Bouzek - Modelling and Design of The Electrochemical Processes and Reactors - Pps

Modelling and Design of the Electrochemical
Processes and Reactors

Karel Bouzek, Roman Kodým
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
identification of the rate determining steps
learning the way of sequential thinking
scientific
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
economical
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
based on the two elementary modes of operation
assessment of the system limits under given assumptions
steady state models

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
dynamic models
description of the non-stationary processes
process start-up and termination
discontinuous processes
most sophisticated problems
Material balance
dc i I
VR  J i  R i VR  e
d niF
modes of operation
batch (discontinuous) processes
continuous processes continuously stirred tank reactor (CSTR)
plug-flow reactor (PFR)
Batch processes
basic characteristics
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
description by the dynamic model only
Batch processes
material balance
high mixing rate – spatially uniform concentration
A  ne   B dc A I e 
VR 
d n AF
dc A j e  a e ae 
Ae

d nAF VR
mass transfer limited reaction jlim  k mcA

concentration decay of component A in time
ja e
galvanostatic process at j < jlim c A  c A,0  
nAF
c A  c A , 0 exp  k m a e 
galvanostatic process at j  jlim
jlim k m c A n A F k m c A , 0 n A F
e    exp  k m a e 
j 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
A  ne   B  c  c   V R
V A ,O A,I R A
 c  c   I e 
V A ,O A ,I
n AF

I a j
galvanostatic process at j < jlim c A ,O  c A , I   c A ,I  e
n A FVR n AF
I lim a j
c A ,O  c A , I   c A ,I  e lim
n A FVR nAF
jlim k m c A ,O n A F
e  
j j
Continuous process - PFR

material balance
negligible axial electrolyte mixing
negligible concentration gradient perpendicular to the flow direction
A  ne   B v
dc A
 R A
dx
  dc A   b j e 
V
 dx  nAF
b – electrode width

j bx
galvanostatic process at j < jlim c A  c A ,I 

nAF V
 k bx 
c A  c A ,I exp   m 
 V 
jlim k m c A ,I n A F  k bx 
e   exp   m 
j j  V 
Steady state models
Background of the electrochemical reactors modelling

basic parameters calculated
local values of the Galvani potential
local current density values
way of the system description

differential or partial differential equations
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
Steady state models
Level of simplification
primary current density distribution

infinitely fast reaction kinetics
infinitely fast mass transfer kinetics
only influencing factors geometry of the system
electrolyte conductivity
secondary current density distribution

reaction kinetics considered
more regular current density distribution
sufficient approximation for the majority of the industrially relevant systems
tertiary current density distribution

mass transfer kinetics and electrolyte hydrodynamics considered
additional reduction of the local extremes
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
symmetry of the system
consequences of the increase in the number of dimensions

one-dimensional model described by the differential equations
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)
available for the extremely simple configurations only
strongly limited applicability in the industrially relevant systems
numerical mathematics
able to describe complicated geometries and complex systems
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 FDM
FEM
BEM
Steady state models
Basic model equations for electrochemical systems
equation of the mass and charge transfer in the electrolyte solution

 
Ji  D ici  u i ci   vci
Nernst-Planck equation
current density value

   
ji  z i FJi j  F z i J i
i
application of the Faraday law
 
j  F z i Dici  F z i u i ci  Fv z i ci z c
i
i i 0
i i i electroneutrality condition
electrolyte solution with no concentration gradients


j  F z i u i ci 
i j      F z i u i ci
i
electrolyte conductivity definition
Steady state models
electrolyte solution with concentration gradients


j F
     Di z ici
  i
current less system
F
    Di zici
 i
liquid junction potential
t i0
 dln ci 
RT
d  
F i zi
one dimensional case
Steady state models
mass balance in the electrolyte volume
c i
 J i   i 

introducing Nernts-Planck equation after multiplication by ziF
F z iJ i  F z i i  0 z 
i
i i 0
i i electroneutrality condition
F z iJ i  j  0
i charge conservation
introducing expression for j no concentration gradients
 c u z     u z c   D z  c
i
i i i
2
i
i i i
i
i i
2
i 0  2  0
modified Laplace equation Laplace equation
Steady state models
Boundary conditions
significant variability according to the particular conditions

