1.

8 TRANSPORT OF IONS IN
FLUIDS
1.8.1 Diffusion in a homogeneous non-
adsorbing system
1.8.2 Adsorption in a porous solid
1.8.3 Diffusion with Adsorption
1.8.4 Electromigration
Salt dissolving into a solution
Flux
Diffusion Coefficient
The diffusion coefficient is defined from the
equation:
F = D dC kg/m
2
/s
dx
where: F is the flux in kg/m
2
/s
D is the diffusion coefficient in m
2
/s
C is the concentration in kg/m
3

x is the position.
Thus dC/dx is the concentration gradient.
Equations for diffusion
Considering a small element of the system the rate at
which the concentration changes with time will be
proportional to the difference between the flux into it
and the flux out of it: O dC = A AF
dt
where O is the volume of the element, A is the cross
sectional area and L = O/A is the length
AF = L dF thus: dC = dF
dx dt dx
and: dC = D d
2
C
dt dx
2

Diffusion
through a
barrier
Increasing time
Position
Concentration
Concrete
Strong
Solution
Weak
Solution
1.8 TRANSPORT OF IONS IN
FLUIDS
1.8.1 Diffusion in a homogeneous non-
adsorbing system
1.8.2 Adsorption in a porous solid
1.8.3 Diffusion with Adsorption
1.8.4 Electromigration
Definitions
Absorbed water is drawn in to the pores of a
solid by capillary suction or osmosis.
Adsorbed ions are bound into the matrix of
a solid and cannot move.


Concentrations
The concentration of ions in a porous solid (in
which the pores are filled with fluid) may be
measured in two different ways:
C
l
kg/m
3
is the concentration of ions per unit
volume of liquid in the pores
and
C
s
kg/m
3
is the total concentration (including
adsorbed ions) per unit volume of the solid.
Acid and water soluble
If the "acid soluble" concentration is
measured C
s
is obtained
If the "water soluble" concentration is
measured C
l
is obtained.
Ions in solution are the only ones that will
cause corrosion.
The ratio of the two concentrations is the
capacity factor:
l C
C
s
= o
Pore fluid expression cell
Distribution ratio
The distribution ratio K
d
is defined as the number of
adsorbed ions per unit mass of the solid divided by
the number of dissolved ions per unit volume of the
pore fluid thus
K
d
= (C
s
- cC
l
) m
3
/kg
C
l

where c is the porosity and is the density thus:
o = c + K
d
.
Linear isotherm
A simple approximation of the amount of
material which is adsorbed onto the matrix
may be obtained by assuming that at all
concentrations it is proportional to the
concentration of ions in the pore fluid (note
that this implies that the adsorption is
reversible). Thus o and k
d
are constant for all
concentrations.
1.8 TRANSPORT OF IONS IN
FLUIDS
1.8.1 Diffusion in a homogeneous non-
adsorbing system
1.8.2 Adsorption in a porous solid
1.8.3 Diffusion with Adsorption
1.8.4 Electromigration
Effect of Capacity Factor
The equation for the rate of change of concentration
will be for the total concentration:
dC
s
= dF
dt dx
thus: dC
l
= dF
dt o dx
From this it may be seen that a high value of o will
make the concentration change much more slowly -
i.e. if chlorides are penetration into a wall it will
delay the start of corrosion of the steel
Apparent Diffusion Coefficient
The apparent diffusion coefficient D
a
(which
is what can be measured by testing the solid
using measurements of total concentration C
s
)
is defined from:

F = D
a
dC
s
kg/m
2
/s
dx
Intrinsic Diffusion Coefficient
The intrinsic diffusion coefficient (which is the
diffusion coefficient for the pore solution) is defined
from:
F ' = D
i
dC
l
kg/m
2
/s
dx
where F ' is the flux per unit cross sectional area of
the liquid in the pores. Thus:
F = c D
i
dC
l
kg/m
2
/s
dx
Diffusion Coefficients
It may be seen that:

o = D
i

c D
a


for a typical concrete D
i
= 5 10
-12
m
2
/s
Diffusion Cells
Detail of Diffusion Cells
The NIREX concept
Spent Fuel Repository
Transport from
spent fuel
Diffusion
Data
Typical Landfill Arrangement
Permeability Control
Time years
-2
0
2
4
6
8
10
12
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Depth m
C
o
n
c
e
n
t
r
a
t
i
o
n

k
g
/
m
3

o
f

s
o
l
i
d
40 80 400
k = 10
-9
m/s D = 5 10
-12
m
2
/s
Diffusion Control
Time years
-2
0
2
4
6
8
10
12
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Depth m
C
o
n
c
e
n
t
r
a
t
i
o
n

k
g
/
m
3

o
f

s
o
l
i
d
100 500 5000
k = 10
-12
m/s
Output of contaminants from
base of barrier
0
2
4
6
8
10
12
14
16
18
0 2000 4000 6000
Time years
C
u
m
u
l
a
t
i
v
e

o
u
t
p
u
t

k
g
/
m
2
Permeability
control
(base case)
Diffusion
control
Effect of Capacity Factor
1
10
100
1000
10000
1 10 100
Capacity Factor
B
r
e
a
k
t
h
r
o
u
g
h

t
i
m
e



Y
e
a
r
s
Base
case
Diffusion
Control
1.8 TRANSPORT OF IONS IN
FLUIDS
1.8.1 Diffusion in a homogeneous non-
adsorbing system
1.8.2 Adsorption in a porous solid
1.8.3 Diffusion with Adsorption
1.8.4 Electromigration
Electromigration

