Handbook

of
Electrochemical Impedance Spectroscopy
0.2 E
corr
0.2
1
0
1
EV
i
f

i
d
O

i
f
i
fM
i
fO
0 R
ct
R
p
0
0.4
Re Z

I
m
Z
1R
ct
C
dl

CORROSION
REACTIONS LIBRARY
J.-P. Diard, C. Montella, N. Murer
LEPMI, Bio-Logic
Hosted by Bio-Logic @ www.bio-logic.info
July 17, 2012
2
Contents
1 Reactions without adsorbed species 5
1.1 Reactions without mass transport limitation . . . . . . . . . . . . 5
1.1.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.1.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . . 5
1.1.3 Steady-state conditions . . . . . . . . . . . . . . . . . . . 5
1.1.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . . 6
1.2 Reactions with mass transport limitation . . . . . . . . . . . . . 8
1.2.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.2 Example: Iron in aerobic solution [4] . . . . . . . . . . . . 8
1.2.3 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.4 Steady-state conditions . . . . . . . . . . . . . . . . . . . 8
1.2.5 Faradaic impedance [3] . . . . . . . . . . . . . . . . . . . . 9
2 Reactions involving one adsorbate 11
2.1 Volmer-Heyrovsk y (V-H) corrosion reaction . . . . . . . . . . . . 11
2.1.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . . 11
2.1.3 Steady-state conditions . . . . . . . . . . . . . . . . . . . 12
2.1.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . . 13
2.2 (V-H) corrosion reaction with mass transport limitation . . . . . 15
2.2.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.3 Steady-state conditions . . . . . . . . . . . . . . . . . . . 15
2.2.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . . 16
2.3 Volmer-Tafel (V-T) corrosion reaction . . . . . . . . . . . . . . . 19
2.3.1 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.3.2 Kinetic equations . . . . . . . . . . . . . . . . . . . . . . . 19
2.3.3 Steady-state conditions . . . . . . . . . . . . . . . . . . . 19
2.3.4 Faradaic impedance . . . . . . . . . . . . . . . . . . . . . 20
3
4 CONTENTS
Chapter 1
Electrochemical reactions
without adsorbed species
1.1 Electrochemical reactions without mass trans-
port limitation
1.1.1 Mechanism
M
K
o1
M
n
1
+
+ n
1
e

O + n
2
e
K
r2
R
1.1.2 Kinetic equations
Butler-Volmer kinetic, kinetic irreversibility of electrochemical reactions (k
r1
=
k
o2
= 0), no mass transport limitation (O(0, t) = O

).
K
o1
= k
o1
exp(
o1
n
1
f E) , K
r2
= k
r2
exp(
r2
n
2
f E) , f = F/(RT)
Current density vs. step rates
i
f
(t) = F (n
1
v
1
(t) n
2
v
2
(t))
Step rates
v
1
(t) = K
o1
(t), v
2
(t) = K
r2
(t) O

1.1.3 Steady-state conditions

Step rates
v
1
= K
o1
, v
2
= K
r2
O

Current density
i
f
= F (n
1
K
o1
n
2
K
r2
O

) (1.1)
5
6 CHAPTER 1. REACTIONS WITHOUT ADSORBED SPECIES
1.1.4 Faradaic impedance
Faradaic impedance
Z
f
(s) = R
ct
(1.2)
Charge transfer resistance
R
ct
=
1
f F (n
2
2
O

K
r2

r2
+ n
2
1
K
o1

o1
)
(1.3)
Polarization resistance
R
p
= R
ct
Relation between R
ct
, R
p
and i
corr
R
ct
(E
corr
) = R
p
(E
corr
) =
1
f F (n
2
2
O

K
r2
(E
corr
)
r2
+ n
2
1
K
o1
(E
corr
)
o1
)
i
corr
=
1
f (
o1
n
1
+
r2
n
2
) R
ct
(E
corr
)
Stern-Geary relationship [5].
Electrode impedance
Z(s) =
Z
f
(s)
1 + s C
dl
Z
f
(s)
=
R
ct
1 + s C
dl
R
ct
(1.4)
E
corr
i
corr
i
corr
E
i
f
i
f
i
fM
i
fO
0 R
p
R
ct
0
Re Z

