Symbols
3
J : molecular flux per unit area;
N: molecular number concentration;
: mean thermal speed of gas molecules;
k : Boltzmanns constant; p

: the ambient partial pressure;

n
z
: the net rate of molecules added to (or leave) the droplet;
d
p
: the droplet diameter;

c
: the condensation coefficient or the coefficient for the
molecules to stick on the droplet; N
a
: Avogadros number;
M : molecular weight, mass per mole (kg/mole);
m : molecular weight, mass per molecule;
v
m
: volume of a molecule;
: mean free path of vapor molecules;
D : the diffusion coefficient for vapor molecules;
: the flux on a surface; r : generic radial direction location;
c
List of Symbols
4
N
d
: molecular concentration at the surface of the droplet;
N

: molecular concentration in the ambient;

T
d
: temperature at the surface of the droplet;
T

: temperature in the ambient;

: correction term for the diffusional growth rate;
m
s
: mass of the dissolved salt;
i: number of ions each molecule of salt forms when it dissolves (2)
M
w
: molecular weight of solvent;
M
s
: molecular weight of salt;
: solvent density;
t : time

Air Quality and Aerosol Mechanics Spring 2013
Jing Wang, IfU, ETHZ 2
Outline
5
Condensation, evaporation and saturation
Kelvin effect
Homogeneous nucleation
Condensation grow rate
Nucleated condensation
Evaporation
Condensation particle counters

Importance
6
Cloud physics Aerosol generation
Humidification Spray drying
Combustion Particle measurement

water vapor
air molecule
liquid water
Water Cycle
7
Definitions
8
Partial pressure: the pressure of a gas (or vapor) in a gas mixture
would have if it were to occupy, by itself, the entire volume
occupied by the gas mixture.
water vapor
air molecule
liquid water
The volume fraction of gas A is p
A
/p
T
, where p
A
is the partial
pressure of gas A, and p
T
is the total pressure of the mixture.
Saturation vapor pressure (vapor
pressure) p
s
, when the condensation of
the vapor is in equilibrium with the
evaporation from the plane liquid
surface.
Function of temperature
Air Quality and Aerosol Mechanics Spring 2013
Jing Wang, IfU, ETHZ 3
Water Vapor Pressure
9
Empirical equation for water (accurate within 0.5% for 273 373 K)
)
37
4060
7 . 16 exp(

=
T
p
s
kPa
p
s
= 2.3 kPa at T = 293K, p
s
= 101 kPa (1 atm) at T = 373 K.
Saturation ratio
s
R
p
p
S = S
R
< 1 unsaturated, S
R
>1 supersaturated.
S
R
= 0.5, relative humidity (RH) = 50%, S
R
=1.1, RH = 110%.
How to achieve supersaturation?
Supersaturation
10
Cooling, adiabatic expansion, mixing
Adiabatic expansion: change of volume without heat exchange.
1
2
1
1
2

|
|
.
|

\
|
=
k
v
v
T
T
where is the specific heat ratio, =1.4 for air.
Example: air saturated with water vapor at 20 C is expanded
adiabatically by 18%. What are the new temperature and
saturation ratio?
18 . 1
1
2
=
v
v
2 . 274 ) 18 . 1 / 1 ( 293
4 . 0
1
2
1
1 2
= =
|
|
.
|

\
|
=
k
v
v
T T
3 . 2 )
37 293
4060
7 . 16 exp( ) (
1
=

= T p
s
66 . 0 ) (
2
= T p
s
8 . 2
66 . 0
) 18 . 1 / 1 ( * 3 . 2
66 . 0
/ * 3 . 2
4 . 1
1 2
= = =
p p
S
R
Kelvin Effect
11
p
s
is the equilibrium pressure for a flat liquid surface. For surface
of a droplet, the attractive forces between surface molecules need
to account for surface tension, thus it is easier for molecules to
leave the droplet surface.
To maintain the equilibrium for a
droplet with diameter d
*
(no
condensation, no evaporation), the
partial pressure must be higher than
p
s
. This saturation ratio is the Kelvin
ratio K
R
,
|
|
.
|

\
|
= =
*

4
exp
Td R
M
p
p
K
l s
d
R

surface tension
M: molecular weight of the vapors

l
: density of the liquid
: 8.314 Joule K
-1
mole
-1
R

p
d
: partial pressure near
the droplet surface
Kelvin Equation Derivation
12
h g p
v
d d =
Assume perfect gas law for vapor
T
M
R
p
v

