1

1
Electrochemical kinetics
2
Contents
Electrochemical rate theory
Equilibrium
Polarization
General rate theory
Mixed potential theory
Mass transfer limiting currents
Chemical reaction limiting currents
Mass transfer in electrolytes
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
3
Electrochemical rate theory
4
Rate of an electrochemical
reaction
H e H
b
k
+
+
H e H
f
k
+
+
cathodic
anodic
chemical vs. electrochemical reactions
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
2
5
Rate of an electrochemical
reaction
water solution
steel
e
-
e
-
e
-
e
-
e
-
e
-
e
-
e
-
H
H
+
H
+
H
+
H
+
H
+
H
+
H
+
H
+
H
+
H
+
H
+
H
+
e
-
H H
+
e
-
H
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
6
Rate of a cathodic reaction
|
p
o
t
e
n
t
i
a
l

/

V





+
rate of reaction / ( kmol m
-2
s
-1
)
more
electrons
available
fewer
electrons
available
log scale
H e H
f
k
+
+ Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
7
Rate of a cathodic reaction
+

H
c log pH
|
p
o
t
e
n
t
i
a
l

/

V





+
log (reaction rate) / ( kmol m
-2
s
-1
)
pH 4
pH 3
pH 5
H e H
f
k
+
+ Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
8
|
p
o
t
e
n
t
i
a
l

/

V





+
log (reaction rate) / ( kmol m
-2
s
-1
)
Rate of an anodic reaction
H e H
b
k
+
+
bar p
H
1
2
=
bar p
H
10
2
=
bar p
H
1 . 0
2
=
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
3
9
Equilibrium
10
|
p
o
t
e
n
t
i
a
l

/

V





+
log (reaction rate) / ( kmol m
-2
s
-1
)
Reversible potential and the
exchange current density
H
+
+

e
-

H
H

+ +
e

-
H
E
rev
i
o
log (current density) / (A m
-2
)
H e H
b
k
+
+
H e H
f
k
+
+
= i
c
= i
a
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
11
Reversible potential and the
Nernst equation
O dH bB ne mH aA
2
+ + +
+
( ) ( )
( ) ( )
d
O H
b
B
m
H
a
A
2
n c c
c c
F
RT
E E
o
rev rev
+
+ = log
3 . 2
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
12
Reversible potential for
hydrogen reduction
at 25
o
C
2.3 RT/F=0.059 V
H e H
f
k
+
+
a = 0
n = 1
b = 1, B H
d = 0
O dH bB ne mH aA
2
+ + +
+
( ) ( )
pH E E
H H
o
rev H H rev
059 . 0 = + +
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
4
13
Exchange current density
exchange current density
(equilibrium reaction rate) :
|
.
|

\
|
=
|
|
.
|

\
|
=
RT
G
RT
G
i
b
f
o
exp exp
b f
k k
O dH bB ne mH aA
2
k
k
f
b
+ + +

+
rate forward = rate backward
at equilibrium:
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
14
|
p
o
t
e
n
t
i
a
l

/

V





+
Exchange current density
H e H
b
k
+
+
H e H
f
k
+
+
E
rev
log (current density) / (A m
-2
)
on Hg
10
-8
on Fe
10
-3
on Pt
10
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
15
Polarization
16
Polarization
V
e
-
e
-
A
+ - - +
ions
WE CE
RE
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
5
17
|
p
o
t
e
n
t
i
a
l

/

V





+
Cathodic polarization
H
+
+

e
-

H
H

+ +
e

-
H
E
rev
i
o
log (current density) / (A m
-2
)
i
a
i
c
c rev applied
E E =
a c applied
i i i =

c
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
18
Anodic polarization
a rev applied
E E + =
c a applied
i i i =
|
p
o
t
e
n
t
i
a
l

/

V





+
H
+
+

e
-

H
H

+ +
e

-
H
E
rev
i
o
log (current density) / (A m
-2
)
i
c
i
a

a
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
19
Experimental polarization
V
e
-
e
-
A
+ -
ions
WE CE
RE
E
a
p
p
l
i
e
d
/

