Bouzek - Modelling and Design of The Electrochemical Processes and Reactors

Modelling and Design of the Electrochemical
Processes and Reactors

Karel Bouzek, Roman Kodm
Department of Inorganic Technology,
Institute of Chemical Technology Prague
Mathematical modelling and process design
Role of the mathematical modelling in the electrochemical engineering
pedagogical
deep understanding of the process
scientific
economical
identification of the rate determining steps
learning the way of sequential thinking
analysis of the problem on the local scale based on the global experimental data
evaluation of not directly accessible parameters
verification of the theories developed
process scale-up
process optimisation
identification of the possible bottlenecks
costs reduction
Levels of the mathematical modelling
material balance
based on the macroscopic kinetics data
steady state models
dynamic models
based on the two elementary modes of operation
assessment of the system limits under given assumptions
detail description of the space distribution of the process parameters in steady state
allows evaluation of the construction and operational parameters suitability
sufficient for the majority of cases
description of the non-stationary processes
process start-up and termination
discontinuous processes
most sophisticated problems
Material balance
modes of operation
batch (discontinuous) processes
basic characteristics
continuous processes
processes in a closed systems (no mass exchange with the surroundings)
no steady state is reached before the reaction equilibrium
suitable mainly for the small scale processes
typical design - stirred tank reactor
continuously stirred tank reactor (CSTR)
plug-flow reactor (PFR)
Batch processes
description by the dynamic model only
F n
I
V R J
d
dc
V
i
e
R i i
i
R
1
+ A =
t
Batch processes
material balance
high mixing rate spatially uniform concentration
B ne A p +

)
F n
I
d
dc
V
A
e A
R
1
=
t
)
F n
a j
d
dc
A
e e A
1
=
t
R
e
e
V
A
a =
mass transfer limited reaction
A m lim
c k j =
galvanostatic process at j < j
lim
t =
F n
ja
c c
A
e
0 , A A
concentration decay of component A in time
galvanostatic process at j > j
lim
) t =
e m 0 , A A
a k exp c c
) t = = = 1
e m
A 0 , A m
A A m lim
e
a k exp
j
F n c k
j
F n c k
j
j
Continuous process - CSTR
material balance
high mixing rate spatially uniform concentration
equal inlet and outlet flow rates independent on time
constant reactor volume and mean residence time
B ne A p +

)
A R I , A O , A
R V c c V =
)
)
F n
I
c c V
A
e
I , A O , A
1
=
F n
j a
c
FV n
I
c c
A
e
I , A
R A
I , A O , A
= =
lim
lim
j
F n c k
j
j
A O , A m
lim
e
= = 1
F n
j a
c
FV n
I
c c
A
lim e
I , A
R A
lim
I , A O , A
= =
Continuous process - PFR
material balance
negligible axial electrolyte mixing
negligible concentration gradient perpendicular to the flow direction
B ne A p +

A
A
R
dx
dc
v =
)
F n
j
b
dx
dc
V
A
e A
1
=
'
+
'
V
bx
F n
j
c c
A
I , A A
=
lim
lim
'
+
'
= = 1
V
bx k
exp
j
F n c k
j
j
m
A I , A m
lim
e
'
+
'
=
V
bx k
exp c c
m
I , A A
b electrode width
Steady state models
Background of the electrochemical reactors modelling
basic parameters calculated
local values of the Galvani potential
local current density values
division of the mathematical models
according to the level of simplification primary current density distribution
secondary current density distribution
tertiary current density distribution
according to the number of dimensions considered one dimensional
two dimensional
three dimensional
according to the mathematical methods used analytical
numerical
way of the system description
differential or partial differential equations
Steady state models
Level of simplification
primary current density distribution
infinitely fast reaction kinetics
infinitely fast mass transfer kinetics
tertiary current density distribution
mass transfer kinetics and electrolyte hydrodynamics considered
additional reduction of the local extremes
secondary current density distribution
reaction kinetics considered
only influencing factors geometry of the system
electrolyte conductivity
more regular current density distribution
sufficient approximation for the majority of the industrially relevant systems
extremely complicated used only in a strictly limited number of cases
Steady state models
Number of dimensions considered
selection criteria
homogeneity of the system
significance of the local irregularities
consequences of the increase in the number of dimensions
one-dimensional model described by the differential equations
symmetry of the system
more dimensions requires partial differential equations
significantly more complicated mathematics
geometrically increasing hardware demands
three dimensional models
simplified models
mainly focus on the critical element of the complex system
important mainly in the tertiary current distribution models
Steady state models
Mathematical methods used
analytical solution of the model equations
most accurate way
general validity of the equations derived (for the given system)
numerical mathematics
able to describe complicated geometries and complex systems
available for the extremely simple configurations only
less significant simplification assumptions
results valid only for the particular system solved
question of results accuracy
methods of numerical mathematics used
strongly dependent on the dimensions number
one dimensional case - classical integration methods (Runge-Kutta, collocation, shooting, )
more dimensional tasks rapid development with improving hardware
strongly limited applicability in the industrially relevant systems
FDM
FEM
BEM
Steady state models
Basic model equations for electrochemical systems
equation of the mass and charge transfer in the electrolyte solution
current density value
electrolyte solution with no concentration gradients
i i i i i i
c v c u c D J
T
T
+ \ \ =
Nernst-Planck equation
i i i
J F z j
T T
=