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
arbitrary definition
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)

in special cases flux continuity used
Electrode / electrolyte interface

simplification considered: primary vs. secondary (tertiary) current density distribution
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: linear
Tafel
Butler-Volmer
Steady state models
Linear kinetics
historical question computational demands

physical models
nowadays overcome
Tafel kinetics
considers just one part of the polarisation curve
  a  b ln j
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
b j  j
 j  j0e   b ln   j  j0e
e j0  j0 
Steady state models
Butler - Volmer kinetics
general description of the charge transfer kinetics

more complicated kinetic evaluation (requires additional numerical procedure)
 csred  zF  csox  zF  
j  j0  0 exp 1   C    0 exp   C  
 red
c  RT  ox
c  RT 
mass transfer limited kinetics - concentration polarisation

 1   zF   1   zF   
j  j0 1   exp 1   C   
  j1   exp    C  

 jlim, A  RT  lim, C  RT 

charge transfer limited kinetics
  zF   zF  
j  j0 exp 1   C    exp   C  
  RT   RT 
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
Taylor's expansion used for linearisation
y i 1  y i  y
x
'
 y i''
x   y ''' x     
2 3
i i
1! 2! 3!
y i 1  y i  y
x
'
 y i''
x   y ''' x     
2 3
i i
1! 2! 3!
symmetrical formulas for the first and second derivative
y i 1  y i 1  2 y
x
'
 2 y i'''
x     
3
y i 1  2 y i  y i 1  y
2x 
''
2
 y iv '
2x 
4
 
i i
1! 3! 2! 4!
y i 1  2 y i  y i 1
y i' 
y i 1  y i 1
 
  x 2 y i''   
  x 2
2x x  2
Steady state models
asymmetrical formulas – boundary conditions
yi2  yi  y
2x
'
 y i''
2x   y ''' 2x     
2 3
i i
1! 2! 3!
4 y i 1  y i  2  3y i  2 y
x
'
 y i'''
2x     
3
4 y i 1  y i  2  3y i  2 y
x
'
 4 y i'''
x     
3
i i
1! 3! 1! 3!
 3y i  4 y i 1  y i  2 3y i  4 y i 1  y i  2
y i' 
2x
 
  x 2 y i' 
2x
 
  x 2
Steady state models
method of replacement of the partial derivatives in the Laplace equation
principle of the Laplace equation

divergence of the flux equal to zero
 i , j1
 1 
 i 1, j
 i , j 
jx  ,i 1   i 1, j  2 
x  ,i 1
 i1, j   i , j  i1, j
i , j   1 
 i , j 
jx ,i    i , j  2 
x ,i 
i , j1 etc.
i 1, jx ,i i 1, j  i , jx ,i 1i , j
jx ,i    jx  ,i 1  1 

 i , j 
 2 
i 1, jx ,i   i , jx  ,i 1
jx  ,i 1  
1
x ,i  x  ,i 1
 i , j  i 1, j 

 i , j   i 1, j
Steady state models
flux divergence in the final differences
j 
x  ,i   
 jx  ,i  y  j  jy , j  jy  , j x i   0
Ci , j,1i 1, j  Ci , j, 2 i 1, j  Ci , j,3i , j1  Ci , j, 4 i , j1  Ci , j,5 i , j  0
y  j x i 
Ci , j,1  Ci , j,3  
x i  x i 1 y  j y  j1
 
 i , j  i 1, j  i , j  i , j1
y  j x i 
Ci , j, 2   Ci , j, 4  
x i  x i 1 y  j y  j1
 
 i , j  i 1, j  i , j  i , j1
Ci , j,5   Ci , j,1  Ci , j, 2   Ci , j,3  Ci , j, 4 