V
log i
applied
/ (A m
-2
)
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
20
Experimental polarization
1. reference electrode
2. gas in
3. gas out
4. Luggin capillary
5. counter electrode
6. rotating cylinder
7. temperature probe
8. pH electrode
9. working electrode
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
6
21
Experimental polarization
(small cathodic overpotential)
E
a
p
p
l
i
e
d
/

V
log i
applied
/ (A m
-2
)
H
+
+

e
-

H
H

+ +
e

-
H
i
applied
i
a
i
c
a c applied
i i i =
E
rev
E
applied
c rev applied
E E = Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
22
Experimental polarization
(large cathodic overpotential)
E
a
p
p
l
i
e
d
/

V
log i
applied
/ (A m
-2
)
H
+
+

e
-

H
H

+ +
e

-
H
E
rev
i
o
i
a
0 i
c
i
applied
c a c applied
i i i i =
c rev applied
E E =
E
applied
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
23
Experimental polarization
(small anodic overpotential)
E
a
p
p
l
i
e
d
/

V
log i
applied
/ (A m
-2
)
H
+
+

e
-

H
H

+ +
e

-
H
i
applied
i
c
i
a
a c applied
i i i =
E
rev
E
applied
a rev applied
E E + = Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
24
Experimental polarization
(large anodic overpotential)
E
a
p
p
l
i
e
d
/

V
log i
applied
/ (A m
-2
)
H
+
+

e
-

H
H

+ +
e

-
H
E
rev
i
o
i
c
0 i
a
i
applied
a a c applied
i i i i =
a rev applied
E E + =
E
applied
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
7
25
General rate theory
26
General rate equation
|
.
|

\
|
=
RT
F
i i
o c
n
exp
( )
|
.
|

\
|
=
RT
F
i i
o a
n 1
exp
cathodic reaction rate:
anodic reaction rate:
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
27
General rate equation
polarization (applied) current:
a c applied
i i i =
( )
|
.
|

\
|
|
.
|

\
|
=
RT
F
i
RT
F
i i
o o applied
n n 1
exp exp
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
28
Tafel behavior
(charge transfer polarization)
cathodic reaction: anodic reaction:
|
|
.
|

\
|
=
o
c
c
i
i
b log
|
|
.
|

\
|
=
o
a
a
i
i
b log
p
o
t
e
n
t
i
a
l

/

V
log i / (A m
-2
)
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
b
a
, b
c
- Tafel slopes
( ) F
RT
b
a
n
=
1 303 . 2
F
RT
b
c
n 303 . 2
=
8
29
Faradays law and the
iron dissolution reaction
F
ItM
F
QM
m
w w
n n
= =
F
iM
At
m
CR
w
n
= =
+
+ 2e Fe Fe
2
(
(
(
(

e
e
kmol
C
kmol
kmol
kmol
kg
s A
| | = kg
(
(
(
(

e
e
kmol
C
kmol
kmol
m
kg
kmol
kg
m
A
3
2
=
(

y
mm
metal loss:
corrosion rate:
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
30
Mixed potential theory
31
|
p
o
t
e
n
t
i
a
l

/

V




+
Mixed potential theory
H

+
+
e

-

H
H

H

+ +

e

-
log i / (A m
-2
)
F
e

F
e

2+ +
2
e

F
e
2
+
+

2
e

F
e
( ) H H rev
E +
( )
+ 2
/ Fe Fe rev
E
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
32
|
p
o
t
e
n
t
i
a
l

/

V




+
Total cathodic current
H

H

+ +

e

-
log i / (A m
-2
)
F
e

F
e

2+ +
2
e

( )
+
+
H H a
i
( )
=
+ 2
Fe Fe a
i
to
ta
l a
n
o
d
ic
( ) total a
i
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
9
33
|
p
o
t
e
n
t
i
a
l

/

V




+
Total cathodic current
H

+
+
e

-

H
log i / (A m
-2
)
F
e
2
+
+

2
e

F
e
( )
=
+
H H c
i
( )
+
+ 2
Fe Fe c
i
( ) total c
i
to
ta
l c
a
th
o
d
ic
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
34
|
p
o
t
e
n
t
i
a
l

