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Mass Diffusion
Mass diffusion refers
to the mass transfer that
occurs across a
stationary fluid or solid
in which a concentration
gradient exists. The
Consider two species A and B at
the same T and p, but initially
mass transport is driven
separated by a partition.
by the gradient without
In contrast, convention refers requiring bulk motion.
Eventually, uniform
to mass transfer that occurs
across a moving fluid in which concentration for all
species (A & B) are
concentration gradient also
achieved.
exist.
Volume [m 3 ]
Re UL/
Subscripts
Nu = hL/k
Pr = c p/k
A, B, C.... Species
Sh = h m L/D A-B
x, y, z........ Coordinates
Sc = /(D A-B )
xO2 M O2
xN 2 M N 2 xO2 M O2 x Ar M Ar
(0.209)(32)
0.231
(0.781)( 28) (0.209)(32) (0.009)( 46)
The corresponding mass fraction is m N 2 0.755, mO2 0.231,
m Ar 0.014.
mol
m A
m
m
, jAy DA A , jAz DA A
x
y
z
jA DAm A
jA DA A , if is a constant.
The last of the above equations is in vector form. It has been assumed that
the material is isotropic, i.e., and D A are direction - independen t.
jA cD Ax A
*
jA DAc A
where c A cx A is the moles of species A per unit volume of the solution,
i.e., the molar concentrat ion of species A. In a dilute solution, the molar
density of the solution, c, is essentiall y constant.
Mass Diffusion
Through a Plan
Wall
0
mA, 0
A
A
( m A, 0 m A, L )
Then we obtain the result : J A
. This solution is analog
L /( DA A)
Homework #2
a) Find the three components of Ficks law based on
cylindrical coordinates, r, , z for both mass and
molar flux of species A due to diffusion?
Concentrations at Interface
Although temperature is continuous
across a phase, concetration is usually
dicontinuous. In order to clearly define
concentrat ion, the subscripts u and s
denote the regions on the two sides of
the interface.
As shown in the water - air interface figure, u and s represent the water
and air phases, respectively, where air containing certain amount vapor
(moisture). If we ignore the small amount of air in the water and let
x H 2O,u 1, what is the water vapor concentrat ion along the interface in
the air - vapor phase?? The temperatures, Tu and Ts are 310 K and the
total pressure, Ps , is 105 Pa. It is also assumed that the thermodynamic
equilibrum exists at the interface.
Concentration
at Interface
At the equilibriu m conditon, the water vapor concentrat ion along the
water - air interface in the s - surface should be in the saturation
condition. Equilibri um saturation data for water - air systemsis available
in a conventional steam table. At Ts 310 K, the saturation vapor
pressure is 6,224 Pa. If the total pressure is 105 Pa, x H 2O can be found as
x H 2O,s
ci pi 6,224
0.06224
5
c
p
10
and
(0.06224) 18
m H 2O,s
0.0396
(0.06224) 18 (1 - 0.06224) 29
where the molecular weight of air was assumed to be 29 u.
Concentration at Interface in a
Salt-Water System
In many processes, solubility data can be found in a chemical handbook.
For an example, consider a slab of salt dissolving in water at 30 oC and 1
bar (105 Pa), the corresponding solibility of salt in water is 36.3 g/100g
(usually in cgs unit). If the salt is pure, m NaCl, u 1, the NaCl concentrat ion
along the salt - water interface in the s - side at the equilibriu m conditon
can be found as
36.3
0.266
100 36.3
On average, seawater in the oceans has a salinity of about 3.5% (35 g/kg),
m NaCl,s
which means that every kilogram (roughly one litre by volume) of seawater
has approximately 35 grams of dissolved salts (predominantly sodium (Na )
and chloride (Cl - ) ions).
t
z
Letting z and t approaching to infinitesmally small, one
A
j
has
A
t
z
Introducing Fick' s law, i.e., jAz D A-Bdm A /dz, gives
A ( m A )
dm A
D A -B
t
t
z
dz
m A - m A,0
z
erfc
4D t
m A,u - m A,0
A- B
e
z
z
e
z
D A-B t
From the Fick' s law, jAz D A
jAz
m A
z
(z 2 /4DA B t)
(m A,u m A,0 )e
t/DA-B
z 0
m A,u m A,0
D A-B t
m A,u m A,0
p
.
The solution for the above problem is
erfc
m A,u - m A,0
4D A-B t
Since m A,0 0.002, m A,u 0.015, m A 0.008, and z 0.001m,
m A - m A,0
0.008 - 0.002
z
erfc
0.462
4D t 0.015 0.002
A- B
z
0.52
4D A-B t
z2
(0.001) 2
t
1650s 0.46 h.