I
m
Z

c
1R
ct
C
dl

Figure 1.1: Typical i

f
vs. E curve calculated with Eq. (1.1) and Nyquist impedance
diagram calculated at the corrosion potential with Eqs. (1.3)-(1.4).
1.1. REACTIONS WITHOUT MASS TRANSPORT LIMITATION 7
Equivalent circuit
R
ct
C
dl
Figure 1.2: Equivalent circuit of the electrode impedance (Eq. (1.4)).
8 CHAPTER 1. REACTIONS WITHOUT ADSORBED SPECIES
1.2 Electrochemical reactions with mass trans-
port limitation
1.2.1 Mechanism
M
K
o1
M
n
1
+
+ n
1
e

O + n
2
e
K
r2
R
1.2.2 Example: Iron in aerobic solution [4]
Fe Fe
2+
+ 2e

O
2
+2H
2
O + 4e

4OH

1.2.3 Kinetic equations

Butler-Volmer kinetic, kinetic irreversibility of electrochemical reactions (k
r1
=
k
o2
= 0), mass transport limitation.
K
o1
= k
o1
exp(
o1
n
1
f E) , K
r2
= k
r2
exp(
r2
n
2
f E) , f = F/(RT)
Mass balance equations
Flux of soluble species
J
O
(0, t) = v
2
(t)
Current density vs. step rates
i
f
(t) = F (n
1
v
1
(t) n
2
v
2
(t))
Step rates
v
1
(t) = K
o1
(t), v
2
(t) = K
r2
(t) O(0, t)
1.2.4 Steady-state conditions
Steady-state equations
Soluble species
J
O
(0) = m
O
(O

O(0))
m
O
= D
O
/
O
,
O
= 1, 611 D
1/3
O

1/6

1/2
, m
O
= 0, 620 D
2/3
O

1/6

1/2
Steady-state solutions
Soluble species
O(0) =
O

m
O
K
r2
+ m
O
Current density
i
f
= F
(
n
1
K
o1

n
2
O

K
r2
m
O
K
r2
+ m
O
)
(1.5)
1.2. REACTIONS WITH MASS TRANSPORT LIMITATION 9
i
f
= i
fM
+ i
fO
, i
fM
= n
1
F K
o1
, i
fO
=
n
2
F O

K
r2
m
O
K
r2
+ m
O
i
dO
= lim
E
i
f
= n
2
F O

m
O
1.2.5 Faradaic impedance [3]
Faradaic impedance
Z
f
(s) = R
ct
+ Z
O
(s) (1.6)
Charge transfer resistance
R
ct
=
1
f F (n
2
2
O(0) K
r2

r2
+ n
2
1
K
o1

o1
)
(1.7)
Concentration impedance
Soluble species
Z
O
(s) =
R
ct
n
2
2
O(0)M
O
(s)K
2
r2

r2
n
2
2
O(0)K
r2

r2
+ n
2
1
K
o1

o1
(M
O
(s)K
r2
+ 1)
(1.8)
M
O
(s) =
1
m
O
th

dO
s

dO
s
,
dO
=

O
D
O
Z
O
(s) = k
O
th

dO
s

dO
s
1 +
th

dO
s

dO
s
,
=

o1
n
2
1
K
o1
K
r2
m
O
(
o1
n
2
1
K
o1
+ O(0)
r2
n
2
2
K
r2
)
, k
O
=
R
ct
n
2
2
O(0)K
2
r2

r2
m
O
(
o1
n
2
1
K
o1
+
r2
n
2
2
K
r2
O(0))
R
O
(s) = lim
s0
Z
O
(s) =
k
O
1 +
Polarization resistance
R
p
= R
ct
(
1 +
n
2
2
O(0)K
2
r2