=
i
i i
J z F j
T T
application of the Faraday law

+ \ \ =
i
i i
i
i i i
i
i i i
c z v F c u z F c D z F j
T
T
electroneutrality condition
0 c z
i
i i
=
\ =
i
i i i
c u z F j
T
\ i = j
T
= i
i
i i i
c u z F
electrolyte conductivity definition
Steady state models
electrolyte solution with concentration gradients
current less system
\
i
i
= \
i
i i i
c z D
F j
T
\
i
= \
i
i i i
c z D
F
liquid junction potential
)
=
i
i
i
0
i
c ln d
z
t
F
RT
d
one dimensional case
Steady state models
mass balance in the electrolyte volume
introducing Nernts-Planck equation after multiplication by z
i
F
)
i i
i
J
c
G + \ =
t
0 z F J z F
i
i i
i
i i
= G + \

0 j J z F
i
i i
= \ = \
charge conservation
0 z
i
i i
= G
electroneutrality condition
introducing expression for j
0 c z D c z u z u c
i
i
2
i i
i
i i i
i
2
i i i
= \ + \ \ + \

modified Laplace equation
0
2
= \
Laplace equation
no concentration gradients
Steady state models
Boundary conditions
significant variability according to the particular conditions
arbitrary definition
in agreement with general types of boundary conditions
constant value, i.e. Galvani potential
constant flux, i.e. current density
Boundary condition constant potential value
requirements:
no influence of the current load
constant composition, i.e. constant properties
typical choices:
electrode current leads potentials
electrode body potential
arbitrary values typically used:
cathode potential equal to zero
anode potential equal to the cell voltage
special case electrode / electrolyte interface
Steady state models
Boundary condition constant flux
typically the cell walls and electrolyte surface (no flux)
simplification considered: primary vs. secondary (tertiary) current density distribution
in special cases flux continuity used
Electrode / electrolyte interface
linear
Tafel
Butler-Volmer
potential rate determining steps in the electrode reaction kinetics
kinetics of the mass transfer to the electrode
adsorption
charge transfer kinetics
desorption of the products
kinetics of the product transfer from the electrode
possible homogeneous reactions
mass transfer kinetics subject of the individual lecture
types of the charge transfer kinetics used:
Steady state models
Linear kinetics
historical question
nowadays overcome
Tafel kinetics
considers just one part of the polarisation curve
j ln b a + = g
'
+
'
= g
0
j
j
ln b e j j
0
>
computational demands
physical models
suitable for the systems far from equilibrium
simple kinetics evaluation from the model results
linearisation of the low current densities part -
- minimisation of the divergence danger
0
j
j
e
b
= g e j j
0
Steady state models

Butler - Volmer kinetics
general description of the charge transfer kinetics
more complicated kinetic evaluation (requires additional numerical procedure)
)
)
`
|
,
|
g =
RT
zF
exp
c
c
RT
zF
1 exp
c
c
j j
C
0
ox
s
ox
C
0
red
s
red
0
mass transfer limited kinetics - concentration polarisation
)
,
|
'
+
'
'
+
'
=
RT
zF
exp
j
1
1
RT
zF
1 exp
j
1
1 j j
C
C lim,
C
A lim,
0
charge transfer limited kinetics
)
)
`
|
,
|
g =
RT
zF
exp
RT
zF
1 exp j j
C C 0
Steady state models
Classical approach finite differences
first detail models of the electrochemical reactors
transformation of the partial differential equation to the set of linear equations
) )
+
A
+
A
+
A
+ =
+
! 3
x
y
! 2
x
y
! 1
x
y y y
3
' ' '
i
2
' '
i
'
i i 1 i
symmetrical formulas for the first and second derivative
)