4D A-B (0.52) 2 4(5.6 10 10 )(0.52) 2
Comments
1. The diffusion coefficien t of C 2 in iron increases exponentially with temperature,
D A D o e -Q/R uT , where Do is a proportionconstan, and Q is the activation energy. The
process normally is carried out at relatively high temperatureto the time required.
2. The boundary condition of m(0, t) was specified using the maximum value. To
have a more accurate result, m A,u requires the solubility data by considerin g the
diffusion in the specific carbonaceo us material.
m A - m A,0
m - m A,b
z
z
or A
erfc
erf
4D t m A,0 - m A,b
4D t
m A,b - m A,0
A- B
A- B
where erf and erfc is the error and the error complement ary functions, respectively.
a. The above error function conversion can be proved as follows
erf
m A,0 - m A,b
m A,b - m A,0
m A,b - m A,0 m A,b - m A,0
4D A-B t
m A m A,0
m A m A,0
z
z
z
1
erf
1 - erf
erfc
m A,b - m A,0
m A,b - m A,0
4D A-B t
4D A-B t
4D A-B t
where erfc( ) 1 - erf( ).
b. Let z/ 4D A-B t and erf( )
2 2
One has
[erf( )]
e
,
z
z
2 2
e d & erf(0) 0, erf( ) 1.
0
m A m A,0 m A,b z 2/(4DA-Bt)
e
z
D A B t
m
h
jAr r R -D A-B A
h m ( A,b - A, ) If is a constant, A
m (m A,b - m A, )
r r R
r r R D A-B
where h m is the convective mass transfer coefficien t and is in [m/s]; R is the radius
of the droplet; the subscripts b represents the value at the boundary or interface while
indicates the value at the ambient condition or the location away from the boundary.
The above convective boundary condition can also be expressed as
c
x
- D A- B A
h m ( cA,b - cA, ) If c is a constant, D A-B A
h m (x A,b - x A, )
r r R
r r R
Here, the mass transfer coefficien t, h m , is analog to the heat transfer coefficien t, h.
Many analogies, such as Chilton and Colburn analogy, Reynolds analogy, Prandtl
Taylor analogy had been developed to directly relate heat transfer coefficients,
mass transfer coefficients, with different degrees of accuracy.
Evaporative Cooling
If qadd 0, qcon qevap
R uT
, where m*m is molar mass in
*
mm
[kg/kmol], and R u is the ideal gas constant equal to 8.314 J/K - mol . The relative humidity
is defined as, rh
p H 2O, (T )
p H 2O,sat (T )
the mixture (air) and p H 2O,sat (T ) is the saturated vapor pressure of water at T .
Based on the ideal gas law,
R u T
R u T
&
p
(
T
)
(T
)
.
H 2O, sat
H 2O, sat
m*m
m*m
p H 2O, (T ) H 2O, (T )
substituting the above two equations into the defination rh , one has
H O, (T )R u T / m*m H O, (T )
rh
*
p H O,sat (T ) H O,sat (T )R u T / m m H O,sat (T )
p H 2O, (T )
2
.
A,sat (T )
h A,sat (T ) A,sat (T )
(T )
Since A, RH , the relative humidity,
A,sat (T )
A,sat (Tb )
A,sat (Tb )
(T Tb ) h
(T Tb ) h
RH
RH
A,sat (T ) A,sat (T )h fg h m
A,sat (T )
A,sat (T )h fg hm
where the horizontal line over the variable denotes the mean of the variable.
The coefficien t ratio, h / h m is evaluated using a more simple correlatio n reported
by Knudsen & Katz (1958) :
Nu d hd / k CRedm Pr1/ 3 and Sh d h m d / D A B CRedm Sc1/ 3 ,
where the constants C and m depend on Re d and all propertiesare evaluated at film
temperature, (Tb T )/2 308K.
* J.D. Knudsen, D. L. Katz, Fluid Dynamics and Hat Transfer McGraw - Hill,
New York, 1958.
h m D A B
1/ 3
Pr
Sc
k
1.135 1007 23.7 x10 6
1/ 3
1/3
Le
0.878
D A B
27 x10 6
h
J
960.67 3
,
m K
hm
where Le is the Lewis number and k c p .
A,sat (Tb )
A,sat (T ) 15.52
The term
can be found to be
0.351 and
A,sat (T )
A,sat (Tb ) 44.25
A,sat (T ) 1 / A,sat (T ).