/

V




+
Corrosion potential and
corrosion current
H

+
+
e

-

H
H

H

+ +

e

-
log i / (A m
-2
)
F
e

F
e

2+ +
2
e

F
e
2
+
+

2
e

F
e
( ) H H rev
E +
( )
+ 2
/ Fe Fe rev
E
to
ta
l a
n
o
d
ic
to
ta
l c
a
th
o
d
ic
corr
E
corr
i
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
35
Mixed potential theory
by having a more negative reversible potential,
the Fe/Fe
2+
reaction has polarized the H
+
/H
reaction cathodically, i.e. the anodic portion of
that reaction became insignificant
and vice versa
by having a more positive reversible potential,
the H
+
/H reaction has polarized the Fe/Fe
2+
reaction anodically, i.e. the cathodic portion of
that reaction became insignificant
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
36
Mass transfer limiting currents
10
37
Mass transfer
limiting current
e
-
e
-
e
-
e
-
e
-
e
-
e
-
e
-
H
H
+
H
+
H
+
H
+
H
+
H
+
H
+
H
+
H
+
H
+
H
+
H
+
e
-
H
slow
steel water solution
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigationc
38
Diffusion
H
+
c
x
t=0
t=
steel water solution
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
39
Diffusion
H
+
c
x
at low current density -
charge transfer control
at high current density -
mass transfer (diffusion) control
mixed control
steel water solution
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
40
Diffusion and convection
(turbulent flow)
steel
diffusion
water solution
H
+
turbulent mixing
x
c
more
even
b
o
u
n
d
a
r
y

l
a
y
e
r
slope at the
wall flux
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
11
41
Limiting currents
|
p
o
t
e
n
t
i
a
l

/

V




+H

+
+
e

-

H
log i / (A m
-2
)
turbulent
mixing
diffusion
more
turbulent
mixing
even
more
turbulent
mixing
lim
i
lim
i
lim
i
lim
i
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
42
Limiting currents in
turbulent pipe flow
|
p
o
t
e
n
t
i
a
l

/

V




+H

+
+
e

-

H
log i / (A m
-2
)
pipe flow
at 1 m/s
stagnant
or laminar
pipe flow
at 2 m/s
pipe flow
at 5 m/s
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
43
Flow-dependent limiting
current and corrosion rate
|
p
o
t
e
n
t
i
a
l

/

V




+
H

+
+
e

-

H
log i / (A m
-2
)
1 m/s 2 m/s 5 m/s
F
e

F
e

2+ +
2
e

lim
i i
corr
<
stagnant
lim
i i
corr
=
lim
i i
corr
<<
lim
i
lim
i
corr
i
lim
i
lim
i
corr
i
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
44
Flow-dependent
corrosion rate
c
o
r
r
o
s
i
o
n

c
u
r
r
e
n
t

(
r
a
t
e
)
flow velocity
flow
dependent
corrosion
rate
flow
independent
corrosion
rate
Introduction
Electrochemical
thermodynamics
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kinetics
reaction rates
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polarization
general rate theory
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theory
mass transfer
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
12
45
Flow dependent limiting
current - experimental
1. reference electrode
2. gas in
3. gas out
4. Luggin capillary
5. counter electrode
6. rotating cylinder
7. temperature probe
8. pH electrode
9. working electrode
Introduction
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thermodynamics
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kinetics
reaction rates
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general rate theory
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theory
mass transfer
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
46
Flow dependent limiting
current - experimental
Potentiodynamic sweep conducted in an HCl solution at pH 4,
t=22 C, 3% NaCl, using a rotating cylinder electrode d=1 cm.
-1
-0.8
-0.6
-0.4
-0.2
0
0.1 1 10 100
i /(A/m
2
)
E

/
(
V

v
s
.