r2
n
2
2
O(0)K
r2
m
O

r2
+ n
2
1
K
o1

o1
(K
r2
+ m
O
)
)
Relation between R
ct
, R
p
and i
corr
R
ct
(E
corr
) =
1
f F (n
2
2
O(0, E
corr
) K
r2
(E
corr
)
r2
+ n
2
1
K
o1
(E
corr
)
o1
)
i
corr
=
1
f (
o1
n
1
+
r2
n
2
) R
ct
(E
corr
)
i
corr
=
1
f
(

o1
n
1
+
r2
n
2
(
m
O
m
O
+ K
r2
(E
corr
)
))
R
p
(E
corr
)
Limiting case
k
o1
E
corr
i
corr

1
f
o1
n
1
R
p
(E
corr
)
= i
dO
10 CHAPTER 1. REACTIONS WITHOUT ADSORBED SPECIES
Electrode impedance
Z(s) =
Z
f
(s)
1 + s C
dl
Z
f
(s)
(1.9)
Equivalent circuit
R
ct
Z
O
C
dl

O
R
ct
R'
O
C
dl
Figure 1.3: Equivalent circuits of the electrode impedance (Eq. (1.9)). Z
W

O
=
R

dO
th

dO
s

dO
s
, R

dO
= k
O
, R

O
= k
O
/.
0.2 E
corr
0.2
1
0
1
EV
i
f

i
d
O

i
f
i
fM
i
fO
0 R
ct
R
p
0
0.5
Re Z

I
m
Z
1R
ct
C
dl

2.54
0.2 E
corr
0.2
1
0
1
EV
i
f

i
d
O

i
f
i
fM
i
fO
0 R
ct
R
p
0
0.4
Re Z

I
m
Z
1R
ct
C
dl

Figure 1.4: Typical i

f
vs. E curve calculated with Eq. (1.5) and Nyquist impedance
diagrams calculated at the corrosion potential with Eqs. (1.6)-(1.8) [2, 1].
Chapter 2
Electrochemical reactions
involving one adsorbate
2.1 Volmer-Heyrovsk y (V-H) corrosion reaction
2.1.1 Mechanism
H
+
+ s + e

K
r1
H,s
H
+
+ H,s + e

K
r2
H
2
+ s
M,s
K
o3
M
2+
+ s + 2 e

2.1.2 Kinetic equations

No mass transport limitations, Langmuir isotherm
H
+
(0, t) H
+
, M, s s
K
r1
= k
r1
exp(
r1
f E) , k
r1
= k

r1
H
+
K
r2
= k
r2
exp(
r2
f E) , k
r2
= k

r2
H
+
, K
o3
= k
o3
exp(2
o3
f E)
Transformation rates
v
s
(t) = v
1
(t) + v
2
(t), v
H
(t) = v
1
(t) v
2
(t)
Mass balance equations
Rate of production of adsorbed species
d
s
(t)
dt
=
v
s
(t)

,
d
H
(t)
dt
=
v
H
(t)

Current density vs. step rates

i
f
(t) = F (v
1
(t) + v
2
(t) 2 v
3
(t))
11
12 CHAPTER 2. REACTIONS INVOLVING ONE ADSORBATE
Step rates
v
1
(t) = K
r1
(t)
s
(t), v
2
(t) = K
r2
(t)
H
(t), v
3
(t) = K
o3
(t)
s
(t)
2.1.3 Steady-state conditions
Steady-state equations
Adsorbed species
d
s
/dt = 0,
H
+
s
= 1
Steady-state solutions
Adsorbed species

s
=
K
r2
K
r1
+ K
r2
,
H
=
K
r1
K
r1
+ K
r2
Current density
i
f
=
2 F (K
o3
K
r2
K
r1
K
r2
)
K
r1
+ K
r2
(2.1)
i
f
= 0 E = E
corr
=
1
(
r1
+ 2
o3
) f
ln
(
k
r1
k
o3
)
i
corr
=
2 F K
o3
(E
corr
) K
r2
(E
corr
)
K
r1
(E
corr
) + K
r2
(E
corr
)
=
2 F K
r1
(E
corr
) K
r2
(E
corr
)
K
r1
(E
corr
) + K
r2
(E
corr
)
=
2 F k
r1
k
r2
k
r1
(
k
r1
k
o3
)