Finite differences example
Current density simulation in the parallel plate cell
current density distribution in the zinc electrowinning cell

potential / V
X
Y
K. Bouzek, K. Borve, O.A. Lorentsen, K. Osmudsen, I. Roušar, 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
0.9 0.9
1.0 0.9
1.1
1.1 1.0
1.2 1.2
1.3
1.3
1.3
1.2 1.2
1.1
1.1 1.0
1.0
0.9 0.9
Y
0.9 0.9
1.0 1.0
1.1
1.1 1.0
1.2 1.2
1.3
1.3
1.3
1.2 1.2
1.1
1.1
1.0 1.0
1.0
0.9 0.9
K. Bouzek, K. Borve, O.A. Lorentsen, K. Osmudsen, I. Roušar, J. Thonstad, J. Electrochem. Soc. 142 (1995) 64.
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
Recent approach – finite element method (FEM)
original approach based on the calculus of variations

doesn’t 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
finite elements method

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
Galerkin’s 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

approximate expression by the means of FEM
N
U   i a i
i 0
simplification for the one-dimensional case

approximate expression takes following form
N
u ( x )   i ( x ) u i
i 0
 2 u (x)  
FEM is optimising value of ui in such a way, that  is close to 0

Steady state models
simplest linear basis function

i(x)
x
0
x x1 xi-1 xi xi+1 xN-1 xN
 x1  x
 ( x0  x  x1 ) 0
 0 ( x)   x1  x0 0
0 ( x0  x  xi 1 )
( x1  x  xN ) 

 x  xi 1 ( xi 1  x  xi )
 x  x
 i ( x)   i i 1
0 ( x0  x  xN 1 ) x x ( xi  x  xi 1 )
 i 1
  xi 1  xi
 N ( x)   x  x N 1
 ( xN 1  x  xN ) 
 0 ( xi 1  x  xN )
 x N  x N 1
Examples of the FEM applications
Parametric study of the narrow gap cell
current density distribution in the channel with parallel plate electrodes

Curved boundary
presence of the gas bubble in the interelectrode space

Optimisation of the direct electrochemical water disinfection cell
evaluation of the process efficiency
2.4 cm
5 cm
0.5 cm 0.3 cm
10 cm
A C A C
y 5 cm
x
evaluation of the process efficiency – plate electrodes
anode
cathode
anode
U = 6.04 V
Javer. = 50 A m-2
s = 667 mS cm-1
 = 4.92 %
evaluation of the process efficiency – plate electrodes
U = 6.04 V
Javer. = 50 A m-2
s = 667 mS cm-1
 = 4.92 %
evaluation of the process efficiency – expanded mesh electrodes
cathode
3 mm
anode
1.5 mm z
5 mm
1.4 mm y x
evaluation of the process efficiency – expanded mesh electrodes
U = 4.76 V
Javer. = 42.4 A m-2
s = 667 mS cm-1  = 4.12 %
Finite volumes method
Alternative to FEM handling flux densities
principle of the method

solution of partial differential eqs.
based on the PDE integration
over the volume surrounding ( i-1, j+1 ) ( i , j+1 ) ( i+1, j+1 )
controlled grid point
controlled domain covered
by the controlled volumes
integration leads formally to
equation identical with FDE
i 1, j  i , j   i 1, j ( i-1, j ) (i,j) ( i+1, j )

s h  s i, j h
h h
  i , j   i , j1
 s i , j1 h  s i, j h0
h h
( i-1, j-1 ) ( i , j-1 ) ( i+1, j-1 )

Application to the bipolar electrode function simulation
model system under study
Terminal Cathode Terminal Anode
Electrolyte
14
1.5 Bipolar Pt electrode
[mm] 55 780
Cylindrical coordinate system

r r - radius
x – position
x
I = 40 mA; U =4 V
I = 40 mA; U =4 V
comparison of the model and experimental results

Tertiary current density distribution
Potential and current density distribution in three dimensional electrode

simplified sketch of the cell construction
3 6 5 7
8
1
4 2
1 – electrolyte inlet 5 – anode feeder

