2c.chap27.UNSteady State Molecular Diffusion (Fall 2013)

2c.
Differential MT Equations for

Unsteady-State Molecular
Diffusion (USS-MD)
CHME 313:
Mass Transfer I
Lecture Notes Prepared by Dr. Shaheen Al-Muhtaseb 2013
2
1. USS-MD into a semi-infinite
medium
Consider that a slab has an
infinite sink for A.
This is valid for:
1. Low diffusion rates
2. Short times
3. Thick slab (long diffusion path)
N
A
0
z
sink for A
3
Assumptions:
1. In solids & liquids, bulk flow = 0 c
A
.V = 0
2. Dilute A UMD approaches EMCD (same
as point 1)
3. No Reaction (R
A
= 0)
4. Constant T and P
T
c
T
= constant
5. Binary Mixture
4
IC:
c
A
(z,0) = c
A0
@ t = 0 & all z
BCs:
c
A
(0,t) = c
As
@ z = 0 & all t
c
A
(,t) = c
A0
@ z = & all t
Model:
A
A A
c
N R
t
c
V + =
c
A
A AB A
c
N D c V
z
c
= +
c
2
2
A A
AB
c c
D
z t
c c
=
c c
5
Solution:
( )
0
erf erf
2
As A
As A
AB
c c z
c c
D t
|
| |
= =
|
|
\ .
Er r or Funct ion
NOTE:
erf(0) = 0
erf() = 1
( ) ( )
0
0
1 erf erfc
A A
As A
c c
c c
| |
= =

Compl ement ar y
Er r or Funct ion
Tabulatedin
AppendixL
.
BuiltinfunctioninExcel
6
Prove This Result
Hint:
Flux at z = 0:
| |
| |
0
0
0
0
A
A AB
z
z
As A
AB
AB
AB
As A
c
N D
z
c c
D
D t
D
c c
t
t
t
=
=
c
=
c
| |

=
|
|
\ .
=
( )
( )
2 2
erf .
2
exp
a z
a
a z
z
t
( c

=
c
Example:
A large tanker truck overturns and spills a herbicide
over a field. The diffusivity of the herbicide within the
water-saturated soil matrix is 1.0x10
-8
m
2
/sec and the
pure herbicide liquid remains as a pool on top of the
soil for 1800 seconds before evaporating completely.
Determine the depth into the soil at which plant and
insect life is likely to be destroyed if the lethal
concentration of herbicide is 0.1% by weight in the
water-saturated soil matrix. Be sure to draw a sketch of
your physical system, and the portion of your physical
system that you will focus your analysis on.
7
Solution:
8
100% herbicide, 1
As
= e

Water-saturated soil (B = O H
2
)
0
Ao
= e
s m 10 0 . 1 D
2 8
AB

=

Liquid Herbicide is on the surface for t = 1800 s

After 1800 s, determine depth z at which concentration of A in water saturated
soil is 0.1 wt% (
A
w = 0.001)

t
c
R N
A
A A
c
c
= + V ,
z
c
D N
A
AB A
c
c
= (dilute UMD) so
t
c
z
c
D
A
2
A
2
AB
c
c
=
c
c

This is a semi-infinite problem. Use error function solution:

1
2
A Ao
As Ao
AB
c c z
erf
c c
D t
(
( =
(

Since
A
A
A
M
w
c

=
&
A
M is big,
A
c is small
so dilute system
9
10
Example 27.1
Find z at which the
concentration becomes
1% of c
As
after 1 hr
c
As
= 2.5x10
20
atoms/cm
3
c
A0
= 0 atoms/cm
3
D
AB
= 6.5x10
-13
cm
2
/s
Microsoft Office Excel
Worksheet
See Example
27.1
11
2. USS-MD in a Medium with Finite
Dimensions and Simple Geometry
Slab with uniform boundary and initial conditions
c
As
c
As
z = 0 z = L
N
A
N
A
L/2 L/2
Assumptions:
1. In solids & liquids, bulk flow = 0
c
A
.V = 0
2. Dilute A UMD approaches EMCD
(same as point 1)
3. No Reaction (R
A
= 0)
4. Constant T and P
T
c
T
& D
AB
=
constant
5. Binary Mixture
12
Solution
A
A A
c
N R
t
c
V + =
c
A
A AB A
c
N D c V
z
c
= +
c
2
2
A A
AB
c c
D
z t
c c
=
c c
IC: c
A
(z,0) = c
A0
BCs:
c
A
(0,t) = c
As
c
A
(L,t) = c
As
c
A
(L/2,t)/z = 0
13
( )
2 2
0
2
1
4
cos exp 1, 3,
A AB AB
A AB As A
n
c D D t z
N D c c n n n
z L L L
t t
=
c
| | | |
= = =
| |
c
\ . \ .

2 2
2
1
0
4 1
sin exp 1, 3,
A As AB
n
A As
c c D t z
Y n n n
c c n L L
t t
t

=
| | | |
= = =
| |
\ . \ .

Concentration profile of A, i.e., c
A
(z, t):
Terms in summation decay to zero rapidly; you
usually need to calculate the first 4 to 10 terms
Flux of A, i.e., N
A
(z, t):
( )
2 2
0
2
2
1
4
cos exp =0
2
A AB AB
L
A AB As A
z
n
c D D t n
N D c c n
z L L
t
t
=
=
c
| | | |
= =
| |
c
\ . \ .

14
Fraction of total moles transferred:
Let :
( ) ( )
2 2
0
2
1
0
4
0, exp ; 1,3,
A AB AB
A AB As A
n
z
c D D t
N t D c c n n
z L L
t
=
=
c
| |
= = =
|
c
\ .

mol
A0
= c
A0
Area L [@ t = 0]
mol
A
= c
As
Area L [@ t = ]
( ) ( )
( )
2 2 2
0
0
/
0 0
0
1
2 0,
4
2 e
AB
t
A A z
t
n D t L
AB
A As A
n
mol t mol Area N t dt
D
mol Area c c dt
L
t
=
= +
= +
}
}
15
( ) ( )
2 2 2
0 0
2 2 2
1
8 1 1
e
AB
n D t L
A A As A
n
Area L
mol t mol c c
n n
t
t

=

(
= +
(

2
2
n=1
1
note:
8 n
t
( ) ( )
( )
2 2 2
0
0
0
2 2
1
8
1
e
AB
A As A
A
A As As
As A n D t L
n
As
mol t Area L c c
c Area L
mol c Area L c Area L
Area L c c
c Area L n
t
t
=

= + +

( )
2 2 2
2 2
1
0 0
8 1
e
AB
A A n D t L
A
n
A A A
mol mol t
mol
mol mol mol n
t
t

| |
=
|
\ .
( )
2 2 2
0
2 2
1
8 1
1 1 e
AB
A n D t L
A
n
A A
mol t
mol
mol mol n
t
t

=

| |
=
|
\ .