r2
2
o3
+
r1
+ k
r2
(
k
r1
k
o3
)

r1
2
o3
+
r1
0.4 0.2 E
corr
0.02
0
0.02
EV
i
f

A
c
m

Figure 2.1: i
f
vs. E curve calculated with Eq. (2.1) for k
r1
= 1 s
1
, k
r2
= 1 s
1
,
k
o3
= 10
1
s
1
,
r1
= 0.8,
r2
= 0.3,
o3
= 0.4, = 10
9
mol cm
2
, f = 38.9 V
1
,
F = 96485 C mol
1
.
2.1. VOLMER-HEYROVSK

Y (V-H) CORROSION REACTION 13

2.1.4 Faradaic impedance
Faradaic impedance
Z
f
(s) = R
ct
+ Z
H
(s) + Z
s
(s)
Z
f
(s) =
(K
r2
+ K
r1
)(K
r2
+ K
r1
+ s)
fFK
r2
(
r1
K
r1
(2(K
o3
+ K
r2
) + s) + 4
o3
K
o3
(K
r2
+ K
r1
+ s) +
r2
K
r1
(2K
o3
+ 2K
r1
+ s))
Charge transfer resistance
R
ct
=
1
f F (
r2

H
K
r2
+ (4
o3
K
o3
+
r1
K
r1
)
s
)
=
K
r2
+ K
r1
f F K
r2
(4
o3
K
o3
+ (
r1
+
r2
) K
r1
)
Polarization resistance
R
p
=
(K
r2
+ K
r1
)
2
2 f F K
r2
(2
o3
K
o3
(K
r2
+ K
r1
) + K
r1
(
r1
(K
o3
+ K
r2
) +
r2
(K
r1
K
o3
)))
No simple relation between R
p
and i
corr
.
Relation between R
ct
and i
corr
R
ct
(E
corr
) =
1
f F (
r2

H
(E
corr
) K
r2
(E
corr
) + (4
o3
K
o3
(E
corr
) +
r1
K
r1
(E
corr
))
s
(E
corr
))
i
corr
=
1
(2
o3
+ (
r1
+
r2
)/2) f R
ct
(E
corr
)
14 CHAPTER 2. REACTIONS INVOLVING ONE ADSORBATE
0 0.5 1 R
ct
R
p
0
0.5
Re ZR
p

I
m
Z

R
p
E E
corr
Z
f
Z
0 0.5 1 R
ct
R
p
0
0.5
Re ZR
p

I
m
Z

R
p
EV E
corr
0.04
Z
f
Z
2 0 2 4
1
0
lograds
l
o
g

R
p

E E
corr
Z
f
Z
0 5
0.2
0
lograds
l
o
g

R
p

EV E
corr
0.04
Z
f
Z
Figure 2.2: Two typical Nyquist impedance and Bode diagrams for the Volmer-
Heyrovsk y (V-H) corrosion reaction (Thick lines: Faradaic impedance, thin lines:
electrode impedance). Parameters value as in Fig. 2.1 and C
dl
= 10
5
F.
2.2. (V-H) CORROSIONREACTIONWITHMASS TRANSPORT LIMITATION15
2.2 Volmer-Heyrovsk y (V-H) corrosion reaction
with mass transport limitation
2.2.1 Mechanism
H
+
+ s + e

K
r1
H,s
H
+
+ H,s + e

K
r2
H
2
+ s
M,s
K
o3
M
2+
+ s + 2 e

2.2.2 Kinetic equations

Butler-Volmer kinetic, Langmuir isotherm, with mass transfer limitation,
M, s s.
K
r1
= k
r1
exp(
r1
f E) , K
r2
= k
r2
exp(
r2
f E) ,
K
o3
= k
o3
exp(
o3
2 f E), f = F/(RT)
Mass balance equations
Flux of soluble species
J
H
+(0, t) = v
1
(t) v
2
(t)
Rate of production of adsorbed species
d
s
(t)
dt
=
v
1
(t) + v
2
(t)