2 – particle electrode 6 – anode
3 – channels connecting 7 – separator
individual drums 8 – electrolyte outlet
4 – cathode feeder
simplified flow patterns inside the cell - electrolyte

simplified flow patterns inside the cell – electric current

basic equations describing the system
d 2 m Nomenclature
m   jel, x  a e
dx 2
m – Galvani potential of the electrode phase
electrode phase s – Galvani potential of the electrolyte phase

m – conductivity of the electrode phase
s – conductivity of the electrolyte phase
d 2s ae – electrode spec. surface
s 2
 jel,x  a e jel – current density corresponding
dx
to the electrode reaction
electrolyte phase x – coordinate
basic equations describing the system – definition of jel
electrode reactions considered:

cathode Cu2+ + 2e- Cu
2 H+ + 2e- H2
anode 2 H2O 4 H+ + O2
overall electrode reaction current density:
jel  jCu  jH 2   jO 2
resistivity to the charge transfer: electrode potential

basic equations describing the system – electrode reaction kinetics
   z F   1   Cu ,c z Cu F 
 j0,Cu , x exp   Cu ,c Cu  Cu , x   exp   Cu , x 
jCu , x    RT   RT 
j0,Cu , x   Cu ,c z Cu F 
1  exp    Cu , x 
jlim,Cu , x  RT 
  z F 
jH ,x   j0,H  exp   H ,c H  H , x 
 RT 
Ea  1.41  0.1055  ln j a
polarisation curves
dcCu jCu ,x A
jlim,Cu , x  kAc Cu , x zF 
dx z Cu Fv
E   m  s
reversible potentials: Nernst equation
RT
E r ,x E 
0
r ln  ci , x
zF i
mass transfer coefficient evaluation
   
1 1
1.09 3 3 52.8 Re r
Sh  Re p Sc   1  exp  125  1.04 106 Re r  Re p
 2498  Re r
significant complication – evaluation of the linear electrolyte flow rate

selected results – influence of the current load

1st drum
th
6 drum
0
-5
-2
j/Am
-10
flow
electrolyte
-15
cur 10
ren 0.00
t lo 0.05
ad / 15 0.10
A 0.15
20 0.20
0.25 /m
position
cCu0 = 7.87 mol m-3 V = 4.5·10-5 m3 s-1 k = 4.19·10-6 m s-1

cH0 = 100 mol m-3 w = 0.047 Hz particle diameter 0.002 m

1.0
selected results – influence of the current load
efficiency / %
0.8
0.6
th
1st drum 0.4
0 1 2 3 4 5 6 7
6 drum
drum number
8.0 I=6A I = 20 A
7.5
-3
lm
7.0
c Cu2+ / mo
6.5
6.0
flow
5.5 electrolyte
cur 10
ren 0.00
t lo
ad 15 0.10
0.05
/A 0.15
20 0.20
0.25 /m
position

selected results – cell with different particle sizes
st th
1 drum 6 drum
0
-10
-2
-20
j/Am
-50
3.5 mm 3.0 mm 2.5 mm 2.0 mm 1.5 mm 1.0 mm
dp
-60
electrolyte flow
-70
0.00 0.05 0.10 0.15 0.20 0.25
position / m
cCu0 = 7.87 mol m-3 cH0 = 100 mol m-3 V = 4.25·10-5 m3 s-1
cCu0 = 4.00 mol m-3 I = 15 A k = 1.64·10-6 m s-1
selected results – cell with different particle sizes
4 1.0
current load / A
efficiency / %
0.8
0.6
1
0 0.4
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
drum number drum number
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
charge located on the walls
used typically for the purposes
of mathematical description
theory of the membrane selectivity: 1 2 3 4
Donnan potential and exclusion
Don2,1  2  1 Don4,3  4  3 1
~ m ~ ~ m ~ RT  a  ,1  z
m m Don2,1  2  1  ln 
 1 2   1 2 
F  a  , 2 
1
m0  RT ln a ,1  z  F1  m0  RT ln a , 2  z  F2 RT  a ,1  z
 ln
m0  RT ln a ,1  z  F1  m0  RT ln a , 2  z  F F  a , 2 
1 1 1
 a  ,1  z a  z a  zi
z  c  , 2  z c , 2  z M c M  0
    ,1    i ,1 
a 
 ,2   a , 2   a i,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
D 
N i   Di ci  ci  i  zi F  ci v
 RT 
ci
material balance:  i  divN i