A
A
=
+
! 3
x
y 2
! 1
x
y 2 y y
3
' ' '
i
'
i 1 i 1 i
Taylor's expansion used for linearisation
) )
+
A
A
+
A
=
! 3
x
y
! 2
x
y
! 1
x
y y y
3
' ' '
i
2
' '
i
'
i i 1 i
) )
+
A
+
A
= +
+
! 4
x 2
y
! 2
x 2
y y y 2 y
4
' v
i
2
' '
i 1 i i 1 i
)
2 1 i 1 i '
i
x
x 2
y y
y A o +
A
=
+
)
)
2
2
1 i i 1 i ' '
i
x
x
y y 2 y
y A o +
A
+
=
+
Steady state models
asymmetrical formulas boundary conditions
)
+
A
A
=
+ +
! 3
x 2
y
! 1
x
y 2 y 3 y y 4
3
' ' '
i
'
i i 2 i 1 i
)

A
A
=

! 3
x
y 4
! 1
x
y 2 y 3 y y 4
3
' ' '
i
'
i i 2 i 1 i
)
2 2 i 1 i i '
i
x
x 2
y y 4 y 3
y A o +
A
+
=
+ +
)
2 2 i 1 i i '
i
x
x 2
y y 4 y 3
y A o +
A
+
=

) )
+
A
+
A
+
A
+ =
+
! 3
x 2
y
! 2
x 2
y
! 1
x 2
y y y
3
' ' '
i
2
' '
i
'
i i 2 i
Steady state models
method of replacement of the partial derivatives in the Laplace equation
) )
)
) 1 i ,
j , 1 i
j ,
2
1
i
j , 1 i 1 i , x
x
j
+
'
+
'
+
A

i =
) j , i
) j , 1 i+
) j , 1 i
) 1 j , i +
) 1 j , i
principle of the Laplace equation

divergence of the flux equal to zero
) )
)
) i ,
j ,
2
1
i
j , i
j , i i , x
x
j
'
+
'
A

i =
) ) 1 i , x i , x
j j
+
=
) ) ) ) ) )
) ) ) ) 1 i , j , i i , j , 1 i
j , i 1 i , j , i j , 1 i i , j , 1 i
j ,
2
1
i
x x
x x
+

'
+
'
A i + A i
A i + A i
=
)
)
)
)
)
) )
. J
j , 1 i j , i
j , 1 i
1 i ,
j , i
i ,
1 i , x
x x
1
j
+
+

i
A
+
i
A
=
etc.
Steady state models
flux divergence in the final differences
) )
. J
) ) )
. J
)
0 x j j y j j
i j , y j , y j i , x i , x
= A + + A +
+ +
) ) ) ) ) ) ) ) ) )
0 C C C C C
j , i 5 , j , i 1 j , i 4 , j , i 1 j , i 3 , j , i j , 1 i 2 , j , i j , 1 i 1 , j , i
= + + + +
+ +
)
)
)
)
)
) j , 1 i
1 i
j , i
i
j
1 , j , i
x x
y
C
i
A
+
i
A
A
=
)
)
)
)
)
) j , 1 i
1 i
j , i
i
j
2 , j , i
x x
y
C
+
+
i
A
+
i
A
A
=
)
)
)
)
)
) 1 j , i
1 j
j , i
j
i
3 , j , i
y y
x
C
i
A
+
i
A
A
=
)
)
)
)
)
) 1 j , i
1 j
j , i
j
i
4 , j , i
y y
x
C
+
+
i
A
+
i
A
A
=
) ) ) ) ) 4 , j , i 3 , j , i 2 , j , i 1 , j , i 5 , j , i
C C C C C + + + =
p
o
t
e
n
t
i
a
l