See Example
27.2 (solved
in Excel)
16
Typical Concentration Profiles
for slab with Finite Boundaries
Sink System
Source
System
t
c
As
c
A0
z = 0
z = L/2
N
A
t
c
A0
c
As
z = 0
z = L/2
N
A
17
Time-Concentration Charts
(Appendix F) for USS-MD
The solution of
D
AB
2
c
A
= c
A
/ t
is summarized in a graphical form for:
simple initial and boundary conditions and
systems of defined and simple geometries:
1. Slabs (Appendix F.1)
2. Cylinders (Appendix F.2)
3. Spheres (Appendix F.3)
18
Using Time-Concentration
Charts:
1. Find the characteristic length for symmetry
(x
1
= position from symmetry axis to
surface)
2. Define Y = (c
A1
c
A
)/(c
A1
c
A0
)
3. Define X = D
AB
.t / x
1
2
4. Define n = x/x
1
5. Define m = D
AB
/k
c
x
1
Relative
concentration
Relative time
Relative
position
Relative
Resistance
19
How to measure x
1
and x?
Slab Cylinder (radial
symmetry)
Sphere (radial
symmetry)
L
x = 0
x = x
1
x = x
1
x
1
= L/2
x
1
= L/2
c
As
c
As
x
L
x = 0
x = x
1
x
1
= L
c
As
x
x = r
x
1
= R
c
As
This imagecannot currently be displayed.
x = r
x
1
= R
c
As
20
What is the relative resistance (m)?
If m = 0 c
As
= c
Ab
(surface concentration equals
the bulk concentration, no convective mass
transfer resistance)
1
1
1 convective mass transfer resistance
1 molecular mass transfer resistance
c AB
c AB
k x D
m
k x D
= = =
What is the relative position (n = x/x
1
)?
If x = x
1
n = 1 (surface) c
As
If x = 0 n = 0 (line of symmetry) c
A
/ z = 0
21
X
Y
m=0,
n=1
m=1
m=0
m=2
m=
m=6
Variable n
Log scale!
Figures F.1 to F3
22
23
24
25
Figures F.4 to F.9 can also be used by changing o to
D
AB
and (T-T
)/ (T
0
-T
) to Y
(
T
-
T
)
/

(
T
0
-
T
)
2
1
t x o
n = ##
m = 0
m = 100
26
27
28
29
Example:
Determine the time that it is necessary to reduce
the center moisture content of a 5-cm-thick slab
of clay to 10 wt% if the slab is placed on a belt
passing through a continuous drier, thus
restricting the drying to only one of the flat
surfaces. The initial moisture content will be 15
wt% and the surface moisture content under the
constant drying conditions will be maintained at 4
wt%. The effective diffusivity of water through clay
is 1.3 x 10
-4
cm
2
/sec.
30
Solution:
31

As
e surface
x
1
= L = 5 cm
x =
2
L
= 2.5 cm
x = 0

t
c
R N
A
A A
c
c
= + V

( )
A
A AB A A B
c
N D x N N
x
c
= + +
c

t
c
x
c
D
A
2
A
2
AB
c
c
=
c
c
I.C. ( )
Ao A
c 0 , x c =
B.C. ( )
As A
c t , 5 c =
d ( ) 0 / , 0 = dz t c
A

545 . 0
15 4
10 4
y
Ao As
A As
=
=
e e
e e
=
dilute UMD
since
A
A
A
M
c
e
=

( )
mole / g 18
cm g 1 15 . 0
3
=
=
3
cm
mole
0083 . 0 dilute
32
m = 0 no convective resistance
|
|
.
|
\
|
= =
resistance diffusion
resistance convective
x k
D
m
c
AB

5 . 0
5
5 . 2
x
x
n
1
= = =
From Appendix F.7, get X:

analogy between heat & mass transfer
: 6 . 0 n at X
: 4 . 0 n at X
=
=

14 . 0 X
25 . 0 X
=
=
205 . 0 X
Ave
=

Since
2
1
AB
x
t D
205 . 0 X = =

( ) ( )
hr 68 . 10 s 497 , 38
sec
cm
10 3 . 1
cm 5 205 . 0
D
x 205 . 0
t
2
4
2
AB
2
1
= =
= =
33
What if you have an object with more than
one symmetry plane?
Solution:
Solve for each symmetry alone, then:
Y
overall
= Y
sym1
Y
sym2
Y
sym3
See Example
27.3

2c.chap27.UNSteady State Molecular Diffusion (Fall 2013)

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2c.chap27.UNSteady State Molecular Diffusion (Fall 2013)

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Copyright:

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2c.

Differential MT Equations for

Lecture Notes Prepared by Dr. Shaheen Al-Muhtaseb 2013

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