,
d
H
(t)
dt
=
v
1
(t) v
2
(t)

Current density vs. step rates

i
f
(t) = F (v
1
(t) + v
2
(t) 2 v
3
(t))
Step rates
v
1
(t) = K
r1
(t) H
+
(0, t)
s
(t), v
2
(t) = K
r2
(t) H
+
(0, t)
H
(t), v
3
(t) = K
o3
(t)
s
(t)
2.2.3 Steady-state conditions
Steady-state equations
Soluble species
J
H
+(0) = m
H
+(H
+
H
+
(0))
m
H
+ = D
H
+/
H
+,
H
+ = 1, 611 D
1/3
H
+

1/6

1/2
, m
H
+ = 0, 620 D
2/3
H
+

1/6

1/2
Adsorbed species
d
s
/dt = 0,
H
+
s
= 1
16 CHAPTER 2. REACTIONS INVOLVING ONE ADSORBATE
Steady-state solutions
Soluble species
H
+
(0) =
H
+*
(K
r1
+ K
r2
) m
H
+
2K
r1
K
r2
+ (K
r1
+ K
r2
) m
H
+
,
Adsorbed species

s
=
K
r2
K
r1
+ K
r2
,
H
=
K
r1
K
r1
+ K
r2
Current density
i
f
=
2FK
r2
(
m
H
+ (K
r1
+ K
r2
)
(
K
o3
H
+*
K
r1
)
+ 2K
o3
K
r1
K
r2
)
(K
r1
+ K
r2
) (m
H
+ (K
r1
+ K
r2
) + 2K
r1
K
r2
)
(2.2)
0 0.1 0.2 0.3
0.04
0
0.04
EV
i
f

A
c
m

Figure 2.3: i
f
vs. E curve calculated with Eq. (2.2) for k
r1
= 10
7
mol
1
cm
3
s
1
,
k
r2
= 10
7
mol
1
cm
3
s
1
, k
o3
= 10
2
s
1
,
r1
= 0.8,
r2
= 0.3,
o3
= 0.5, D
H
+ = 10
6
cm
2
s
1
, = 10
2
cm
2
s
1
, = 100 rpm, = 10
9
mol cm
2
, f = 38.9 V
1
,
F = 96485 C mol
1
.
2.2.4 Faradaic impedance
Faradaic impedance
Z
f
(s) = R
ct
+ Z
H
+(s) + Z

(s), Z

(s) = Z
s
(s) + Z
H
+(s)
Z
f
(s) =
a
f1
+ sa
f2
+ a
f3
M
H+
(s) + sa
f4
M
H+
(s)
b
f1
+ sb
f2
+ b
f3
M
H+
(s) + sb
f4
M
H+
(s)
a
f1
= (K
r1
+ K
r2
) H
+
(0), a
f2
= 1, a
f3
= 2K
r1
K
r2
H
+
(0), a
f4
= (K
r2

H
+ K
r1

s
)
b
f1
= 2fFH
+
(0)
(

H
K
r2

r2
(
K
r1
H
+
(0) K
o3
)
+
s
(
K
r1

r1
(
K
r2
H
+
(0) + K
o3
)
+ 2K
o3

o3
(K
r1
+ K
r2
)
))
b
f2
= fF
(

H
K
r2

r2
H
+
(0) + K
r1

r1

s
H
+
(0) + 4K
o3

o3

s
)
b
f3
= 4fF
2
K
o3
K
r1
K
r2

s
H
+
(0) (
H
(
r1

r2
) + 2
o3
) , b
f4
= 4fF
2
K
o3

o3

s
(
H
K
r2
+ K
r1

s
)
2.2. (V-H) CORROSIONREACTIONWITHMASS TRANSPORT LIMITATION17
Charge transfer resistance
R
ct
=
1
fF(
H
K
r2

r2
H
+
(0) + K
r1

r1

s
H
+
(0) + 4K
o3

o3

s
)
Polarization resistance
R
p
= (m
H
+ (K
r1
+ K
r2
) + 2K
r1
K
r2
) /
(
2fF
(
m
H
+
(