/

V
X
Y
Finite differences example
Current density simulation in the parallel plate cell
current density distribution in the zinc electrowinning cell
K. Bouzek, K. Borve, O.A. Lorentsen, K. Osmudsen, I. Rouar, J. Thonstad, J. Electrochem. Soc. 142 (1995) 64.
X
Y
1.0
1.0
1.0
1.0
0.9
0.9
0.9
0.9
0.9
0.9
0.9
1.0
1.0
0.9
0.9
1.0
1.0
1.0
1.0
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.1
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.3
1.3
1.3
1.3
1.3
1.3
K. Bouzek, K. Borve, O.A. Lorentsen, K. Osmudsen, I. Rouar, J. Thonstad, J. Electrochem. Soc. 142 (1995) 64.
Finite differences example
Current density simulation in the parallel plate cell
current density distribution in the zinc electrowinning cell
Steady state models
FDM applicable for solving of any type of partial differential equation
complications may be expected in the case of complex boundary conditions form
slow convergence
problems often related to the anistropic media
difficulties by solving systems with the irregular geometries
alternative approaches searched
Steady state models
original approach based on the calculus of variations
finite elements method
Recent approach finite element method (FEM)
doesnt solve the equation directly (approximation method)
searching for the function giving extreme by replacing the differential equation
such function approximated by a sum of the basis functions (unknown coefficients)
coefficients determined by solving a system of linear algebraic equations
drawbacks largely depends on the choice of the basis functions
cannot be satisfied for too complicated geometries
the function is not searched for the whole domain integrated
domain is divided into the a number of subdomains
in each subdomain solution approximated by a simple function
Galerkins method of weighted residuals, i.e. parameters of the basis function
modifications maybe derived by the choice of the weighting functions
necessary condition is that the combination of basis functions fulfil boundary conditions
Steady state models
application onto the solution of the Laplace equation
simplification for the one-dimensional case
approximate expression takes following form
approximate expression by the means of FEM
i
N
0 i
i
a U
=
=
i
N
0 i
i
u ) x ( ) x ( u
=
=
FEM is optimising value of u
i
in such a way, that I is close to 0
I = \ ) x ( u
2
Steady state models
simplest linear basis function
,
|
=
0
) ( 0 1
1
0
x x
x x
x
) (
1 0
x x x
,
|
=
+
+
0
0
) (
1
1
1
1
i i
i
i i
i
i
x x
x x
x x
x x
x
) (
1 0

i
x x x
) (
1 N
x x x
) (
1 i i
x x x
) (
1 +

i i
x x x
) (
1 N i
x x x
+
,
|
1
1
0
) (
N N
N
N
x x
x x
x
) (
1 0

N
x x x
) (
1 N N
x x x
x
0
x
1
x
i
x
i-1
x
i+1
x
N
x
N-1
i
(x)
x
1
0
Examples of the FEM applications
current density distribution in the channel with parallel plate electrodes
Parametric study of the narrow gap cell
Curved boundary
presence of the gas bubble in the interelectrode space
evaluation of the process efficiency
Optimisation of the direct electrochemical water disinfection cell
10 cm
5 cm
5 cm
0.5 cm
0.3 cm
2.4 cm
A A C C
x
y
U = 6.04 V
J
aver.
= 50 A m
-2
J = 4.92 %
anode
cathode
anode
W = 667 QS cm
-1
evaluation of the process efficiency plate electrodes
U = 6.04 V
J
aver.
= 50 A m
-2
J = 4.92 %
W = 667 QS cm
-1
evaluation of the process efficiency plate electrodes
evaluation of the process efficiency expanded mesh electrodes
3 mm
5 mm
1.4 mm
1.5 mm
cathode
anode
x
z
y
evaluation of the process efficiency expanded mesh electrodes
U = 4.76 V
J
aver.
= 42.4 A m
-2
J = 4.12 % W = 667 QS cm
-1
Alternative to FEM handling flux densities
Finite volumes method
principle of the method
( i , j ) ( i-1, j ) ( i+1, j )
( i , j-1 )
( i , j+1 ) ( i-1, j+1 ) ( i+1, j+1 )
( i+1, j-1 ) ( i-1, j-1 )
solution of partial differential eqs.
based on the PDE integration
over the volume surrounding
controlled grid point
controlled domain covered
by the controlled volumes
integration leads formally to
equation identical with FDE
+