ci
stationary state: 0

no chemical reaction:  0

electroosmotic flux: v

zM ,k cM ,k F  p
Treatment of non-idealities
flux of ion i inside the membrane
Ni   Di
(s j )   ln  i( s j )  ( s j ) ( s j )  Di( s j ) 

  ln ci
(s j )
 1  
 i

c  ci 
 RT  i



z F  
(sj )
 ci
(sj ) 

z  c
M ,s j M ,s j F  
(sj )
  p
(sj )

solvent flux considered as well (including solution density variation)
  ln  i( s j )  ( s j ) ( s j )  Di
(sj )

N   D        
(s j ) (sj ) (sj ) (sj )
 1 i c c   i
z F c v
  ln ci
i i (s j ) i i
i i  i  RT  i
after rearrangement and derivation
F F 2 (s j )
0  j  zi Di j ci j     zi Di j ci j  ctotj v j  ctotj v j
(s ) (s ) (s ) (s ) (s ) (s ) (s ) (s ) (s )
RT i RT i
membrane
expression for electroosmotic flux inside the membrane remains unchanged
(Schlögel’s equation)
solution flux divergence – derivative of Schlögel’s equation (pressure profile)
equation for the density dependence on the composition of the solution

(s j )
 f c  (s j )
,T , p 
electroneutrality equation
N io n s
z c  z M ,s j c M ,s j  0
(s j )
i i
i
current density N io n s
j  F  ziNi
i
membrane
membrane – electrolyte solution interface (Donnan equilibrium):

1
k 1
RT  a i  zi
k 1, k )
(Don  k 1  k   ln  k  
F  ai 
membrane – electrolyte solution interface (molar flux continuity):
Ni  Ni
xlk  l xs j  0
k
interface
Activity coefficients evaluation

cation
 
ln(  M )  z M
2
F   ma  2BMa  ZCMa    mc  2 Mc   ma  Mca    ma m a ,  Maa ,  z M  mc m a Cca
a c  a  a a , c a
anion
 
ln(  X )  z X2 F   mc  2BcX  ZCcX    ma  2 Xa   mc  cXa    ma m a ,  cc,X  z X  m m c a Cca
c a  a  c a , c a
where
F  f    mc m a B'ca   mc m c, 'cc,   ma m a , 'aa ,
c a c c, a a ,
  I1 2 2 12 
f  A    ln( 1  bI )
 1  bI12
b 
K.S. Pitzer: Activity Coefficients
BMX  MX
0
 MX
1
 
g 1I1 2  MX
2

g  2 I1 2  in Electrolyte Solutions.
CRC Press, London 2000.
Methods used to solve the equations

boundary problem Algebraic-Ordinary Differential Equations (A-ODEs)
solution - shooting method

integration of system A-ODEs for individual parts - initial problemimplicit
method based on the BDF Gears formulas (DDASPK1)
calculation of consistent initial conditions-system of linear equations

(DLSLRG2)
Donnan potential at boundary interfaces sj-li sj-sj+1- non-linear equation
(DZREAL2)
Boundary conditions - system non-linear equations  modified 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
Results – influence of the current load
current f
low dir ection
20000
-3
/ mol m
10000
+
cNa
2500
2000
-2
1500
m
0 1000
A
0.6
500
j/
0.4
coord 0.2 0
i nate / 0.0
mm
simplified model
input parameters
anolyte: 5 kmol NaCl m-3, catholyte:

pH = 2 13 kmol NaOH m-3
simplified model
input parameters
anolyte: 5 kmol NaCl m-3, catholyte:

pH = 2 13 kmol NaOH m-3
input parameters 20
+
anolyte: 5 kmol NaCl m-3, Na
pH = 2 10
-2 -1
J / mmol m s
catholyte:
-
13 kmol NaOH m-3 Cl
0
Na+ selectivity 52 % at 1500 A m-2 -10