H
K
r2

r2
(
K
r1
H
+
(0) K
o3
)
+
s
(
K
r1

r1
(
K
r2
H
+
(0) + K
o3
)
+2K
o3

o3
(K
r1
+ K
r2
))) + 2K
o3
K
r1
K
r2

s
(
H
(
r1

r2
) + 2
o3
)))
No simple relation between R
p
and i
corr
.
Relation between R
ct
and i
corr
R
ct
(E
corr
) =
1
fF(
H
(E
corr
)K
r2
(E
corr
)
r2
H
+
(0, E
corr
) + K
r1
(E
corr
)
r1

s
(E
corr
)H
+
(0, E
corr
) + 4K
o3
(E
corr
)
o3

s
(E
corr
))
i
corr
=
1
(2
o3
+ (
r1
+
r2
)/2) f R
ct
(E
corr
)
18 CHAPTER 2. REACTIONS INVOLVING ONE ADSORBATE
0 0.5 1
0
0.5
Re ZR
p

I
m
Z

R
p
E E
corr
Z
f
Z
0 0.5 1
0
0.5
Re ZR
p

I
m
Z

R
p
EV E
corr
0.06
Z
f
Z
0 5
0.2
0
lograds
l
o
g

R
p

E E
corr
Z
f
Z
0 5
0.2
0
lograds
l
o
g

R
p

EV E
corr
0.06
Z
f
Z
Figure 2.4: Two typical Nyquist impedance and Bode diagrams for the Volmer-
Heyrovsk y (V-H) corrosion reaction with mass transport limitation (Thick lines:
Faradaic impedance, thin lines: electrode impedance). Parameters value as in Fig. 2.3
and C
dl
= 5 10
5
F.
2.3. VOLMER-TAFEL (V-T) CORROSION REACTION 19
2.3 Volmer-Tafel (V-T) corrosion reaction
2.3.1 Mechanism
H
+
+ s + e

K
r1
H,s
2 H,s
k
d2
H
2
+ 2 s
M,s
K
o3
M
2+
+ s + 2 e

2.3.2 Kinetic equations

No mass transport limitations, Langmuir isotherm, H
+
(0, t) H
+
, M, s s,
K
r1
= k
r1
exp (
r1
f E) , k
r1
= k

r1
H
+
K
o3
= k
o3
exp(2
o3
f E) , k
o1
=
0, k
r3
= 0.
Mass balance equations
Rate of production of adsorbed species
d
s
(t)
dt
=
v
1
(t) + 2 v
2
(t)

,
d
H
(t)
dt
=
v
1
(t) 2 v
2
(t)

Current density vs. step rates

i
f
(t) = F (v
1
(t) 2 v
3
(t))
Step rates
v
1
(t) = K
r1
(t)
s
(t), v
2
(t) = k
d2
(
H
(t))
2
, v
3
(t) = K
o3
(t)
s
(t)
2.3.3 Steady-state conditions
Steady-state equations
Adsorbed species
d
s
/dt = 0,
H
+
s
= 1
Steady-state solutions
Adsorbed species

s
=
4k
d2
+ K
r1

K
r1

8k
d2
+ K
r1
4k
d2
,
s
+
H
= 1
Current density
i
f
=
4F
2
k
d2
(2K
o3
K
r1
)
4k
d2
+ K
r1
+

K
r1

8k
d2
+ K
r1
(2.3)
i
f
= 0 E = E
corr
=
1
f (2
o3
+
r1
)
log
(
k
r1
2k
o3
)
20 CHAPTER 2. REACTIONS INVOLVING ONE ADSORBATE
i
corr
=
2
3exp
2
F
2
k
d2
k
o3
(
k
o3
k
r1
)
exp
2
2
exp
1
k
r1
(
k
o3
k
r1
)
exp
1
+ 4k
d2
+