W

W
+
h
h
h
h
j , 1 i j , i j , i j , 1 i
0 h
h
h
h
1 j , i j , i j , i 1 j , i
=

W

W +
+
Application to the bipolar electrode function simulation
model system under study
Bipolar Pt electrode
Electrolyte
Terminal Cathode Terminal Anode
780
14
55
x
r
Cylindrical coordinate system
r - radius
x position
1.5
[mm]
I = 40 mA; U =4 V
I = 40 mA; U =4 V
comparison of the model and experimental results
Potential and current density distribution in three dimensional electrode
Tertiary current density distribution
simplified sketch of the cell construction
1
3
4
5
5
6
8
7
2
1 electrolyte inlet
2 particle electrode
3 channels connecting
4 cathode feeder
5 anode feeder
individual drums
6 anode
7 separator
8 electrolyte outlet
simplified flow patterns inside the cell - electrolyte
simplified flow patterns inside the cell electric current
basic equations describing the system
e x , el
2
m 2
m
a j
dx
d
=
i
e x , el
2
s 2
s
a j
dx
d
=
i
electrode phase
electrolyte phase
m
Galvani potential of the electrode phase
s
Galvani potential of the electrolyte phase
i
m
conductivity of the electrode phase
i
s
conductivity of the electrolyte phase
a
e
electrode spec. surface
j
el
current density corresponding
to the electrode reaction
x coordinate
Nomenclature
basic equations describing the system definition of j
el
electrode reactions considered:
cathode
overall electrode reaction current density:
anode
Cu
2+
+ 2e
-
Cu
2 H
+
+ 2e
-
H
2
2 H
2
O
4 H
+
+ O
2
2 2
O H Cu el
j j j j = + =
resistivity to the charge transfer: electrode potential
basic equations describing the system electrode reaction kinetics
)
'
+
'
'
+
'
'
+
'

=
x , Cu
Cu c , Cu
x , Cu lim,
x , Cu , 0
x , Cu
Cu c , Cu
x , Cu
Cu c , Cu
x , Cu , 0
x , Cu
RT
F z
exp
j
j
1
RT
F z 1
exp
RT
F z
exp j
j
'
+
'
=
x , H
H c , H
H , 0 x , H
RT
F z
exp j j
a a
j ln . . E + = 1055 0 41 1
polarisation curves
zF kAc j
x , Cu x , Cu lim,
=
Fv z
A j
dx
dc
Cu
x , Cu
Cu
=
s m
E =
reversible potentials: Nernst equation
|
=
i
x , i
0
r x , r
c ln
zF
RT
E E
mass transfer coefficient evaluation
) . J ,
p r
6
r
r 3
1
3
1
p
Re Re 10 04 . 1 125 exp 1
Re 2498
Re 8 . 52
Sc Re
09 . 1
Sh +
+
+
I
=

significant complication evaluation of the linear electrolyte flow rate
-15
-10
-5
0
0.00
0.05
0.10
0.15
0.20
0.25
10
15
20
j

/

A

m
-
2
p
o
sitio
n
/ m
c
u
r
r
e
n
t

l
o
a
d

/

A
electrolyte flow
1
st
drum
6
th
drum
selected results influence of the current load
V = 4.510
-5
m
3
s
-1
c
Cu
0
= 7.87 mol m
-3
c
H
0
= 100 mol m
-3
k = 4.1910
-6
m s
-1
particle diameter 0.002 m [ = 0.047 Hz
selected results influence of the current load
5.5
6.0
6.5
7.0
7.5
8.0
0.00
0.05
0.10
0.15
0.20
0.25
10
15
20
c
C
u
2
+

/

m
o
l

m
-
3
p
o
sitio
n
/ m
c
u
r
r
e
n
t

l
o
a
d

/

A
electrolyte flow
1
st
drum
6
th
drum
drum number
0 1 2 3 4 5 6 7
e
f
f
i
c
i
e
n
c
y

/

%
0.4
0.6
0.8
1.0
I = 6 A I = 20 A
selected results cell with different particle sizes
I = 15 A
c
Cu
0
= 7.87 mol m
-3
c
H
0
= 100 mol m
-3
k = 1.6410
-6
m s
-1
V = 4.2510
-5
m
3
s
-1
c
Cu
0
= 4.00 mol m
-3
position / m
0.00 0.05 0.10 0.15 0.20 0.25
j