= h
T R
pMg
p d

d =
T R
Mgh
p
p
s
d

ln =
Surface tension
gh p
l
= A
d d p t t = A 4 /
2
Thus
|
|
.
|

\
|
=
Td R
M
p
p
l s
d

4
exp

Air Quality and Aerosol Mechanics Spring 2013
Jing Wang, IfU, ETHZ 4
Example for Kelvin Effect
13
Condensation
Evaporation
What saturation ratio is needed
to maintain the size of 50 nm
pure water droplets at 20 C?
|
|
.
|

\
|
= =
*

4
exp
Td R
M
p
p
K
l s
d
R

=0.0727 N/m, surface tension
between air and water at NTP.
M=18/1000 kg/mol

l
=1000 kg/m
3

= 8.314 Joule K
-1
mole
-1
R

T=293 K; d
*
= 5010
-9
m.
K
R
=1.044
Even at saturation, small
droplets evaporate and
disappear.
Homogeneous Nucleation
14
Homogeneous nucleation (self-nucleation) is the formation of
particles from the supersaturated vapor without the assistance of
condensation nuclei or ions.
What is the value of S
R
if condensation were to start from
individual water molecules?
Homogeneous nucleation
usually starts with clusters of
molecules. Pure water at 293
C will form particles when S
R

> 3.5, corresponding to d
*
=1.7
nm.
Homogeneous nucleation
contributes to photochemical
smog.
Condensation Growth: free molecular
15
p
d
p

c N j
4
1
=
m
kT
c
t
8
= NkT p =

Thus the net rate of molecules added to the droplet is

c
d
p z
mkT
p p
d n o
t
t
2
2

=

d
p
is the droplet diameter, p

is the ambient partial pressure, p

d
is the
pressure to maintain the equilibrium according to the Kelvin equation,

c
is the condensation coefficient or the coefficient for the molecules
to stick on the droplet, 0.04 is often used.
3
6
p
d v
t
= m z
v n
dt
dv
=
a l
m
N
M
v

=
mkT N
p p M
dt
d d
a l
d c p
t
o
2
) ( 2 ) (
=

Thus
N
a
= Avogadros
number
for d
p
< .
Condensation Growth: diffusion limited
16
N
N
d
N

When d
p
> , diffusion of vapor molecules
determines the growth rate. D is the
diffusion coefficient for vapor molecules.
dr
dN
D j = 2
4 r
j
t
u
=
For steady state diffusion, the flux is constant
} }

=
=
=
=
u
=
N N
N N
r
d r
d p
DdN
r
dr
2 /
2
4t
) ( 2
d p
N N D d = u

t
Using perfect gas law and n
z
= at the droplet surface
|
|
.
|

\
|
=

d
d p
z
T
p
T
p
k
D d
n
t 2
|
|
.
|

\
|
=

d
d
p l
p
T
p
T
p
R d
DM
dt
d d

4 ) (

for d
p
> .
Air Quality and Aerosol Mechanics Spring 2013
Jing Wang, IfU, ETHZ 5
Correction and Temperature Effect
17
The diffusion limited growth equation needs to be corrected because the
diffusion equation breaks down within one free path of the droplet
surface. The correction given by Fuchs (1959) and Davies (1978) is
|

|
|
.
|

\
|
=

d
d
p l
p
T
p
T
p
R d
DM
dt
d d

4 ) (
and

|
42 . 3 ) / ( 33 . 5
2
2
+ +
+
=
p p
p
d d
d
The correction reduces the growth rate.
For slow growth 1.0 < S
R
< 1.05
d
T T ~

For fast growth, empirical equation

R
R
d
S T
S T T
T T
) 00782 . 0 082 . 0 ( 1
) 1 )( 0031 . 0 345 . 0 65 . 6 (
2

+ +
+ +
=
T

in C, for 0<S
R
<5 and 273<T

< 313.
Nucleated Condensation
18
Nucleated condensation, or heterogeneous nucleation is the formation
and growth of particles in the presence of condensation nuclei or ions.
Insoluble nuclei: passive site for vapors to condense on
behaves like a droplet of the same size
Under favorable conditions, d
*
and critical S
R

determined by Kelvin equation
Ions: clusters of air molecules with electrical charges
slightly changes the relation between d
*
and critical S
R

facilitate droplet formation when S
R
> 2.0.
Soluble nuclei: most important formation mechanism.