S
H
E
)
100 rpm
1000 rpm
4000 rpm
Introduction
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mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
47
Calculation of mass transfer
limiting current

s b
c c
D F i

= n
lim
(
(
(

m
m
kmol
s
m
kmol
C
kmol
kmol
e
e
3
2
=
(

2
m
A
diffusion limited current:
turbulent mass transfer limited current:

b
Dc F n
=
b m
c k F i n =
lim
(

3
m
kmol
s
m
kmol
C
kmol
kmol
e
e
=
(

2
m
A
Introduction
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thermodynamics
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kinetics
reaction rates
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general rate theory
mixed potential
theory
mass transfer
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
48
Chemical reaction
limiting currents
13
49
Mass transfer limiting
current in HCl corrosion
Potentiodynamic sweep conducted in an HCl solution at pH 4,
t=22 C, 3% NaCl, using a rotating cylinder electrode d=1 cm.
-1
-0.8
-0.6
-0.4
-0.2
0
0.1 1 10 100
i /(A/m
2
)
E

/
(
V

v
s
.

S
H
E
)
100 rpm
1000 rpm
4000 rpm
Introduction
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thermodynamics
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kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
50
Chemical reaction limiting
current in CO
2
corrosion
-1
-0.8
-0.6
-0.4
-0.2
0
0.1 1 10 100
i /(A/m
2
)
E

/
(
V

v
s
.

S
H
E
)
100 rpm
1000 rpm
4000 rpm
Potentiodynamic sweep conducted in a CO
2
solution at pH 4,
t=22 C, 3% NaCl, using a rotating cylinder electrode d=1 cm.
Introduction
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reaction rates
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theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
51
Adapted Vetters theory
3 2 2 2
1
CO H O H CO
k
+

+ +
3 2 2
1
3 2
HCO H e CO H
when an electrochemical reaction is
preceded by a slow chemical reaction,
for example:
this leads to a limiting current
slow
fast
Introduction
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thermodynamics
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reaction rates
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general rate theory
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theory
mass transfer
limiting currents
chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
52
Chemical reaction limiting
current in CO
2
corrosion
H
2
CO
3
H
steel water solution
CO
2
H
2
O
HCO
3
-
slow
step
distance from the steel surface x
e
-
e
-
e
-
e
- e
-
e
-
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
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general rate theory
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theory
mass transfer
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
14
53
Rate of chemical reaction
if we assume that the hydration/dehydration
reaction is a first order chemical reaction,
then the rate of change of H
2
CO
3
concentration is:
43 42 1 3 2 1
n dehydratio
1
hydration
1
3 2 2
CO H CO
c k c k v

=
.
2
const c
CO

3 2
1 CO H o
c k v v

=
c k v v
o 1
=
then:
Introduction
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thermodynamics
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mass transfer
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
54
Equilibrium
in equilibrium:
0
1
= =

c k v v
o
c k v
o 1
=
( ) u v
c
c
v v
o o
= |
.
|

\
|
= 1 1
u is the nondimensional concentration of H
2
CO
3
;
it is the maximum gradient of u (concentration),
i.e. flux of H
2
CO
3
at the metal surface, that will give
us the desired chemical reaction limiting current
therefore:
Introduction
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mass transfer
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
55
Mass balance
To obtain the concentration ( u ) profile
the steady state mass balance (Fick's
second law) for the case of an
accompanying homogeneous chemical
reaction has to be solved:
v
x
c
D
x t
c
+
|
|
.
|

\
|
=

( )
0
1
2 2
2
=

+
r
u
x
u

or:
Introduction
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thermodynamics
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reaction rates
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mass transfer
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
56
Boundary conditions
at the metal surface, in the limiting current
case, the concentration of the reduced
species ( H
2
CO
3
) is approaching zero, so
for:
0 = x
for the bulk of the fluid due to flow and
turbulence the fluid is well mixed and in
equilibrium, so for:
0 = =
c
c
u
m
x = 1 = =
c
c
u
( ) = x
in stagnant fluids (Vetter)
Introduction
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chemical reaction
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mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
15
57
Integration
yields the concentration profile
(nondimensional):
1 1
1
2 2

+ =

r m
r
r m
r
e
e
e
e
u
x x

where the thickness

of the reaction
boundary layer is:
1
=
k
D
r

and the thickness of

the diffusion
boundary layer is:
m
m
k
D
=
Introduction
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thermodynamics
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reaction rates
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general rate theory
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mass transfer
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
58
Diffusion and reaction
boundary layers
1
10
100
1000
0 2 4 6 8 10
v / (m/s)