/

A

m
-
2
-70
-60
-50
-20
-10
0
1
st
drum 6
th
drum
electrolyte flow
1.0 mm 1.5 mm 2.0 mm 2.5 mm 3.0 mm 3.5 mm
d
p
selected results cell with different particle sizes
drum number
0 1 2 3 4 5 6 7
c
u
r
r
e
n
t

l
o
a
d

/

A
0
1
2
3
4
drum number
0 1 2 3 4 5 6 7
e
f
f
i
c
i
e
n
c
y

/

%
0.4
0.6
0.8
1.0
Charge flux across the ion selective membrane
Principle of the ion selective membrane function
role of the membrane structure
simplified model: parallel cylindrical pores with an electrical
used typically for the purposes
theory of the membrane selectivity:
Donnan potential and exclusion
l

2

1

4
) 1 2 1 , 2 Don
= A
) 3 4 3 , 4 Don
= A
) ) 2 1
~ ~
+ +
Q = Q
) ) 2 1
~ ~

Q = Q
2 2 ,
0
1 1 ,
0
F z a ln RT F z a ln RT + + Q = + + Q
+ + + + + +
+
+ + Q = + + Q F z a ln RT F z a ln RT
2 ,
0
1 1 ,
0
)
=
'
+
'
= = A
+
+
+
z
1
2 ,
1 ,
1 2 1 , 2 Don
a
a
ln
F
RT
charge located on the walls
of mathematical description
'
+
'
z
1
2 ,
1 ,
a
a
ln
F
RT
i
z
1
2 , i
1 , i
z
1
2 ,
1 ,
z
1
2 ,
1 ,
a
a
a
a
a
a
'
+
'
'
+
'
'
+
'
+
+
+
0 c z c z c z
M M 2 , 2 ,
= + +
+ +
Donnan distribution coefficient electroneutrality condition
Principle of the ion selective membrane function
role of the membrane structure
advanced structure models perfluorinated sufonated materials
dry membrane, 0 vol.% swollen membrane, 0-20 vol.% percolation, 20-40 vol.%
structure inversion, 40-60 vol.% connected network, 60-80 vol.% colloidal dispersion, 80-100 vol.%
K.A. Mauritz, R.B. Moore, Chemical Reviews 104 (2004) 4535
Basic equations for ideal behavior
Nernst-Planck equation is used to describe ion transport
material balance:
v N
i i
i
i i i i
c F z
RT
D
c c D + \
'
+
'
\ =
i i
i
div
c
N =
J
t
stationary state: 0 =
t
i
c
no chemical reaction:
0 = J
electroosmotic flux: ) p F c z
k , M k , M
\ \ =
g
v
v
Treatment of non-idealities
flux of ion i inside the membrane
solvent flux considered as well (including solution density variation)
)
( ) ( )
( ) ( ) ( ) ( ) ( ) ( ) ( )
, , ( )
ln
1
ln
j j
j j j j j j j
j j j
s s
s s s s s s s
i i
i i i i i M s M s s
i
D
D c c z F c z c F p
RT
c
K v

i
+ +
= + \ \ + \ \

' ' ' '

i
N
( ) ( )
( ) ( ) ( ) ( ) ( ) ( )
( )
ln
1
ln
j j
j j j j j j
j
s s
s s s s s s
i i
i i i i i s
i i i i
i
D
D c c z F c
RT
c
K
+ +
= + \ \ +

' ' ' '

i
N v
after rearrangement and derivation
( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( )
2
0
j j j j j j j j j j
s s s s s s s s s s
i i i i i i tot tot
i i
F F
z D c z D c c c
RT RT
= \ \ + \ \ \

v v
membrane
expression for electroosmotic flux inside the membrane remains unchanged
equation for the density dependence on the composition of the solution
current density
)
( ) ( )
, ,
j j
s s
f T p V = c
electroneutrality equation
(Schlgels equation)
solution flux divergence derivative of Schlgels equation (pressure profile)
0 c z c z
j j
ions
j
s , M s , M
N
i
) s (
i i
= +
=
ions
N
i
i i
z F N j
membrane
membrane electrolyte solution interface (molar flux continuity):
membrane electrolyte solution interface (Donnan equilibrium):
) )
)
)
i
z
1
k
i
1 k
i
k 1 k ) k , 1 k (
Don
a
a
ln
F
RT
= = A
+
+ +
0 = =
=
j
s
k
l k
l
x
i
x
i
N N
o
interface
Activity coefficients evaluation
cation
K.S. Pitzer: Activity Coefficients
where
)
2
M M a Ma Ma c Mc a Mca a M c a ca
a Maa
a c a a c a a
z F m 2B ZC m 2 m m m z m m C
, ,
,
ln( )
+
K = + + + 1 + + +