significantly promotes droplet formation even at
saturation or unsaturated conditions.
NaCl is most important nuclei.
Effect of Salt on Condensation
19
The salt has high affinity with water. Dissolved salt molecules
lower the vapor pressure at the water surface, thus promote
condensation.
|
|
.
|

\
|
+
|
|
.
|

\
|
= =
3
6
1
4
exp
p s
w s
p
w
s
d
R
d M
M im
RTd
M
p
p
S
t

m
s
: mass of the dissolved salt
i: number of ions each
molecule of salt forms when it
dissolves (2 for NaCl).
M
w
: molecular weight of
solvent (water)
M
s
: molecular weight of
salt
: solvent density
Kohler Curve
20
Saturation ratio vs. droplet size for 10
-16
g NaCl (Solid sphere of
45 nm in diameter). At saturation, the particle becomes a stable
0.23-m droplet.
Air Quality and Aerosol Mechanics Spring 2013
Jing Wang, IfU, ETHZ 6
Evaporation Rate and Time
21
A pure liquid droplet under S
R
below the Kelvin ratio, will
completely evaporate. The time for this is the droplet lifetime or
drying time.
Evaporation is the opposite of condensation. The right-hand
side is negative and d
p
is decreasing
|

|
|
.
|

\
|
=

d
d
p l
p
T
p
T
p
R d
DM
dt
d d

4 ) (
for d
p
> .
Time t for a droplet with diameter d
1
to completely evaporate
} } |
|
.
|

\
|
=

t
d
d
l
p
d
p
dt
T
p
T
p
R
DM
d d d
0
0

4
) (
1

|
|
.
|

\
|

=

T
p
T
p
DM
d R
t
d
d
p l
8

for d
p
> 1m.
Evaporation Time
22
Evaporation of pure water droplet at 293 K and 50% of relative
humidity
Droplets of 0.1 0.8 m. Dashed
lines show the effect of T
.

Droplets of 4 15 m.
Example
23
Example: how long does it take a 20-m droplet of pure water to
evaporate completely in dry air at 293 K?
|
|
.
|

\
|

=

T
p
T
p
DM
d R
t
d
d
p l
8

2
0 =

p
0 ) 20 00782 . 0 082 . 0 ( 1
) 1 0 )( 20 0031 . 0 20 345 . 0 65 . 6 (
20
2
+ +
+ +
=
d
T
Dry air C 20 293
o
= =

K T
K T
d
2 . 278 C 2 . 5
o
= =
kPa 876 . 0 )
37 2 . 278
4060
7 . 16 exp( =

=
d
p
The diffusion coefficient of water vapors at 293 K and 1 atm
5
10 4 . 2

= D
m
2
/s
s 31 . 0
293
0
2 . 278
876
1000
18
10 4 . 2 8
) 10 20 ( 1000 31 . 8
5
2 6
=
|
.
|

\
|


=

t
Condensation Particle Counters
24
CPC grows aerosols by condensing vapors of working fluid onto
them, then detects the aerosol by optical scattering. It is the
primary method to detect and count aerosols in the nm range.
Lower detection limit
1 nm 20 nm, depending
on the nuclei, working
liquid and temperatures
Air Quality and Aerosol Mechanics Spring 2013
Jing Wang, IfU, ETHZ 7
CPC Design
25
CONDENSER: 10C
SATURATOR: 40C
Sample Aerosol
Lamp Photo Detector
time
V
o
l
t
s
Butanol
Saturation
1
3nm
6nm
>10nm
Schematic of unltrafine CPC (TSI 3025,
Stolzenburg & McMurry, 1991)
Nuclei grow to about
10 m, regardless of
their initial sizes.
Flowrate: 0.3 or 1.5 lpm
Response time ~ 1 sec
Concentration:
single particle counting
< 310
5
p/cc;
photometric counting
up to 10
6
p/cc.
error 10 % at < 310
5

p/cc
Specification for TSI 3776
Aerosol Generation
26
Condensation
Aerosol
Generator
Po-210
CPC
AP
AP
P
Upstream Particle Count
Downstream Particle Count
Face Velocity
Pressure
Drop
Voltage
L
D
M
A
Power Supply
Filter
Holder
CPC
1st Furnace
N2
Silver
2nd Furnace
Agglomeration
Chamber
Po-210
Evaporation and
condensation
generation of
metal
nanoparticles
Silver nanoparticles