V
Solution
with supply
of negative
ions
Solution with
supply of
positive ions
+ -
Negative ions, e.g. chloride
Positive ions
Electromigration
The flux due to electromigration is given by the
following equation:


Where: J is the flux in kg/m
2
/s, D is the diffusion coefficient in m
2
/s, z is
the valency of the ion, F is the Faraday constant, E is the electric field in
volts/m, C is the concentration of ions in mol/m
3
,

R = 8.31 J/mol/
o
K, T is
the temperature in
o
K

Rearranging this gives the Nernst-Einstein equation:


Where o is the conductivity
RT
DzECF
= J
i i
i
i
c F z
RT
D
2 2
o
=
Combining Diffusion and
Electromigration
The general law governing the ionic movements in concrete
due to the chemical and electrical potential is known as the
Nernst-Planck equation:




J
i
= flux of species i [mol/m
2
/s]
D
i
= diffusion coefficient of species i [m
2
/s]
R= gas constant [8.31 J/mol/K]
T= absolute temperature [K]
V = Voltage, thus oV/ox = Electric field

x
V
c D
RT
F z
x
c
D J
i i
i i
i i
c
c
+
c
c
=
Solving electromigration and diffusion
the hard way
assuming E is constant
)]
4
erfc(
2
1
e
2
a[ FADc = I
)
16
2
2
2
2
(
o
|

|
o
+
t |
|

|
o

o
o = ax
| = 2a Dt
where
a =
zFE
RT
Salt bridge measurements
sample
cell
cell
Reference
electrode
(connected
to data
logger)
small bore pipe 4 mm drilled
hole
Potassium
chloride
Electromigration /
diffusion cell
Section through sample during test
Voltage
Chloride zone Sodium zone
Low resistance (high D) High resistance (low D)
Electrostatic field E is
gradient
?
?
Modelling a thin slice of the sample for a short time step

Apply Kirchoffs law : current in = current out
Electromigration into element
- set by field E which was
calculated for the last element
Diffusion in and out fixed by
concentration gradient
Electromigration out of
element we can set this for
charge neutrality by adjusting
the field E

Final adjustments are needed to get the correct total voltage across
the sample.
Model output for
current and voltage
Current vs time with no
voltage correction (average)
0.000E+00
5.000E+00
1.000E+01
1.500E+01
2.000E+01
2.500E+01
3.000E+01
0 5 10 15 20
Time hours
T
o
t
a
l

C
u
r
r
e
n
t

m
A
m
p
s
Voltage adjustments at different times
-5
0
5
10
15
20
25
30
35
40
45
0.0 10.0 20.0 30.0 40.0 50.0 60.0
Distance from negative side mm
V
o
l
t
a
g
e
0.000
6.802
17.013
0.000E+00
5.000E+01
1.000E+02
1.500E+02
2.000E+02
2.500E+02
3.000E+02
3.500E+02
4.000E+02
0 5 10 15 20
Time hours
T
o
t
a
l

C
u
r
r
e
n
t

m
A
m
p
s
Concentrations in cells at distances from negative side
in mol/m3 vs time in hours
Hydroxyl
0
50
100
150
200
250
300
350
400
0 5 10 15 20
negative
2.5
7.5
17.5
47.5
positive
Potassium
-50
0
50
100
150
200
0 5 10 15 20
negativ
e
2.5
7.5
17.5
47.5
positive
Sodium
0
100
200
300
400
500
600
0 5 10 15 20
negative
2.5
7.5
17.5
47.5
positive
Chloride
-100
0
100
200
300
400
500
600
0 5 10 15 20
negative
2.5
7.5
17.5
47.5
positive
Current in amps at different times in hours vs position
in mm from the negative side
Time = 0
0.00E+00
5.00E-03
1.00E-02
1.50E-02
2.00E-02
2.50E-02
3.00E-02
2.5 7.5 12.5 17.5 22.5 27.5 32.5 37.5 42.5 47.5
potassium
sodium
chloride
hydroxyl
Time = 7
0.00E+00
2.00E-03
4.00E-03
6.00E-03
8.00E-03
1.00E-02
1.20E-02
1.40E-02
2.5 7.5 12.5 17.5 22.5 27.5 32.5 37.5 42.5 47.5
potassium
sodium
chloride
hydroxyl
Time = 14
0.00E+00
2.00E-03
4.00E-03
6.00E-03
8.00E-03
1.00E-02
1.20E-02
1.40E-02
2.5 7.5 12.5 17.5 22.5 27.5 32.5 37.5 42.5 47.5
potassium
sodium
chloride
hydroxyl
Current from elements in cells at distances from
negative side in amps vs time in hours
Hydroxyl
-0.001
0
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0.008
0 5 10 15 20
2.5
7.5
17.5
47.5
Potassium
-0.005
0
0.005
0.01
0.015
0.02
0 5 10 15 20
2.5
7.5
17.5
47.5
Sodium
0
0.002
0.004
0.006
0.008
0.01
0 5 10 15 20
2.5
7.5
17.5
47.5
Chloride
-0.002
0
0.002
0.004
0.006
0.008
0.01
0 5 10 15 20
2.5
7.5
17.5
47.5