' '

)
2
X X c cX cX a Xa c cXa a X c a ca
a cc X
c a a c c a a
z F m 2B ZC m 2 m m m z m m C
, ,
,
ln( )
+
K = + + + 1 + + +

' '

c a ca c a
c cc a aa
c a c a c a
F f m m B m m m m
, , , ,
, ,
' ' ' K

= + + 1 + 1

1 2
1 2
1 2
I 2
f A 1 bI
1 bI b
ln( )
K
1

= + +

+
|
) )
)
)
)
0 1 2 1 2 1 2
MX MX MX 1 MX 2
B g I g I = + +
in Electrolyte Solutions.
CRC Press, London 2000.
anion
Methods used to solve the equations
boundary problem Algebraic-Ordinary Differential Equations (A-ODEs)
solution - shooting method
Boundary conditions - system non-linear equations pmodified Newton-
Raphson method
1] P. N. Brown, A. C. Hindmarsh, and L. R. Petzold, Consistent Initial Condition Calculation
for Differential-Algebraic Systems, LLNL Report UCRL-JC-122175, August 1995
2] IMSL Numerical Library, 1994
Donnan potential at boundary interfaces s
j
-l
i
s
j
-s
j+1
- non-linear equation
p(DZREAL
2
)
calculation of consistent initial conditions-system of linear equations
p(DLSLRG
2
)
integration of system A-ODEs for individual parts - initial problempimplicit
method based on the BDF Gears formulas (DDASPK
1
)
input parameters
anolyte: 5 kmol NaCl m
-3
, catholyte:
0
10000
20000
0
500
1000
1500
2000
2500
0.0
0.2
0.4
0.6
c
N
a
+

/

m
o
l

m
-
3
j

/

A

m
-
2
c
o
o
rd
in
a
te
/ m
m
current flow
direction
pH = 2 13 kmol NaOH m
-3
simplified model
Results influence of the current load
input parameters
-3
, catholyte:
pH = 2 13 kmol NaOH m
-3
simplified model
input parameters
-3
,
catholyte:
pH = 2
13 kmol NaOH m
-3
j / A m
-2
0 500 1000 1500 2000 2500
J

/

m
m
o
l

m
-
2

s
-
1
-20
-10
0
10
20
OH
-
Na
+
Cl
-
Na
+
selectivity 52 % at 1500 A m
-2
Na
+
selectivity 75 % at 1500 A m
-2
Dynamic models
Model of the cathodically protected pipelines in a soil
aim of the study
theory of the cathodic protection in a soil
proposed alternative theory
difficult experimental evaluation
mathematical model offers simple qualitative alternative to the experiment
0.01 m
insulation insulation
damage
boundary of the domain
x
y
Dynamic models
cathode reaction considered

p + + OH 4 e 4 O H 2 O
2 2
simplifying assumptions
homogeneous environment
no reaction with CO
2
constant oxygen flux to the cathode surface
homogeneous potential distribution on the cathode (damage) surface
water electrolysis consumes negligible portion of the current
2 2
H OH 2 e 2 O H 2 + p +

model equations
0 ) ( = \ W \
) c Bz c ( AD J
i i i i i
\ + \ =
2
K
16
15
K 2 1
K 5 . 0 1
A
+ +
+
=
I
I
=
1
K
RT
F
B =
i
m
i
2
2
c D z A
RT
F
i
= W
Dynamic models
c
0
Na+
= 10 mol m
-3
c
0
Cl-
= 10 mol m
-3
c
0
OH-
= 0 mol m
-3
selected initial conditions
Dynamic models
c
0
Na+
= 10 mol m
-3
c
0
Cl-
= 10 mol m
-3
c
0
OH-
= 0 mol m
-3
selected initial conditions
Conclusion
mathematical modelling provides powerful tool in understanding and optimising
rapid development of commercial software allows faster and more efficient work
understanding of the mathematical methods still essential
two main limits exists
electrochemical as well as chemical processes
hardware limitations
reliable input data

Bouzek - Modelling and Design of The Electrochemical Processes and Reactors

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Bouzek - Modelling and Design of The Electrochemical Processes and Reactors

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Modelling and Design of the Electrochemical

Processes and Reactors

Steady state models

principle of the Laplace equation

' ' ' '

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