/

m
diffusion layer
reaction layer
Thickness of the boundary layers for pipe flow,
t=20C, p
CO2
=1 bar, d
p
=0.1m.
Introduction
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mass transfer
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
59
Boundary layer thickness
ratio
0.1
1
10
100
1000
0 2 4 6 8 10
v / (m/s)
m
r

5
o
C
80
o
C
40
o
C
20
o
C
10
o
C
Boundary layer thickness ratio as a function of velocity and
temperature for pipe flow, p
CO2
=1 bar, d
p
=0.1m.
Introduction
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reaction rates
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mass transfer
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
60
Chemical reaction limiting
current
is obtained for the maximum gradient of
u (concentration), i.e. flux of H
2
CO
3
at the
metal surface:
0 0
) lim(
3 2
= =
= =
x x
CO H
x
u
c FD
x
c
FD i

r m
r m
e
e c FD
r

2
2
1
1

+
=
f D k c F =
1
Introduction
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
16
61
Flow factor
original Vetter's expression for the
chemical reaction limiting current in
stagnant solutions is now recovered:
f D k c F i
CO H
=
1 ) lim(
3 2
( )
r m
r m
r m
e
e
f


coth
1
1
2
2
=

+
=

corrected with the "flow factor f :

for stagnant solutions f=1
Introduction
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mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
62
Flow factor
0
1
2
3
4
5
0 2 4 6 8 10
v / (m/s)
f
l
o
w

f
a
c
t
o
r

5
o
C
80
o
C
40
o
C
20
o
C
10
o
C
Flow factor as a function of velocity and temperature
for pipe flow, d
p
=0.1 m, p
CO2
=1 bar.
Introduction
Electrochemical
thermodynamics
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reaction rates
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general rate theory
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mass transfer
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
63
Chemical reaction limiting
current and CO
2
corrosion
The rate of the cathodic reaction in CO
2
corrosion is limited by the slow hydration step
preceding it.
In stagnant solutions this current can be
calculated by using Vetters theory.
In flowing solutions there is a correction factor.
This correction factor is important for
temperatures lower than 40C and velocities
higher than 1 m/s when the mass transfer layer
is of the similar thickness as the reaction layer
Introduction
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reaction rates
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mass transfer
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
64
Mass transfer in electrolytes
17
65
Electrolytic conduction
SO
4
2-
copper
electrolyte
Cu
2+
copper
+ -
CuSO
4
cathode anode
Introduction
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Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
66
Migration
SO
4
2-
electrolyte
Cu
2+
x
+ -
c
copper
cathode
-
copper
anode
+
Introduction
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Corrosion rate
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Various forms of
corrosion
Corrosion mitigation
67
Migration
copper
cathode
electrolyte
x
copper
anode
+ -
c
Cu Cu
2+
Cu
2+
Cu
e
-
e
-
e
-
e
-
SO
4
2-
Introduction
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Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
68
Diffusion
copper
cathode
electrolyte
x
copper
anode
+ -
c
Cu
2+
Cu
2+
migration
diffusion
additive fluxes !
Introduction
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Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
18
69
Diffusion
copper
cathode
electrolyte
x
copper
anode
+ -
c
migration
diffusion
SO
4
2-
SO
4
2-
no net flux !
Introduction
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Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
70
Turbulent convection
copper
cathode
electrolyte
x
copper
anode
+ -
c
Cu
2+
SO
4
2-
f
l
o
w
Introduction
Electrochemical
thermodynamics
Electrochemical
kinetics
reaction rates
equilibrium
polarization
general rate theory
mixed potential
theory
mass transfer
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chemical reaction
limiting currents
mass transfer in
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Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation
71
Mass transfer in
electrolytes
Diffusion of charged species in electrolytes is
always accompanied with migration and vice
versa.
Turbulent flow leads to formation of boundary
layers.
In CO
2
corrosion the effect of migration is very
small (often negligible).
Turbulent mixing dominates in the bulk solution
while near the steel surface molecular diffusion
takes over.
Introduction
Electrochemical
thermodynamics
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reaction rates
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general rate theory
mixed potential
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mass transfer
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chemical reaction
limiting currents
mass transfer in
electrolytes
Corrosion rate
measurements
Various forms of
corrosion
Corrosion mitigation