2
exp
1
(
k
o3
k
r1
)
exp
1
k
r1

2
exp
1
k
r1
(
k
o3
k
r1
)
exp
1
+ 8k
d2
with
exp
1
=

r1
2
o3
+
r1
, exp
2
=
2
o3
2
o3
+
r1
0.4 0.2 E
corr
0
0.05
EV
i
f

m
A
c
m

Figure 2.5: i
f
vs. E curve calculated with Eq. (2.3) for k
r1
H
+
= 10
3
s
1
, k
d2
= 10
8
mol
1
cm
2
s
1
, k
o3
= 10
1
s
1
,
r1
= 0.7,
o3
= 0.4, n
3
= 1, = 10
9
mol cm
2
,
f = 38.9 V
1
, F = 96485 C mol
1
.
2.3.4 Faradaic impedance
Transfer resistance
R
ct
=
1
fF(4K
o3

o3
+ K
r1

r1
)
s
Concentration impedance
Z
s
(s) =
K
r1
(K
r1
2K
o3
) R
ct

r1
2K
o3
K
r1

r1
+ K
r1
(s + 4k
d2

H
)
r1
+ 4K
o3

o3
(s + K
r1
+ 4k
d2

H
)
Faradaic impedance
Z
f
(s) = R
ct
+ Z
s
(s)
Z
f
(s) = R
ct
(
1 +
K
r1
(K
r1
2K
o3
)
r1
2K
o3
K
r1

r1
+ K
r1
(s + 4k
d2

H
)
r1
+ 4K
o3

o3
(s + K
r1
+ 4k
d2

H
)
)
Polarization resistance
R
p
= R
ct
(
1 +
K
r1
(K
r1
2K
o3
) R
ct

r1
2K
o3
K
r1
(2
o3
+
r1
) + 4k
d2
(4K
o3

o3
+ K
r1

r1
)
H
)
No simple relation between R
p
(E
corr
) and i
corr
.
Relation between R
ct
(E
corr
) and i
corr
i
corr
=
1
f (2
o3
+
r1
) R
ct
(E
corr
)
2.3. VOLMER-TAFEL (V-T) CORROSION REACTION 21
Equivalent circuit
Z
s
=
R
s
1 + R
s
C
s
s
, C
s
=
4K
o3

o3
+ K
r1

r1
K
r1
(K
r1
2K
o3
) R
ct

r1
R
s
=
K
r1
(K
r1
2K
o3
) R
ct

r1
2K
o3
K
r1
(2
o3
+
r1
) + 4k
d2
(4K
o3

o3
+ K
r1

r1
)
A
0 0.5 1
0
0.45
Re ZR
p

I
m
Z

R
p
E E
corr
Z
f
Z
0 0.5 1
0
0.45
Re ZR
p

I
m
Z

R
p
EV E
corr
0.04
Z
f
Z
2 0 2
1
0
lograds
l
o
g

R
p

E E
corr
Z
f
Z
2 0 2
0.5
0
lograds
l
o
g

R
p

EV E
corr
0.04
Z
f
Z
Figure 2.6: Two typical Nyquist impedance and Bode diagrams for the Volmer-
Tafel (V-T) corrosion reaction (Thick lines: Faradaic impedance, thin lines: electrode
impedance). Parameters value as in Fig. 2.5 and C
dl
= 1 10
5
F.
22 CHAPTER 2. REACTIONS INVOLVING ONE ADSORBATE
R
ct
C
dl
C
s
R
s
Figure 2.7: Equivalent circuit for the impedance of (V-T) corrosion reaction.
Bibliography
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book of electrochemical impedance spectroscopy. Diusion Impedances.
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opments. Electrochim. Acta 35 (1990), 14831492.
[3] Montella, C., Diard, J.-P., and B. Le Gorrec. Exercices de cinetique
electrochimique. II. Methode dimpedance. Hermann, Paris, 2005.
[4] Orazem, M. E., and Tribollet, B. Electrochemical impedance spec-
troscopy. John Wiley & Sons, Hoboken, 2008.
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(1957), 5663.
23