Then RH
A,sat (Tb )
(T Tb ) k
1/ 3
Le
A,sat (T ) A,sat (T )h fg D A B
0.351
( 45 25)
960.67 0.351 0.122 0.229
3
(1 / 15.52) x 2443x10
Red 5 / 8
0.62 Re Pr
Nud hd / k 0.3
, for Red Pr 0.2
1
[1 (0.4 / Pr)2 / 3 ]1 / 4 282,000
where all properties are evaluated at the film or mean temperature( Tb T )/2
1/ 2
d
1/ 3
1/ 2
d
1/ 3
0.62 Re Sc
0.3
[1 (0.4 / Sc 2 / 3 ]1 / 4
Red
1
282,000
5/8 4 /5
jA,b A -D A-B A
A h m ( A,b - A, ) A h m (m A,b - m A, )A
r r R
where A is the surface of the droplet equal tod 2 . A mass balance on a droplet requires
that the rate of mass loss equal to the evaporation rate. Since the droplet volume
d 3
dd
2
2 h m (m A,b - m A, )/ w
d w jA,b A h m(m A,b - m A, )d
dt 6
dt
3
d ,
6
dd
d 02
w d 02
10D A-B
(m - m A, )
2
w A,b
20D A-B (m A,b - m A, )
The ambient H 2 0 concentrat ion at T 315K and 1 atm, m A, can be obtained as follows :
The pressure at the saturate condition can be found as p A,sat 0.08135 x 105 Pa (from Text)
p A, ( RH ) p A,sat 0.505 x 0.8135 x105 0.0411x10 5 Pa,
x A, p A, / p 0.0411 / 1.050 0.0391, with M H 2O 18.02kg/kmol; M air 28.97kg/kmol
m A,
0.0391M H 2O
0.0391M H 2O (1 0.0391) M air
0.0391x18
0.0246
0.0391x18 (1 0.0391) x 29
To obtain Tb or m A,b , the boundary condition for the evaporating cooling can be applied :
h(Tb T ) hm [ (Tb )mA,b (Tb ) (T )mA, (T )]h fg . Since h/h m k / DA B was given
DA B h fg
hm
Tb T
h fg [ (T )mA, (T ) - (Tb )mA,b (Tb )]
[ (T )mA, (T ) - (Tb )mA,b (Tb )]
h
k
0.04497(18)
0.8081
0.02835.
0.0449(18) (1 0.0449)(29) 28.5061
D A B h fg
k
27x10 6 2.4x10 6
315
(1.15 0.02835 - 1.12 0.0246) 315 - 11 304K
0.027
Since Tb 304K is close to the assumed T1 , 305K, no further iteration is needed.
0.04242(18)
0.8082
0.02676
0.04242(18) (1 0.04242)(29) 28.5061
w d 02
dd
d 02
w d 02
65.128D A-B
(m A,b - m A, )
2
w
130.256D A-B (m A,b - m A, )
* W. Ranz, W. M arshall, Evaporation from drops, Chem. Eng. Prog., 48, 141 - 146, 1952.
accumulati on inflow
outflow
A generation by to V by diffusion
The mass of component A flowing into and out from V through three pairs of
parallel surface element perpendicular to the x-, y-, and z - coordinates. One has
A u A
j Ax
x yz
A A
Ax
A A
A
Ax
x
x
t
where rA is the rate of species A generation by chemical reaction per unit of volume.
A
t
x
y
z
y
z
x
2 A 2 A 2 A DA A DA A DA A
DA
rA
2
2
2
y
z x x
x y
x z
x
For constant and D A , the above equation becomes
2 A 2 A 2 A
A A
A
A
rA
u x
uy
uz
DA
2
2
2
t
x
y
z
y
z
x
A Personal Note
Acknowledgements
& Thank You!!
The generous funding provided by Czech Ministry of
Education, Youth and Sports through Project No.
HEATEAM - CZ.1.07/2.3.00/20.0188 and professorship by
Brno University of Technology (BUT) for me to stay in Brno
are acknowledged. I am thankful to my host, Professor
Miroslav Raudensk, for providing the wonderful
opportunity for me to work with his talented group. Special
thanks are to Messrs Ondrej Kristof and Tom Vesel for
their technical support in preparing this presentation. I also
like to express my gratitude and appreciation to Miss Hana
Hladilova and Mrs Zuzana Vetenkov for their enormous
patience and hospitality for making my stay in Brno a lovely
experience.