-
OH
Na+ selectivity 75 % at 1500 A m-2
-20
0 500 1000 1500 2000 2500
-2
j/Am
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
boundary of the domain
damage
insulation insulation
y
x 0.01 m
Dynamic models
cathode reaction considered
O2  2H 2O  4e   4OH
simplifying assumptions
homogeneous environment
no reaction with CO2
constant oxygen flux to the cathode surface
homogeneous potential distribution on the cathode (damage) surface
water electrolysis consumes negligible portion of the current
2H 2O  2e   2OH  H 2
model equations
1  0 .5 K
A
(s)  0 15
1  2K  K 2 F2 m
16 s A z 2i Di ci
Ji  ADi (ci  Bz i ci)  F RT í
K B
1  RT
Dynamic models
selected initial conditions

c0Na+ = 10 mol m-3
c0Cl- = 10 mol m-3
c0OH- = 0 mol m-3

Dynamic models
selected initial conditions

c0Na+ = 10 mol m-3
c0Cl- = 10 mol m-3
c0OH- = 0 mol m-3

Conclusion
mathematical modelling provides powerful tool in understanding and optimising

electrochemical as well as chemical processes
rapid development of commercial software allows faster and more efficient work
understanding of the mathematical methods still essential
two main limits exists
hardware limitations
reliable input data

Bouzek - Modelling and Design of The Electrochemical Processes and Reactors - Pps

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Bouzek - Modelling and Design of The Electrochemical Processes and Reactors - Pps

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Modelling and Design of the Electrochemical

Processes and Reactors

Department of Inorganic Technology,

Role of the mathematical modelling in the electrochemical engineering

Levels of the mathematical modelling

steady state models

mass transfer limited reaction jlim  k mcA

Continuous process - CSTR

concentration decay of component A in time

Continuous process - PFR

concentration decay of component A in time

Background of the electrochemical reactors modelling

way of the system description

division of the mathematical models

primary current density distribution

secondary current density distribution

tertiary current density distribution

Number of dimensions considered

consequences of the increase in the number of dimensions

three dimensional models

Mathematical methods used

analytical solution of the model equations

methods of numerical mathematics used

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

Basic model equations for electrochemical systems

electrolyte solution with concentration gradients

current less system

Basic model equations for electrochemical systems

mass balance in the electrolyte volume

introducing Nernts-Planck equation after multiplication by ziF

introducing expression for j no concentration gradients

significant variability according to the particular conditions

Boundary condition – constant potential value

Boundary condition – constant flux

typically the cell walls and electrolyte surface (no flux)

Electrode / electrolyte interface

historical question computational demands

Butler - Volmer kinetics

general description of the charge transfer kinetics

mass transfer limited kinetics - concentration polarisation

charge transfer limited kinetics

Classical approach – finite differences

first detail models of the electrochemical reactors

symmetrical formulas for the first and second derivative

Classical approach – finite differences

asymmetrical formulas – boundary conditions

Classical approach – finite differences

method of replacement of the partial derivatives in the Laplace equation

principle of the Laplace equation

Classical approach – finite differences

flux divergence in the final differences

Ci , j,5   Ci , j,1  Ci , j, 2   Ci , j,3  Ci , j, 4 

Current density simulation in the parallel plate cell

current density distribution in the zinc electrowinning cell

Current density simulation in the parallel plate cell

current density distribution in the zinc electrowinning cell

Classical approach – finite differences

FDM applicable for solving of any type of partial differential equation

Recent approach – finite element method (FEM)

original approach based on the calculus of variations